Adhesive composition, patch, skin protective agent for ostomy accessory, and wound dressing

Abstract

The purpose of the present invention is to provide an adhesive composition which has good adhesive properties and which is less stimulating to the skin, a wound, or a mucous membrane.　The present invention makes it possible to provide an adhesive composition comprising at least a polyurethane which is a cured product of a composition containing a monool-type polypropylene glycol component and an isocyanate component.

Description

Adhesive composition, patch, skin protective agent for ostomy appliance, and wound dressing

[0001] The present invention relates to an adhesive composition, and to a patch, a skin protective agent for ostomy appliances, and a wound dressing each containing the adhesive.

[0002] In general, adhesive compositions are used for applications such as skin, wounds, mucous membranes, etc. (hereinafter also referred to as "skin, etc." in this specification), and can be used, for example, in patches for skin, etc. Patches for skin, etc. can be used to fix medical devices such as gauze, bandages, adhesive plasters, catheters, and ostomy appliances to the skin. Patches for skin, etc. can also be used to protect or treat skin, wounds, and the surrounding area of ​​a stoma, etc.

[0003] Various technologies relating to adhesives for skin have been proposed. For example, Patent Document 1 below describes an adhesive composition for skin containing a resin component that forms an adhesive and a lamellar structure formed from a lipid composition. Patent Document 2 below describes an adhesive for skin in the form of a porous membrane formed by irradiating a radiation-curable resin with radiation.

[0004] International Publication No. WO 2015 / 178438 International Publication No. WO 2015 / 119160

[0005] In general, it is difficult for adhesives for use on the skin, etc. to simultaneously improve adhesion to the skin, etc. and reduce irritation to the skin, etc. This is because adhesives for use on the skin, etc. tend to cause stronger irritation to the skin, etc. as their adhesive strength increases. However, there is a demand for adhesives for use on the skin, etc. that have good adhesion but cause less irritation to the skin, etc.

[0006] Therefore, a main object of the present invention is to provide an adhesive for the skin, wounds, or mucous membranes that has good adhesiveness and is less irritating to the skin, wounds, or mucous membranes.

[0007] The present invention can provide a pressure-sensitive adhesive composition containing at least a polyurethane that is a cured product of a composition containing a mono-ol type polypropylene glycol component and an isocyanate component.

[0008] The present invention provides an adhesive for skin, wounds, or mucous membranes that has good adhesiveness and is less irritating to the skin, wounds, or mucous membranes.

[0009] Preferred embodiments for carrying out the present invention are described below. The embodiments described below are representative of the present invention, and the scope of the present invention is not limited to these embodiments. In this specification, percentages are expressed by mass unless otherwise specified. Furthermore, the upper limit (or less) and lower limit (or more) of each numerical range (to) can be arbitrarily combined as desired. Furthermore, in the descriptions of "1." and other items, overlapping descriptions of polyurethane, mono-, di-, and tri-type polypropylene glycol, isocyanate, prepolymer, etc., and their respective technical features, components, configurations, definitions, terms, and methods, such as their use, preparation, and manufacturing methods, may be omitted as appropriate if they are described elsewhere in the specification. Furthermore, the descriptions of "1.", "2.", etc., and other items can be applied to any of the technologies or embodiments of "1.", "2.", etc., and other items, and the respective technical features can be appropriately adopted in each of the technologies or embodiments.

[0010] 1. Background and Overview of the Invention

[0011] The skin surface has skin furrows and skin ridges. Skin furrows are fine grooves that exist on the skin surface. Skin ridges are small protrusions surrounded by skin furrows. Thus, the skin surface is not smooth but has fine irregularities.

[0012] Furthermore, when conventional adhesives are applied to the skin, they often cannot penetrate into the skin grooves, which are the depressions of the skin. While they may be able to adhere to the skin ridges, which are the protrusions of the skin, they often fail to adhere to the skin grooves, which are the depressions of the skin. As a result, conventional adhesives are actually stuck mainly to the skin ridges, which are the protrusions of the skin, and their vicinity. For this reason, conventional adhesives tend to have a higher adhesive strength to prevent them from peeling off from the skin. However, such adhesives with strong adhesive strength can cause strong irritation to the skin. On the other hand, reducing the adhesive strength to reduce the strong irritation to the skin may result in the adhesive peeling off from the skin. Furthermore, adhesive contact areas other than the skin include wounds and mucous membranes, which often have complex uneven surfaces, and there is a demand for reducing the strong irritation to the skin.

[0013] The present inventors have conducted studies to provide an adhesive composition that has good adhesiveness but is less irritating to the skin.

[0014] As a result of intensive research, the present inventors have found that a polyurethane using a mono-ol type polypropylene glycol component, more preferably a combination of a mono-ol type polypropylene glycol component and an isocyanate component, and an adhesive composition containing said polyurethane, can adhere to the contact area of ​​an adhesive object such as skin and have high adhesive strength to the contact area, and that the adhesive strength does not need to be set higher in the basic design of the adhesive strength in consideration of a decrease in adhesive strength due to a decrease in contact area with fine irregularities such as skin (i.e., there is little irritation to the skin), and have completed the present invention.The present inventors have then achieved the object of providing an adhesive composition that has good adhesiveness but is low in irritation to the contact area of ​​an adhesive object by using this polyurethane, and have solved the problems of the present invention.

[0015] The present invention provides an adhesive composition comprising at least a polyurethane that is a cured product of a composition comprising at least (a1) a mono-ol polypropylene glycol component and (b) an isocyanate component. The present inventors can provide an adhesive composition that has good adhesive properties while causing little irritation to the skin, wounds, or mucous membranes. In this specification, the term "component" such as component (a1) may also be referred to as a "compound" or a "group."

[0016] The present invention will be described in detail below.

[0017] 2. Pressure-sensitive adhesive composition according to this embodiment

[0018] 2-1. Overview

[0019] An invention according to one embodiment of the present invention (hereinafter also referred to as "this embodiment") can provide a polyurethane that is a cured product of a composition containing at least (a1) a monool-type polypropylene glycol component, and (b) an isocyanate component, and it is preferable that the composition further contains or uses a polyol-type polypropylene glycol component. It is preferable that the composition further contains (a) a polyol-type polypropylene glycol component. The (b) isocyanate component is preferably a diisocyanate component, and the diisocyanate component is preferably one or more selected from diisocyanate monomers and diisocyanate reactants obtained from diisocyanate (mono- or oligomer) and polyols. The diisocyanate reactant may be an isocyanate-terminated prepolymer having isocyanate groups at both ends, or a diisocyanate prepolymer having isocyanate groups at both ends (hereinafter also referred to as "diisocyanate prepolymer").

[0020] The polyurethane may be a polyurethane containing at least (a1) a structural unit derived from a monool-type polypropylene glycol component and (b) a structural unit derived from an isocyanate component, and may further contain a structural unit derived from a polyol-type polypropylene glycol component. Since the structural units are derived from the respective raw material components described below, the technical details of the respective raw material components described below can be appropriately adopted. The composition may be a mixture, or may be a curable composition or a thermosetting composition.

[0021] Furthermore, the present embodiment can provide a pressure-sensitive adhesive composition containing at least the polyurethane. In the present embodiment, the pressure-sensitive adhesive composition may be a pressure-sensitive adhesive.

[0022] In addition, as another preferred aspect of the present embodiment, a pressure-sensitive adhesive composition may be provided, which includes a polyurethane that is a cured product of a composition including: (a1) a mono-ol type polypropylene glycol component; (a2) a tri- or higher polyol type polypropylene glycol component; and (b) an isocyanate component.

[0023] In addition, as another preferred aspect of the present embodiment, a pressure-sensitive adhesive composition may be provided, which includes polyurethane that is a cured product of a composition including: (a1) a mono-ol type polypropylene glycol component; (a2) a tri- or higher polyol type polypropylene glycol component; (a3) ​​a diol type polypropylene glycol component; and (b) an isocyanate component.

[0024] 2-2. Polyurethane The polyurethane used in this embodiment is preferably a polyurethane that is a cured product of a composition containing at least: (a1) a mono-ol type polypropylene glycol component; and (b) an isocyanate component. For example, a polyurethane adhesive composition containing the polyurethane resin of this embodiment has the advantage of having good adhesiveness and being less irritating to areas that come into contact with adhesive materials (e.g., skin, wounds, mucous membranes, etc.).

[0025] In a preferred embodiment of the polyurethane, a polyol-type polypropylene glycol component may further be contained or used in the composition, for example, (a2) a tri- or higher polyol-type polypropylene glycol component and / or (a3) ​​a diol-type polypropylene glycol may be contained or used in the composition. In a more preferred embodiment of the polyurethane, (a2) a tri- or higher polyol-type polypropylene glycol component is more preferably contained in the composition, and further, (a2) a tri- or higher polyol-type polypropylene glycol component and (a3) ​​a diol-type polypropylene glycol may be used in combination.

[0026] The polyurethane used in the present embodiment can also be used in techniques related to various applications (compositions, methods for using the polyurethane, methods for producing compositions, etc.) For example, since the polyurethane has adhesive properties, it can be used or contained in compositions for adhesive purposes, etc.

[0027] In another aspect of this embodiment, the polyurethane of this embodiment may be used in an adhesive composition, or may be used for an adhesive composition, or may be used to produce an adhesive composition. This embodiment may provide the polyurethane for adhesive use or the like, or use thereof. This embodiment may also provide the polyurethane for an adhesive composition or the use thereof. This embodiment may also provide the polyurethane for use in producing a composition for adhesive use or the like, or use thereof. This embodiment may also provide the polyurethane for use in producing a composition for adhesive use or the like, or use thereof in producing a composition for adhesive use or the like. This embodiment may also provide a method such as an adhesive method, a method of using an adhesive composition, or a treatment method, using the polyurethane. This embodiment may also provide a method for preparing or producing an adhesive composition using the polyurethane. This embodiment may also be a method for adhering or applying a polyurethane or a composition containing the polyurethane to the skin, wound, or mucous membrane of an animal (human, pet, exhibition animal, farm animal, etc.).

[0028] 2-2-1. Raw material components used to form polyurethane

[0029] The raw material components used in the polyurethane or polyurethane adhesive composition according to the present embodiment and a composition containing the raw material components (hereinafter also referred to as the "composition" or "raw material composition") will be described. The composition or raw material composition may be a mixture or a curable composition.

[0030] In this embodiment, a polyol component (preferably, (A) a polypropylene glycol component) and a (B) isocyanate component (preferably, a diisocyanate component) can be used as polyurethane resin raw materials used to form the polyurethane resin. As the (A) polypropylene glycol component, from the viewpoints of better adhesion to contact areas and less irritation, it is preferable to use at least (a1) a monool-type polypropylene glycol component, and it is more preferable to use (a) a polyol-type polypropylene glycol component. It is preferable to use a tri- or higher polyol type and / or a dipolyol type as the (a) component. As the (B) isocyanate component, a polyisocyanate component is preferred, and a diisocyanate component is more preferred, and it is more preferable to use a diisocyanate monomer and / or a diisocyanate reactant which is a reaction product of a diisocyanate monomer and a polyol.

[0031] 2-2-1-1. (A) Polypropylene glycol component

[0032] The polypropylene glycol component (A) used in this embodiment is a type of polyether and is not particularly limited. Commercially available mono- or polyol-type (di-, tri- or higher) polyalkylene glycols may be used, or the desired mono- or polyol-type may be produced by a known production method. The polypropylene glycol component is preferably a polymer having one or more hydroxyl groups at its terminals in the molecule. The polypropylene glycol component may also have one or more structures having a polypropylene ether skeleton in the molecule, and may have a structure in which the skeleton structure is ether-bonded to an alcohol (monohydric (R—OH), dihydric (propylene glycol), or trihydric or higher alcohol). R of the monohydric alcohol is preferably a group not having a hydroxyl group, and examples of trihydric or higher polyhydric alcohols may be appropriately selected from the examples of "trihydric to octahydric alcohols" described in "2-2-1-2-3. Polyols" described below.

[0033] 2-2-1-1-1. (a1) Monool-type polypropylene glycol component

[0034] The (a1) mono-ol type polypropylene glycol (polyoxypropylene monol) component used in this embodiment is a type of polyether, and a commercially available product that is normally available can be used. There are no particular limitations on the type, and a commercially available mono-ol type may be used, or a desired mono-ol type may be produced by a known production method. The mono-ol type polypropylene glycol component preferably has one terminal hydroxyl group in one molecule. Furthermore, the mono-ol type polypropylene glycol component preferably has one terminal hydroxyl group and one terminal R-O- in one molecule, and R- is a hydroxyl group that is defined as "R" as described below. １ -" or "R ２ -(C=O)-" is acceptable, but "R １ Furthermore, the mono-ol type polypropylene glycol component has a structure having a polypropylene ether skeleton in the molecule, and the skeleton structure and R １ The skeletal structure may be an ether bond structure with —OH, or the skeletal structure may be an ether bond structure with R ２It may have an ester bond structure with -(C=O)-OH. Furthermore, the mono-ol type polypropylene glycol component has a structure having a polypropylene ether skeleton in the molecule, and only one end of the skeleton structure may have -OH and the other end may have R-O-. For example, the following general formula (1) can be mentioned, where p in formula (1) may be an integer. It is desirable that the end on the R side in formula (1) is not a hydroxyl group. The "R" may be appropriately selected from the examples of the "R moiety (e.g., hydrocarbon group, etc.)" derived from a monohydric alcohol or a carboxylic acid described below. The "R" is preferably a hydrocarbon group (e.g., an alkyl group, an aryl group, an alkenyl group, etc.), more preferably an alkyl group. The preferred carbon number may be appropriately selected from the examples of the "R moiety" derived from a monohydric alcohol or a carboxylic acid described below. This makes it possible to provide a polyurethane and an adhesive composition containing the same that have better adhesiveness while causing less irritation to the area in contact with the adhesive material.

[0035]

[0036] The monool-type polypropylene glycol component is, for example, a monohydric alcohol (R—OH: for example, R １ A substance obtained by adding propylene oxide to a carboxylic acid (R —OH, etc.) is preferred, and it is preferable that one hydroxyl group is present in one molecule. ２ -(C=O)-OH: for example, a substance obtained by adding propylene oxide to acrylic acid and / or methacrylic acid is preferred, and it is preferable that one molecule has one hydroxyl group.

[0037] Monohydric alcohol (R １Examples of the monoalcohols of carboxylic acids (for example, R ２ The —(C═O)—OH) is not particularly limited, but examples include (meth)acrylic acid, hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. Mono-, di-, and tricarboxylic acids are available, with monocarboxylic acids having one carboxy group being preferred. The (meth)acrylic acid may be acrylic acid and / or methacrylic acid. In methacrylic acid, one hydrogen atom of the vinyl group is substituted with a methyl group (2-methylacrylic acid). One or more selected from these can be used.

[0038] The R moiety of the mono-ol type polypropylene glycol component (preferably excluding a group in which RO- is a hydroxyl group or an R moiety having a hydroxyl group) is not particularly limited, but may be hydrophobic, hydrophilic, or amphoteric, and is preferably hydrophobic. Examples of the R moiety include R moieties derived from monohydric alcohols or carboxylic acids (e.g., hydrocarbon groups). The hydrocarbon group of the R moiety is not particularly limited, but may be either an unsaturated or saturated hydrocarbon group (straight-chain, branched-chain, acyclic, alicyclic, aromatic, etc.), and examples of unsaturated hydrocarbons include alkenyl groups such as vinyl, isopropenyl, and allyl. More preferred specific examples include chain alkyl groups (e.g., groups having 1, 2, 3, 4, 5, or 1 to 5 carbon atoms, 6 or 12 or more carbon atoms, 24 or 18 or less carbon atoms, 12 to 24, 12 to 18, or 12 to 24 carbon atoms, etc.); alicyclic alkyl groups such as a cyclo group or a dimethylcyclo group; and aryl groups such as a benzyl group, a phenyl group, or an isooctylphenyl group. The number of carbon atoms in the alicyclic alkyl group or aryl group may be appropriately selected from the carbon numbers exemplified for the chain alkyl group. The chain may be either linear or branched. The R moiety may be substituted or unsubstituted, and the substituent group is not particularly limited, and examples thereof include the hydrocarbon groups of the R moiety described above (e.g., alkyl groups such as a methyl group). Furthermore, examples of alkyl groups in the R moiety, substituents, etc. in this embodiment include, but are not limited to, a methyl group, an ethyl group, a propyl group (n-, iso-), a butyl group (n-, sec-, tert-), and a pentyl group. One or more selected from these can be used. Of the examples of the R moiety, an alkyl group is preferred.

[0039] The weight-average molecular weight of the mono-ol polypropylene glycol component is not particularly limited, but the preferred lower limit is, although not particularly limited, preferably 2,000 or more, more preferably 3,000 or more, even more preferably 4,000 or more, more preferably 4,500 or more, and even more preferably 5,000 or more. The preferred upper limit is, although not particularly limited, preferably 50,000 or less, more preferably 40,000 or less, even more preferably 30,000 or less, more preferably 20,000 or less, more preferably 10,000 or less, more preferably 8,000 or less, more preferably 7,000 or less, and more preferably 6,000 or less. The preferred numerical range is, although not particularly limited, preferably 4,000 to 10,000, more preferably 4,500 to 8,000. Furthermore, the preferred weight-average molecular weight of the di- or tri- or higher polyol (preferably tri-) polypropylene glycol used in combination with the mono-ol will be described later, and preferably falls within the preferred range of the weight-average molecular weight of the mono-ol used. The weight-average molecular weight can be measured by a method such as GPC (gel permeation chromatography) analysis.

[0040] Furthermore, the hydroxyl value (mgKOH / g) of the mono-ol type polypropylene glycol component has a suitable upper limit, but is not particularly limited, and is preferably 25 or less, more preferably 20 or less, even more preferably 18 or less, more preferably 16 or less, more preferably 15 or less, more preferably 14 or less, and more preferably 13 or less; a suitable lower limit, but is not particularly limited, and is preferably 5 or more, more preferably 6 or more, more preferably 7 or more, and more preferably 8 or more; and a suitable numerical range, but is not particularly limited, is preferably 5 to 25, and more preferably 6 to 15.

[0041] 2-2-1-1-2. (a2) Tri- or higher polyol polypropylene glycol

[0042] The tri- or higher polyol-type polypropylene glycol component (a2) used in this embodiment is a type of polyether and is not particularly limited. However, commercially available tri- or higher polyol-types may be used, or the desired tri- or higher polyol-type may be produced by a known production method. The tri- or higher polyol-type polypropylene glycol component preferably has three or more terminal hydroxyl groups in the molecule. Furthermore, the tri- or higher polyol-type polypropylene glycol component may have three or more structures having a polypropylene ether skeleton in the molecule, and each skeleton structure may have a hydroxyl group at the end. This makes it possible to provide a polyurethane and an adhesive composition containing the same that have better adhesive properties but cause less irritation to the contact area of ​​the adhesive material. In this embodiment, it is preferable to use a combination of a mono- or higher polypropylene glycol and a tri- or higher polyol-type (preferably a tri- or higher polyol-type) propylene glycol. When only a di- or tri- or higher polyol is used, the polyurethane tends to adhere to polar substances but not to non-polar substances. However, by further using a mono- or higher polyol, the adhesive properties to non-polar substances can be stabilized and improved.

[0043] The number of hydroxyl groups possessed by a tri- or higher polyol-type polypropylene glycol component is not particularly limited, but a suitable lower limit in the molecule is, but is not particularly limited, for example, 3 or more, and a suitable upper limit is, but is not particularly limited, preferably 5 or less, more preferably 4 or less, and the polypropylene glycol component is preferably a triol type. As the triol-type polypropylene glycol (polyoxypropylene triol), a commonly used triol-type polypropylene glycol can be used.

[0044] For example, the tetra- or higher polyol type polypropylene glycol is preferably a substance obtained by adding propylene oxide to a polyhydric alcohol having 4 or more hydroxyl groups in one molecule. For example, the polyhydric alcohol having 4 or more hydroxyl groups is not particularly limited, but examples thereof include pentaerythritol, and one or more of these can be used.

[0045] For example, triol-type polypropylene glycol is preferably a substance obtained by adding propylene oxide to a trihydric alcohol, and preferably has three hydroxyl groups in one molecule. The trihydric alcohol is not particularly limited, but examples include glycerin and trimethylolpropane, and one or more of these can be used. Commercially available tri- or higher polyol-type polypropylene glycol components include, for example, the Sannix GP series (Sanyo Chemical Industries) such as Sannix GP-3000 (for example, the following formula (2): l, m, and n may be integers, or may be the same, two of them may be the same, or all three may be different), Exenol (Asahi Glass), Polypropylene Glycol (Fujifilm Wako Pure Chemical Industries), Polypropylene Glycol (Merck), and Actocol (Mitsui Chemicals Fine).

[0046]

[0047] The weight average molecular weight of the tri or higher polyol type polypropylene glycol component is not particularly limited, but a suitable lower limit is, but is not particularly limited, preferably 500 or more, more preferably 1000 or more, even more preferably 1500 or more, more preferably 2000 or more, more preferably 2500 or more, more preferably 3000 or more; a suitable upper limit is, but is not particularly limited, preferably 100,000 or less, more preferably 50,000 or less, even more preferably 30,000 or less, more preferably 20,000 or less, more preferably 15,000 or less, more preferably 10,000 or less, more preferably 9500 or less, more preferably 9000 or less; and a suitable numerical range is, but is not particularly limited, preferably 2500 to 10,000, more preferably 3000 to 9500, and even more preferably 3000 to 9000. The weight average molecular weight of the triol-type polypropylene glycol can be any suitable upper limit and lower limit of the "weight average molecular weight of the tri- or higher polyol-type polypropylene glycol component" described above, and is not particularly limited, but is preferably 2,000 or more, more preferably 2,000 to 10,000, 2,500 to 9,500, or 2,000 to 9,000. The weight average molecular weight can be measured by a method such as GPC (gel permeation chromatography) analysis.

[0048] Furthermore, the hydroxyl value (mgKOH / g) of the tri or higher polyol-type polypropylene glycol component is not particularly limited as a suitable lower limit, but is preferably 10 or more, more preferably 13 or more, even more preferably 15 or more, and still more preferably 16 or more; the hydroxyl value (mgKOH / g) of the tri or higher polyol-type polypropylene glycol component is not particularly limited as a suitable upper limit, but is preferably 100 or less, more preferably 90 or less, even more preferably 80 or less, more preferably 70 or less, more preferably 65 or less, or 60 or less; and the hydroxyl value (mgKOH / g) of the tri or higher polyol-type polypropylene glycol component is not particularly limited as a suitable numerical range, but is preferably 15 to 80, more preferably 16 to 70.

[0049] 2-2-1-1-3. (a3) ​​Diol-Type Polypropylene Glycol The (a3) ​​diol-type polypropylene glycol component used in this embodiment is a type of polyether and is not particularly limited. However, commercially available diol-type components may be used, or desired diol-type components may be produced by known production methods. The diol-type polypropylene glycol component preferably has two hydroxyl groups in the molecule, with one hydroxyl group at each end. Furthermore, the diol-type polypropylene glycol component may have a polypropylene ether structure as a skeletal structure in the molecule, and may have hydroxyl groups at the ends of these skeletal structures.

[0050] For example, diol-type polypropylene glycol is preferably a substance obtained by adding propylene oxide to propylene glycol, and preferably has two hydroxyl groups in one molecule.

[0051] Commercially available diol-type polypropylene glycol components include, for example, Exenol (Asahi Glass), Polypropylene Glycol (Fujifilm Wako Pure Chemical Industries), Polypropylene Glycol (Merck), Actocols (Mitsui Chemicals Fine), and Sannix PP Series (Sanyo Chemical Industries).

[0052] The weight average molecular weight of the diol-type polypropylene glycol component when used as an optional component of the component (A) is not particularly limited, but a suitable lower limit is, but is not particularly limited, preferably 1,000 or more, more preferably 2,000 or more, even more preferably 2,500 or more, and still more preferably 3,000 or more; a suitable upper limit is, but is not particularly limited, preferably 50,000 or less, even more preferably 15,000 or less, more preferably 12,000 or less, 10,000 or less, 5,000 or less, or 4,000 or less; and a suitable numerical range is, but is not particularly limited, preferably 1,000 to 15,000, and more preferably 3,000 to 12,000.

[0053] The hydroxyl value of the diol-type polypropylene glycol component when used as an optional component of the component (A) is not particularly limited, but a suitable lower limit is, but is not particularly limited, preferably 5 or more, more preferably 8 or more, even more preferably 9 or more, more preferably 10 or more, 13 or more, or 15 or more, more preferably 18 or more, or 20 or more, more preferably 23 or more, 25 or more, or 28 or more; a suitable upper limit is, but is not particularly limited, preferably 120 or less, more preferably 100 or less, even more preferably 50 or less, even more preferably 40 or less, more preferably 35 or less, and more preferably 30 or less; and a suitable numerical range is, but is not particularly limited, preferably 5 to 40, more preferably 9 to 30.

[0054] 2-2-1-2. (B) Isocyanate Component The isocyanate component used in this embodiment may be a compound having two or more isocyanate groups (—NCO), preferably a polyisocyanate component, and the polyisocyanate monomer component may be either monomeric or polymeric. The number of isocyanate groups in the polyisocyanate component is not particularly limited, but may be, for example, 2, 3, 4, 5, 6, 7, or more, and these numbers may be appropriately combined, such as 2 to 4, 2 to 3, etc. Preferred is a diisocyanate component having one isocyanate group at each end of the molecule. More preferred is a diisocyanate component having two isocyanate groups. More preferred is a diisocyanate component having one isocyanate group at each end of the molecule.

[0055] The polyisocyanate component is one or more selected from isocyanate monomers, isocyanate oligomers, and isocyanate reactants of polyols and isocyanates (hereinafter also referred to as "isocyanate reactants" or "isocyanate-terminated prepolymers"). The polyisocyanates can be appropriately selected from the isocyanate monomers described in "2-2-1-2-4. Isocyanate Monomers" below. The isocyanate reactants can be produced by appropriately using the method described in "2-2-1-2-2. Method for Producing Diisocyanate Reactants" below, replacing the raw material diisocyanate with raw material isocyanate. Polyisocyanate reactants other than diisocyanates and their production methods can also be appropriately used. Furthermore, the raw material isocyanate used for the isocyanate monomer, isocyanate oligomer, or isocyanate reactant is preferably an aliphatic polyisocyanate, more preferably an aliphatic diisocyanate monomer, and the diisocyanate monomers described later in "2-2-1-2-5. Isocyanate Monomer" can be used as appropriate.

[0056] The isocyanate group content (NCO%) of the polyisocyanate component (preferably the diisocyanate component) is not particularly limited, but a suitable upper limit is, but is not particularly limited, preferably 70% or less, more preferably 60% or less, and even more preferably 50% or less, and a suitable lower limit is, but is not particularly limited, preferably 1% or more, more preferably 3% or more, and even more preferably 6% or more.

[0057] The isocyanate group content (NCO%) of the isocyanate reactant (preferably a diisocyanate group-terminated prepolymer) is not particularly limited, and suitable upper limits are, but are not particularly limited, preferably 30% or less, more preferably 25% or less, more preferably 24% or less, even more preferably 23% or less, more preferably 22% or less, more preferably 20% or less, more preferably 19% or less or 18% or less, more preferably 17% or less, even more preferably 16% or less, more preferably 15% or less, and more preferably 14% or less. A suitable lower limit is not particularly limited, but is preferably 1% or more, more preferably 1.5% or more, even more preferably 2% or more, more preferably 2.5% or more, more preferably 3% or more, 4% or more, 5% or more, 6% or more, 7% or more, 8% or more, 9% or more, or 10% or more. A suitable numerical range is not particularly limited, but is more preferably 1.0 to 24%, even more preferably 1.0 to 22%, even more preferably 1.0 to 20%, more preferably 1.0 to 25%, and more preferably 1.5 to 20%.

[0058] The isocyanate group content (NCO%) of the diisocyanate reactant (preferably a diisocyanate group-terminated prepolymer) is not particularly limited, but a suitable upper limit is, but is not particularly limited, more preferably 25% or less, 24% or less, 23% or less, or 22% or less, more preferably 20% or less, more preferably 19% or less or 18% or less, more preferably 17% or less, even more preferably 16% or less, more preferably 15% or less, and more preferably 14% or less; a suitable lower limit is, but is not particularly limited, preferably 1% or more, more preferably 1.5% or more, even more preferably 2% or more, more preferably 2.5% or more, more preferably 3% or more, 4% or more, 5% or more, 6% or more, 7% or more, or 8% or more; and a suitable numerical range is, but is not particularly limited, more preferably 1.0 to 25%, and even more preferably 1.5 to 22%. Furthermore, the weight average molecular weight of the isocyanate reactant may be set to a suitable upper limit and a suitable lower limit of the "weight average molecular weight of the diisocyanate reactant" described below.

[0059] The isocyanate group content (NCO%) of the diisocyanate monomer is not particularly limited, but a suitable upper limit is, but is not particularly limited, preferably 70% or less, more preferably 65% ​​or less, even more preferably 60% or less, more preferably 55% or less, 53% or less, or 50% or less; a suitable lower limit is, but is not particularly limited, preferably 1% or more, 5% or more, or 10% or more, more preferably 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, or 40% or more; and a suitable numerical range is, but is not particularly limited, more preferably 30 to 70%.

[0060] The isocyanate group content (NCO%) of the isocyanate oligomer (preferably a trimer) is not particularly limited, but a suitable upper limit is, but is not particularly limited, preferably 25% or less, more preferably 24% or less, even more preferably 23% or less, and more preferably 22% or less; a suitable lower limit is, but is not particularly limited, preferably 1% or more, more preferably 3% or more, 5% or more, 10% or more, or 15% or more; and a suitable numerical range is, but is not particularly limited, more preferably 1.0 to 24%, even more preferably 3 to 25%, and even more preferably 5 to 23%.

[0061] 2-2-1-2-1. (b1) Diisocyanate Component The diisocyanate component used in this embodiment is one or more selected from diisocyanate monomers, diisocyanate oligomers, and diisocyanate reactants of a raw material polyol and a raw material diisocyanate (hereinafter also referred to as "diisocyanate reactants"). The diisocyanate component is preferably a component having two isocyanate groups, more preferably a component having one isocyanate group at each end of the molecule, and even more preferably a component in which both ends of the molecule are isocyanate (NCO) groups (two in total).

[0062] The diisocyanate reactant is preferably an isocyanate-terminated prepolymer obtained from a diisocyanate and a polyol, more preferably an isocyanate-terminated prepolymer having isocyanate groups at at least both ends. The raw diisocyanate used for the diisocyanate reactant may be a monomer or an oligomer, but a monomer is preferred. Furthermore, both NCO terminals of the diisocyanate reactant are preferably derived from the same or different raw isocyanates, more preferably from the same isocyanate.

[0063] The diisocyanate oligomer is not particularly limited, but the diisocyanate oligomers described in "2-2-1-2-6. Isocyanate Oligomers" described below can be used as appropriate. For example, in polymers such as HDI and MDI, when both ends of the molecule have isocyanate groups (two in total), it is preferable to use a diisocyanate oligomer. The diisocyanate oligomer may be a diisocyanate group-terminated oligomer. Note that the diisocyanate oligomer may be used as an oligomer of the raw material diisocyanate used in the diisocyanate reactant.

[0064] The diisocyanate monomer is not particularly limited, but the diisocyanate monomers described below in "2-2-1-2-5. Isocyanate Monomer" can be used appropriately. The diisocyanate monomer may be a diisocyanate group-terminated monomer. The diisocyanate may also be used as a monomer for the raw diisocyanate used in the diisocyanate reactant. The diisocyanate monomer is preferably an aliphatic diisocyanate. Examples of diisocyanate monomers include, but are not limited to, linear aliphatic diisocyanates (preferably having 4 to 22 carbon atoms), alicyclic diisocyanates (preferably having 8 to 18 carbon atoms), aromatic diisocyanates (preferably having 8 to 26 carbon atoms), araliphatic polyisocyanates (preferably having 10 to 18 carbon atoms), and modified products of these diisocyanates. One or more of these may be used. Among these, preferred are chain aliphatic and / or alicyclic diisocyanates, more preferred are chain aliphatic diisocyanates having 4 to 22 carbon atoms and / or diisocyanates having 8 to 18 carbon atoms, and more specifically preferred are ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, isophorone diisocyanate (IPDI), and 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), and even more preferred are HDI, hydrogenated MDI, and MDI, and more preferably HDI. It is preferable that one or more selected from these suitable diisocyanates be used at both ends of the diisocyanate group-terminated prepolymer.

[0065] A preferred embodiment of the diisocyanate component is preferably a diisocyanate group-terminated prepolymer. More preferably, it is an isocyanate group-terminated prepolymer in which both ends of the molecule are derived from a linear aliphatic and / or alicyclic diisocyanate. A more preferred diisocyanate monomer at both ends is preferably one or more selected from HDI, hydrogenated MDI, and MDI, and more preferably hexamethylene diisocyanate (HDI). One or more of these may be used.

[0066] The weight-average molecular weight of the diisocyanate monomer is not particularly limited, but a suitable lower limit is not particularly limited, but is preferably 100 or more, 150 or more, 200 or more, 250 or more, 300 or more, 350 or more, 350 or more, 400 or more, 450 or more, or 500 or more. A suitable upper limit is not particularly limited, but is preferably 8,000 or less, more preferably 7,000 or less, more preferably 6,000 or less, more preferably 5,000 or less, more preferably 4,000 or less, 3,000 or less, 2,000 or less, 1,800 or less, 1,500 or less, 1,000 or less, or 500 or less. A suitable numerical range is preferably 200 to 1,000, and a diisocyanate compound in a specific low molecular weight range is more preferred. The weight-average molecular weight can be measured by a method such as GPC (gel permeation chromatography) analysis. The method for measuring the weight-average molecular weight of the diisocyanate reactant described below can also be measured taking this into consideration.

[0067] The polyols and polyisocyanates used as raw materials for the diisocyanate reactant will be described in detail below in "2-2-1-2-2." to "2-2-1-2-4." Examples of combinations include a combination of a diol-type polypropylene glycol and a diisocyanate monomer, a combination of a dihydric alcohol and a diisocyanate, and a combination of a polyol with two hydroxyl groups and a diisocyanate.

[0068] The weight average molecular weight of the diisocyanate reactant (preferably a diisocyanate group-terminated prepolymer) is not particularly limited, but a suitable lower limit is, but is not particularly limited, preferably 300 or more, 350 or more, 400 or more, 450 or more, 500 or more, 550 or more, or 600 or more; and a suitable upper limit is, but is not particularly limited, preferably 8000 or less, more preferably 7000 or less, more preferably 6000 or less, more preferably 5000 or less, more preferably 4000 or less, 3500 or less, 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1400 or less, 1300 or less, 1200 or less, 1000 or less, 900 or less, or 800 or less; a suitable numerical range is preferably 300 to 2000, and a diisocyanate compound in a specific low molecular weight range is more preferable.

[0069] Furthermore, the isocyanate group content (NCO%) of the diisocyanate reactant can be set to any of the suitable upper and lower limit values ​​of the "isocyanate group content (NCO%) of the isocyanate reactant" described above, and a suitable numerical range is preferably 1.0 to 25%, more preferably 10 to 20%.

[0070] 2-2-1-2-2. Method for Producing Diisocyanate Reactant As a specific example of a method for producing or preparing a diisocyanate reactant, the diisocyanate reactant is obtained by mixing and reacting a polyol and a diisocyanate. This reaction may be carried out in the presence or absence of a solvent. The amounts of polyol and diisocyanate to be reacted are preferably adjusted so that the [NCO / OH] ratio is 2 to 3, with preferred upper limits of 2 or less, 1.8 or less, 1.5 or less, or 1 or less, and preferred lower limits of 0.1 or more, 0.3 or more, 0.4 or more, or 0.5 or more. Adjustment to a range of 0.5 to 1.5 is even more preferable. Such adjustment is more preferable when producing a diisocyanate with a high molecular weight. This allows the diisocyanate reactant to be obtained. The diisocyanate reactant may be a diisocyanate-terminated prepolymer. Examples of the solvent include toluene, xylene, ethyl acetate, butyl acetate, dimethylformamide, acetone, methyl ethyl ketone, and THF.

[0071] The diisocyanate reactant is preferably obtained by reacting a polyol with a diisocyanate monomer in the absence of a solvent. The diisocyanate reactant is preferably a solvent-free reactant of a polyol with a diisocyanate monomer. By using such a solvent-free reactant, a pressure-sensitive adhesive composition can be obtained that does not contain a solvent (e.g., an organic solvent) that is highly irritating to the skin. In other words, by using the solvent-free reactant, a pressure-sensitive adhesive composition using a polyurethane that is less irritating to the skin can be obtained.

[0072] By mixing the raw materials for the diisocyanate reactant, the reaction proceeds in the same manner as in a general polyurethane reaction, and a diisocyanate reactant can be obtained. If necessary, the reaction conditions described later in "2-2-2. Method for producing polyurethane" may be appropriately adopted.

[0073] The mixing and reaction of the polyol and the diisocyanate may be carried out using a reaction apparatus known in the art. The reaction apparatus may be, for example, a mixing tank equipped with a stirrer or a static mixer. The reaction temperature is preferably 10 to 160°C, more preferably 25 to 120°C, from the viewpoints of reactivity and suppression of thermal degradation. During the reaction, it is preferable to replace the gas phase with nitrogen from the viewpoint of stability.

[0074] The hydroxyl value (mg KOH / g) in this specification can be measured in accordance with JIS K 0070 and JIS K 1557-5. This allows, for example, the hydroxyl value (mg KOH / g) of a polyol to be measured. The hydroxyl equivalent is the chemical formula weight per hydroxyl group in a polyol.

[0075] The isocyanate group content in this specification can be measured by potentiometric titration in accordance with JIS K 1603-1:2007. This allows, for example, the isocyanate group content (NCO%) of an isocyanate compound to be measured. The isocyanate equivalent is the chemical formula weight per isocyanate group in the isocyanate compound.

[0076] In the case of a polyisocyanate reactant, the "diisocyanate" in the above-described method for producing or preparing a diisocyanate reactant can be replaced with "polyisocyanate," and for example, a polyol and a polyisocyanate can be mixed and reacted to obtain a polyisocyanate reactant. The reaction may be carried out in the presence or absence of a solvent. The amounts of polyol and polyisocyanate to be reacted can be determined as appropriate using the above-described method for producing a diisocyanate reactant, and it is preferable to adjust the [NCO / OH] ratio to 2 to 3, or 2 or less, or 1 or less, with 0.5 to 1.5 being a preferred range.

[0077] 2-2-1-2-4. Polyol

[0078] The polyol used in the polymerization of an isocyanate reactant (isocyanate group-terminated prepolymer) such as diisocyanate used in this embodiment is preferably a compound having two or more hydroxyl groups (—OH), and examples thereof include those having two hydroxyl groups. Examples of the polyol component include polyether polyols and polyester polyols, and examples of these described below may be used as appropriate. One or more types selected from these may be used.

[0079] In addition to being used as a raw material for an isocyanate reactant such as a diisocyanate, the polyoxyalkylene polyol may also be used as an optional component of a polyol that is a raw material for a polyurethane resin. When a polyoxyalkylene polyol is used as a raw material polyol for a polyurethane resin, the number average molecular weight may be appropriately set to the preferred upper and lower limits of the number average molecular weight of the polyol-type polypropylene glycol described above.

[0080] Examples of polyol components include polyether polyols (e.g., polyoxyalkylene polyols (preferably EO and / or PO addition polymerization), polytetramethylene ether polyols, etc.), polyester polyols (e.g., adipic acid-based polyester polyols, phthalic acid-based polyester polyols, lactone-based polyester polyols, etc.), acid-modified polyester polyols, polycarbonate polyols, polyurethane polyols (e.g., polyols obtained by urethane-modifying polyether polyols, polyester polyols, polycarbonate polyols, etc. with known polyisocyanates), epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, vinyl monomer-modified polyols, polyhydric alcohols, etc. In addition, when "ether" or "ester" is not specifically mentioned in examples of polyols other than polyhydric alcohols, either "ether-based" or "ester-based" may be used. For example, vegetable oil polyols may be classified as vegetable oil-based polyester polyols or vegetable oil-based polyether polyols.

[0081] Examples of polyether polyol components include, but are not limited to, polyoxyalkylene polyols, and examples of the "alkylene" in the "oxyalkylene" include ethylene (-CH2CH2-), propylene (-CH(CH3)CH2-), etc.

[0082] The polyoxyalkylene polyol component is not particularly limited, and examples thereof include polyoxyethylene glycol (diol type), polyoxyethylene triol (triol type), polyoxypropylene glycol (diol type), polyoxypropylene triol (triol type), and monool types of polyoxypropylene glycol and polyoxyethylene glycol.

[0083] In addition, examples of polyols other than those mentioned above are also listed below, but these may also be used appropriately as polyols and are not particularly limited. Examples of polyol components include high-molecular-weight polyols and low-molecular-weight polyols. For example, the low molecular weight may be, in terms of hydroxyl value (mg KOH / g), preferably 100 or more, more preferably 150 or more, and even more preferably 200 or more. In terms of weight-average molecular weight, the weight-average molecular weight may be 2000 or less than 1000, and in terms of number-average molecular weight, the number-average molecular weight may be less than 300. One or more selected from these may be used.

[0084] The high molecular weight polyol is preferably one having two or more hydroxyl groups, and examples thereof include polyether polyol, polyester polyol, acid-modified polyester polyol, polycarbonate polyol, polyurethane polyol, epoxy polyol, vegetable oil polyol, polyolefin polyol, acrylic polyol, vinyl monomer-modified polyol, etc. One or more selected from these can be used.

[0085] The low molecular weight polyol preferably has two or more hydroxyl groups, for example, a compound having 40 or more hydroxyl groups, and examples thereof include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethylpentanediol, 3,3-dimethylolheptane, alkane (C7-20) diol, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol and mixtures thereof, hydrogenated bisphenol A, 1,4-dihydroxy Examples of alcohols that can be used include dihydric alcohols such as 2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol, and dipropylene glycol; trihydric alcohols such as glycerin, trimethylolpropane, and triisopropanolamine; tetrahydric alcohols such as tetramethylolmethane (pentaerythritol) and diglycerin; pentahydric alcohols such as xylitol; hexahydric alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, and dipentaerythritol; heptahydric alcohols such as perseitol; and octahydric alcohols such as sucrose. One or more of these may be used.

[0086] 2-2-1-2-5. Isocyanate Monomer The isocyanate monomer used in this embodiment is preferably a compound having one to three isocyanate groups (-NCO), and more preferably a monomer having two isocyanate groups (diisocyanate) from the viewpoints of better adhesion to contact areas and less irritation. The isocyanate may be a single type or a combination of two or more types.

[0087] Examples of polyisocyanate (preferably diisocyanate) monomers include, but are not limited to, linear aliphatic polyisocyanates (preferably having 4 to 22 carbon atoms; b11), alicyclic polyisocyanates (preferably having 8 to 18 carbon atoms; b12), aromatic polyisocyanates (preferably having 8 to 26 carbon atoms; b13), araliphatic polyisocyanates (preferably having 10 to 18 carbon atoms; b14), and modified products of these polyisocyanates (b15). Note that polyisocyanate monomers may include monomeric and polymeric ones, and examples thereof include diphenylmethane diisocyanate, which is a diisocyanate component, and monomeric MDI (4,4'-diphenylmethane diisocyanate), which is a polyisocyanate component. Examples include polymeric MDI (polymethylene polyphenyl polyisocyanate: n=1, 2, 3, 4, 5, 6, or more, 1 to 2, 2 to 3, etc.).

[0088] Examples of the linear aliphatic polyisocyanate (preferably having 4 to 22 carbon atoms; b11) include diisocyanates such as ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter also referred to as "HDI"), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis(2-isocyanatoethyl)fumarate, bis(2-isocyanatoethyl)carbonate, and 2-isocyanatoethyl-2,6-diisocyanatohexanoate; and triisocyanates such as 1,6,11-undecane triisocyanate.

[0089] Examples of the alicyclic polyisocyanate (preferably having 8 to 18 carbon atoms; b12) include diisocyanates such as isophorone diisocyanate (hereinafter also referred to as "IPDI"), 4,4'-dicyclohexylmethane diisocyanate (hereinafter also referred to as "hydrogenated MDI"), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, and 2,5- or 2,6-norbornane diisocyanate.

[0090] Examples of the aromatic polyisocyanate (preferably having 8 to 26 carbon atoms; b13) include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter also referred to as "TDI"), crude TDI, 4,4'- or 2,4'-diphenylmethane diisocyanate (hereinafter also referred to as "diphenylmethane diisocyanate" (hereinafter also referred to as "MDI"), crude MDI, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenyl Examples include diisocyanates such as methane and 1,5-naphthylene diisocyanate; polyaryl polyisocyanates, 4,4',4"-triphenylmethane triisocyanate and m- or p-isocyanatophenylsulfonyl isocyanate; 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate; and polymeric MDI (n = 1, 2, 3, 4 or more, 1 to 2, 2 to 3, etc.). When n = 1 in the polymeric MDI, the number of NCO groups is preferably 3, and when n = 1 or 2, the number of NCO groups is preferably 3 or 4.

[0091] Examples of the aromatic aliphatic polyisocyanates (having 10 to 18 carbon atoms; b14) include diisocyanates such as m- or p-xylylene diisocyanate and α,α,α',α'-tetramethylxylylene diisocyanate.

[0092] Examples of the modified polyisocyanates (b15) include modified polyisocyanates (such as those containing a urethane group, a carbodiimide group, an allophanate group, a urea group, a biuret group, a uretdione group, a uretoimine group, an isocyanurate group, or an oxazolidone group; those having a free isocyanate group content of preferably 8 to 33% by weight, more preferably 10 to 30% by weight, and particularly preferably 12 to 29% by weight), such as modified MDI (such as urethane-modified MDI, carbodiimide-modified MDI, and trihydrocarbyl phosphate-modified MDI), urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, and isocyanurate-modified IPDI. One or more selected from these may be used.

[0093] From the viewpoints of hue, better adhesion to contact areas, and less irritation, the polyisocyanate (preferably diisocyanate) is more preferably one or more selected from chain aliphatic polyisocyanates (preferably having 4 to 22 carbon atoms; b11), alicyclic polyisocyanates (preferably having 8 to 18 carbon atoms; b12), and aromatic polyisocyanates (preferably having 8 to 26 carbon atoms; b13), and even more preferably chain aliphatic polyisocyanates (b11) having 4 to 22 carbon atoms and / or polymeric MDI. Also preferred are one or more selected from HDI, hydrogenated MDI, and MDI. Oligomers of these may also be used.

[0094] 2-2-1-2-6. Isocyanate Oligomer The isocyanate oligomer is not particularly limited, and examples thereof include oligomers of polyisocyanates having two or more isocyanate groups (polymers of 2, 3, 4, or 5 to 8, 9, or 10 isocyanate monomers; for example, dimers, trimers, tetramers, etc.). Diisocyanate oligomers, in which both ends of the molecule are terminated with isocyanate groups, are preferred. Isocyanate oligomers preferably have a weight-average molecular weight of 1,000 or less. The isocyanate oligomer is not particularly limited, but it is preferable that it does not contain the polyisocyanate reactant obtained by reacting the above-mentioned polyol. The isocyanate oligomer is preferably polymeric.

[0095] Examples of isocyanate oligomers include oligomers obtained by polymerizing an aliphatic diisocyanate monomer such as hexamethylene diisocyanate (HDI); and oligomers obtained by polymerizing an aromatic diisocyanate monomer such as diphenylmethane diisocyanate (MDI). The aliphatic diisocyanate oligomer may be, for example, a dimer or trimer (isocyanurate, biuret, or adduct of trimethylolpropane (TMP)) of an aliphatic diisocyanate. The aliphatic diisocyanate oligomer may be a trimer of HDI (e.g., HDI trimer), such as an HDI trimer having a polyisocyanurate structure. The aromatic diisocyanate polymer may be a polymer of MDI. One or more of these may be used.

[0096] The weight average molecular weight of the isocyanate oligomer is not particularly limited, but a suitable lower limit is not particularly limited, but may be preferably 100 or more, 200 or more, 300 or more, or 400 or more, and a suitable upper limit is not particularly limited, but may be preferably 1000 or less, 900 or less, 800 or less, 700 or less, or 600 or less. Furthermore, the isocyanate group content (NCO %) of the isocyanate oligomer can be appropriately determined from the suitable upper and lower limits of the above-mentioned "isocyanate group content (NCO %) of the isocyanate reactant," and a suitable numerical range is preferably 1.0 to 25%, more preferably 1.5 to 23%.

[0097] 2-2-2. Polyurethane manufacturing method

[0098] The method for producing the polyurethane is not particularly limited, but known polyurethane production methods can be taken into consideration. The heating temperature and heating time in the "Method for producing a polyurethane adhesive composition" described below or the [Production procedure] described in the [Examples] may be appropriately adopted. For example, a suitable heating temperature is 50°C or higher and 120°C or lower, and a suitable heating time is 3 minutes or higher and 15 minutes or lower.

[0099] The polyurethane resin raw materials containing the components (A) and (B) used to form the polyurethane described above, and optional components such as auxiliary raw materials such as catalysts, can be mixed simultaneously or separately to obtain a cured polyurethane product through a polyurethane reaction. A catalyst for a urethane reaction is preferably used as the catalyst in this process. The components (A) and (B) may be mixed simultaneously or separately and then the curing reaction may proceed, or the curing reaction of the mixture may proceed after mixing these components. Alternatively, a composition containing the polyurethane raw material components described above may be prepared, and then the composition may be subjected to a polyurethane reaction to obtain a cured polyurethane product. In addition to the components (A) and (B) described above as polyurethane resin raw materials, a composition may be prepared that appropriately contains a polyol component (e.g., a polyalkylene glycol diol type) and a polyisocyanate component other than the components (A) and (B) used as optional components of the polyurethane resin raw material.

[0100] Furthermore, the method for producing polyurethane according to this embodiment may also be used as a method for producing a pressure-sensitive adhesive composition. In such cases, a component or form that is not dissolved in the raw material such as polyurethane may be appropriately blended, for example, a particulate hydrophilic component.

[0101] In the present embodiment, before curing of the polyurethane resin used in the adhesive composition, "the curable composition or the total amount thereof" may be referred to as "the mixture or the total amount thereof," and "the mixture or the total amount thereof" may be referred to as "the curable composition or the total amount thereof." Furthermore, after curing of the polyurethane resin used in the adhesive composition, "the cured product or the total amount thereof" may be referred to as "the adhesive composition or the total amount thereof," and "the adhesive composition or the total amount" may be referred to as "the cured product or the total amount thereof."

[0102] <Content ratio of each component relative to 100 parts by mass of the total amount of the (A) polyol component and the (B) polyisocyanate component> When the total amount of the (A) polyol component and the (B) polyisocyanate component is taken as 100 parts by mass, it is preferable that each component is contained or used in the following content ratio. Note that "the total amount of the (A) component and the (B) component" may also be "the total amount of the polyurethane resin."

[0103] When the total amount of the component (A) and the component (B) (total amount of polyurethane resin) is 100 parts by mass, from the viewpoint of flexibility, the preferred lower limit of the content of the (a1) monool-type polypropylene glycol component is not particularly limited, but is preferably 15.0 parts by mass or more, more preferably 25.0 parts by mass or more, more preferably 28.0 parts by mass or more, even more preferably 30.0 parts by mass or more, more preferably 35.0 parts by mass or more, and more preferably 40.0 parts by mass or more. Also, from the viewpoint of cohesiveness, the preferred upper limit is not particularly limited, but is preferably 70.0 parts by mass or less, more preferably 65.0 parts by mass or less, even more preferably 60.0 parts by mass or less, and more preferably 55.0 parts by mass or less. The preferred numerical range is preferably 15.0 parts by mass or more and 70.0 parts by mass or less, more preferably 30.0 parts by mass or more and 60.0 parts by mass or less.

[0104] When the total amount of the (A) component and the (B) component (total amount of polyurethane resin) is 100 parts by mass, the content of the (a) polyol-type polypropylene glycol component is not particularly limited, but from the viewpoint of cohesion, a suitable lower limit is not particularly limited, but is preferably 5.0 parts by mass or more, more preferably 10.0 parts by mass or more, even more preferably 20.0 parts by mass or more, more preferably 25.0 parts by mass or more, more preferably 28.0 parts by mass or more, more preferably 30.0 parts by mass or more, and more preferably 35.0 parts by mass or more. Also, a suitable upper limit is not particularly limited, but from the viewpoint of adhesion, is preferably 70.0 parts by mass or less, more preferably 65.0 parts by mass or less, even more preferably 60.0 parts by mass or less, more preferably 55.0 parts by mass or less, and more preferably 50.0 parts by mass or less. The suitable numerical range is preferably 5.0 parts by mass or more and 70.0 parts by mass or less, and more preferably 30.0 parts by mass or more and 65.0 parts by mass or less.

[0105] When the total amount of the (A) component and the (B) component (total amount of polyurethane resin) is 100 parts by mass, the content of the (a2) tri- or higher polyol-type polypropylene glycol component is, from the viewpoint of cohesion, not particularly limited as a suitable lower limit, but is preferably 5.0 parts by mass or more, more preferably 10.0 parts by mass or more, even more preferably 13.0 parts by mass or more, more preferably 15.0 parts by mass or more, and more preferably 20.0 parts by mass or more. The content of the (a2) tri- or higher polyol-type polypropylene glycol component is, from the viewpoint of adhesion, not particularly limited as a suitable upper limit, but from the viewpoint of adhesion, is preferably 70.0 parts by mass or less, more preferably 65.0 parts by mass or less, even more preferably 60.0 parts by mass or less, more preferably 55.0 parts by mass or less, and more preferably 50.0 parts by mass or less. The suitable numerical range is preferably 5.0 parts by mass or more and 70.0 parts by mass or less, and more preferably 20.0 parts by mass or more and 65.0 parts by mass or less. In the case of triol-type polypropylene glycol, suitable lower and upper limits for the "content ratio of tri or higher polyol-type components" described above can be appropriately adopted, and the suitable numerical range is preferably 5.0 parts by mass or more and 70.0 parts by mass or less, and more preferably 20.0 parts by mass or more and 65.0 parts by mass or less.

[0106] When the total amount of the component (A) and the component (B) (total amount of polyurethane resin) is 100 parts by mass, and the amount of the (a2) tri- or higher polyol-type polypropylene glycol component used in the (a) polyol-type polypropylene glycol component is at least half of the main component, the preferred upper limit of the content of the (a3) ​​diol-type polypropylene glycol component is preferably 30.0 parts by mass or less, more preferably 20.0 parts by mass or less, even more preferably 10.0 parts by mass or less, more preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, and may even be substantially free (1, 0.5, or 0.01.0 parts by mass or less, 0.0 parts by mass or less).

[0107] When the total amount of the (A) component and the (B) component (total amount of polyurethane resin) is taken as 100 parts by mass, the content of the polyisocyanate component is not particularly limited as a suitable lower limit, but is preferably 1.0 part by mass or more, more preferably 1.5 parts by mass or more, even more preferably 2.0 parts by mass or more, more preferably 2.5 parts by mass or more, even more preferably 3.0 parts by mass or more, more preferably 4.0 parts by mass or more, and even more preferably 5.0 parts by mass or more. The preferred upper limit is preferably 30.0 parts by mass or less, more preferably 25.0 parts by mass or less, even more preferably 20.0 parts by mass or less, or 15.0 parts by mass or less. The preferred numerical range is preferably 3.0 parts by mass or more to 30.0 parts by mass or less, more preferably 5.0 parts by mass or more to 20.0 parts by mass or less. The content of the diisocyanate component and / or isocyanate oligomer component may appropriately adopt the preferred upper limit and preferred lower limit of the "content of the polyisocyanate component" described above, or a combination thereof. For example, when the total amount of the (A) component and the (B) component (total amount of polyurethane resin) is 100 parts by mass, the content of the diisocyanate reactant is not particularly limited as a suitable numerical range, but is preferably 3.0 parts by mass or more and 30.0 parts by mass or less, more preferably 5.0 parts by mass or more and 20.0 parts by mass or less. For example, when the total amount of the (A) component and the (B) component (total amount of polyurethane resin) is 100 parts by mass, the content of the diisocyanate monomer is not particularly limited as a suitable numerical range, but is preferably 1.5 parts by mass or more and 30.0 parts by mass or less, more preferably 2.0 parts by mass or more and 20.0 parts by mass or less. For example, when the total amount of the (A) component and the (B) component (total amount of polyurethane resin) is 100 parts by mass, the content of the isocyanate oligomer (preferably isocyanate trimer) is not particularly limited, but is preferably 1.5 parts by mass or more and 30.0 parts by mass or less, more preferably 2.0 parts by mass or more and 20.0 parts by mass or less.

[0108] As a preferred aspect of this embodiment, the proportions of each component in the polyurethane resin raw material are shown below. Note that the "proportions" shown below may be mass content ratios in the polyurethane resin raw material, the composition, the curable composition, the mixture, the adhesive composition, etc. Also, the mass content ratios may be mass usage ratios.

[0109] <Ratio of (a) Polyol-Type Polypropylene Glycol Component / (a1) Monool-Type Polypropylene Glycol Component> The mass ratio of the component (a) polyol-type component ((a) polyol-type polypropylene glycol component / (a1) monool-type polypropylene glycol component) to the (a1) monool-type component is not particularly limited, but when the mass of the component (a1) monool-type component is taken as 1, from the viewpoint of cohesion, a suitable lower limit is, but is not particularly limited, preferably 0.4 or more, more preferably 0.5 or more, more preferably 0.6 or more, and more preferably 0.7 or more. Also, a suitable upper limit is, but is not particularly limited, from the viewpoint of flexibility, preferably 2.0 or less, more preferably 1.9 or less, more preferably 1.8 or less, even more preferably 1.7 or less, more preferably 1.5 or less, more preferably 1.4 or less, more preferably 1.3 or less, more preferably 1.2 or less, more preferably 1.1 or less, and more preferably 1.0 or less. The suitable numerical range is, but is more preferably 0.5 or more and 1.9 or less.

[0110] <Ratio of (a2) Tri- or Higher Polyol-Type Polypropylene Glycol Component / (a1) Monool-Type Polypropylene Glycol Component> The mass ratio of the component (a2) tri- or higher polyol-type component to the (a1) monool-type component ((a2) tri- or higher polyol-type polypropylene glycol component / (a1) monool-type polypropylene glycol component) is not particularly limited, but when the mass of the component (a1) monool-type component is taken as 1, from the viewpoint of cohesion, a suitable lower limit is, but is not particularly limited, preferably 0.4 or more, more preferably 0.5 or more, more preferably 0.6 or more, and more preferably 0.7 or more. Also, a suitable upper limit is, but is not particularly limited, from the viewpoint of flexibility, preferably 2.0 or less, more preferably 1.9 or less, more preferably 1.8 or less, even more preferably 1.7 or less, more preferably 1.5 or less, more preferably 1.4 or less, more preferably 1.3 or less, more preferably 1.2 or less, more preferably 1.1 or less, and more preferably 1.0 or less. The suitable numerical range is, but is not particularly limited, more preferably 0.5 or more and 1.9 or less. The tri- or higher polyol type may be a triol type, and the mass ratio of [triol-type polypropylene glycol component / (a1) monool-type polypropylene glycol component] may be any suitable upper limit value and suitable lower limit value, or combination thereof, of the mass content ratio of [(a2) tri- or higher polyol-type polypropylene glycol component / (a1) monool-type polypropylene glycol component] described above. The suitable numerical range is not particularly limited, but is more preferably 0.5 or more and 1.9 or less.

[0111] In addition, when producing the polyurethane, a curable composition may be obtained by further using or blending an optional ingredient raw material, and after curing the curable composition, a cured product may be obtained as a polyurethane, which may be used in the adhesive composition. In addition, when producing the adhesive composition, the polyurethane may be mixed with the optional ingredient to prepare the adhesive composition. The optional ingredient is not particularly limited, but it is preferable to appropriately employ, for example, "2-3. Optional ingredient (other raw material)" described below.

[0112] 2-3. Optional ingredients (raw materials other than polyurethane resin raw materials)

[0113] 2-3-1. Skin care ingredients

[0114] The other raw materials may be, for example, skin care ingredients. The mixture used in this embodiment and the cured product thereof may further contain, for example, skin care ingredients.

[0115] As used herein, the term "skin care ingredient" refers to an ingredient capable of maintaining and / or improving the health and / or appearance of skin. "Maintaining and / or improving the health and / or appearance of skin" can include, for example, maintaining healthy skin, preventing skin problems (e.g., itching, rash, redness, etc.), improving skin problems, preventing skin problems from worsening, maintaining skin appearance, and improving skin appearance. Examples of the skin care ingredient include, but are not limited to, skin protection ingredients (e.g., mineral oil), moisturizing ingredients (e.g., ceramide), ingredients for improving rough skin, anti-inflammatory ingredients, and whitening ingredients. In this embodiment, one or a combination of two or more of these skin care ingredients may be used. Hereinafter, "of the total amount of the curable composition" refers to "of the total amount of the composition" or "of the mixture," but it may also refer to "of the total amount of the composition" or "of the mixture."

[0116] The ceramide is not particularly limited, but includes natural ceramides such as bioceramide and cerebroside; human ceramides such as ceramide 2 and ceramide 3; plant ceramides such as rice bran glycosphingolipid; pseudoceramides such as hexadecyloxy PG hydroxyethylhexadecanamide; and the like, and one or more of these can be used. Among these, human ceramides are preferred, and ceramide 2 is more preferred.

[0117] The content of the skin care ingredient in the total amount of the curable composition is not particularly limited, but is, for example, 0.01% by mass or more and 10.0% by mass or less, preferably 0.05% by mass or more and 5.0% by mass or less, and more preferably 0.1% by mass or more and 3.0% by mass or less. A content of the skin care ingredient of, for example, 0.01% or more can contribute to obtaining the effects of the skin care ingredient.

[0118] The content of ceramide in the total amount of the curable composition is not particularly limited from the viewpoint of moisturizing or pH buffering, but a suitable lower limit is, but is not particularly limited, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, and a suitable upper limit is, but is not particularly limited, preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less. The content of human ceramide (preferably ceramide 3) can be determined by appropriately adopting the suitable upper and lower limits of the above-mentioned "ceramide content," and is more preferably 0.01 to 1% by mass.

[0119] Furthermore, the content ratio of the skin care ingredient relative to 100 parts by mass of the total amount of the component (A) and the component (B) is not particularly limited, but is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, even more preferably 0.1 parts by mass or more, and is also preferably 5 parts by mass or less, more preferably 3 parts by mass or more, and even more preferably 1 part by mass or more.

[0120] 2-3-2. hydrophilic component

[0121] The other raw material may be, for example, a hydrophilic component. The mixture used in this embodiment and its cured product (polyurethane) may further contain, for example, a hydrophilic component. The hydrophilic component may also be a hydrophilic powder.

[0122] The hydrophilic component can absorb liquid components (e.g., body fluids such as blood, exudate, and pus, sweat, and excrement). Generally, if a liquid component remains between the adhesive and the skin surface for a long period of time, the adhesive strength of the adhesive decreases and skin troubles tend to occur. The adhesive composition of the present invention containing the hydrophilic component can absorb the liquid component, and therefore can suppress the decrease in adhesive strength and skin troubles caused by the liquid component.

[0123] When the adhesive composition according to the present embodiment is used to cover a wound, the hydrophilic component can absorb exudate from the wound surface to maintain a moist environment, thereby contributing to promoting wound healing. Such a wound treatment method is called moist environment therapy, and can promote wound healing by retaining polymorphonuclear leukocytes, macrophages, enzymes, cell growth factors, and the like contained in the exudate on the wound surface.

[0124] The hydrophilic component may be blended for the purposes of, for example, absorbing sweat, impregnating and releasing medicine, and moisturizing.

[0125] An example of a hydrophilic component is a hydrophilic polymer. The hydrophilic polymer may be, for example, a natural, semi-synthetic, or synthetic hydrophilic polymer. "Semi-synthetic," also referred to as partial chemical synthesis, refers to chemical synthesis using compounds isolated from natural sources, such as plant materials, microorganisms, or cell cultures, as starting materials. Furthermore, the polymer may be in the form of one or more salts selected from alkali metal salts and alkaline earth metal salts, such as sodium and calcium. Furthermore, when sodium or calcium is mentioned in the specific exemplary compounds below, the salts may also be salts (alkali metal salts and alkaline earth metal salts), such as CMC salts and polyacrylates.

[0126] Examples of natural hydrophilic polymers include plant-based polymers such as gum arabic, tragacanth gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, and starch (e.g., rice, corn, potato, and wheat starch); microbial-based polymers such as xanthan gum, dextrin, dextran, succinoglucan, mannan, locust bean gum, and pullulan; and animal-based polymers such as casein, albumin, and gelatin.

[0127] Examples of semi-synthetic hydrophilic polymers include starch-based polymers such as carboxymethyl starch and methylhydroxypropyl starch; cellulose-based polymers such as methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, hydroxypropylcellulose, carboxymethylcellulose, and sodium carboxymethylcellulose; and alginic acid-based polymers such as sodium alginate, calcium alginate, and propylene glycol alginate. "Semi-synthetic" may also mean that natural materials (e.g., starch, cellulose, alginic acid, etc.) are used as raw materials and are partially chemically modified by chemical treatment.

[0128] Examples of synthetic hydrophilic polymers include vinyl polymers such as polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, and carboxyvinyl polymers; acrylic polymers such as sodium polyacrylate and polyacrylamide; and polyethyleneimine.

[0129] In the present embodiment, one or a combination of two or more of these hydrophilic polymers may be used. The hydrophilic polymer is preferably one or more selected from the group consisting of natural hydrophilic polymers such as carboxymethylcellulose salts (e.g., sodium carboxymethylcellulose), pectin, karaya gum, mannan, locust bean gum, and gelatin; and acrylic polymers such as polyacrylates, more preferably one or more selected from the group consisting of sodium carboxymethylcellulose, pectin, gelatin, and polyacrylates, even more preferably one or more selected from sodium carboxymethylcellulose, pectin, and sodium polyacrylate, and more preferably sodium carboxymethylcellulose and / or pectin. An adhesive composition containing such a hydrophilic polymer has good absorbency of liquid components, and can therefore effectively suppress a decrease in adhesive strength and skin troubles caused by the liquid components.

[0130] Another example of the hydrophilic component is an inorganic compound having water absorption or hygroscopicity. A specific example of such an inorganic compound is silica. Another example of the hydrophilic component is a substance having adsorptive properties. A specific example of such a substance is activated carbon.

[0131] The content of the hydrophilic component in the total amount of the curable composition is not particularly limited, but a suitable lower limit is, but is not particularly limited, preferably 1.0 mass% or more, more preferably 5.0 mass% or more, more preferably 10.0 mass% or more, and more preferably 15.0 mass% or more. Also, a suitable upper limit is, but is not particularly limited, preferably 60.0 mass% or less, more preferably 50.0 mass% or less, and even more preferably 45.0 mass% or less. The suitable numerical range is, but is not particularly limited, more preferably 10.0 mass% or more and 50.0 mass% or less. Such a content ratio is preferable to obtain a polyurethane adhesive composition that has good adhesiveness and also absorbs liquid components. In this specification, when the hydrophilic component is a combination of two or more components, the "content ratio of the hydrophilic component" means the total content ratio of the two or more components. Furthermore, with respect to the content of the hydrophilic polymer or synthetic hydrophilic polymer in the total amount of the curable composition, a suitable lower limit is not particularly limited, but is preferably 5.0 mass% or more, more preferably 10.0 mass% or more, and more preferably 15.0 mass% or more. A suitable upper limit is not particularly limited, but is preferably 60.0 mass% or less, more preferably 50.0 mass% or less, and even more preferably 45.0 mass% or less. The suitable numerical range is not particularly limited, but is more preferably 10.0 mass% or more and 50.0 mass% or less.

[0132] The content ratio of the hydrophilic component relative to 100 parts by mass of the total amount of the component (A) and the component (B) is not particularly limited, and a suitable lower limit is not particularly limited, but is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more. A suitable upper limit is not particularly limited, but is preferably 60 parts by mass or less, more preferably 50 parts by mass or more, and even more preferably 45 parts by mass or more.

[0133] 2-3-3. Viscosity imparting agent

[0134] The other raw material may be, for example, a viscosity imparting agent. The mixture used in this embodiment and its cured product (polyurethane) may further contain, for example, a viscosity imparting agent.

[0135] As used herein, the term "tackifier" refers to an additive that imparts viscosity to a polyurethane pressure-sensitive adhesive composition. Examples of the viscosity-imparting agent include alcohols. Examples of the alcohol include polyols, monohydric alcohols, and polyolefin resins that are not blended as the polyols in the mixture and its cured product (polyurethane).

[0136] Examples of the polyol include glycols. Examples of glycols include hexanediol, pentanediol, nonanediol, and polypropylene glycol. Examples of the monohydric alcohol include saturated monohydric alcohols. Examples of saturated monohydric alcohols include propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, and decanol. Examples of the polyolefin resin include polybutene.

[0137] In the present embodiment, one or a combination of two or more of these viscosity imparting agents may be used. The viscosity imparting agent contained in the above mixture and its cured product preferably contains a glycol and a polyolefin resin, more preferably a glycol and a polybutene, even more preferably one or more selected from hexanediol, pentanediol, and nonanediol and a polybutene, and particularly preferably a pentanediol and a polybutene. By using such a viscosity imparting agent, a polyurethane adhesive composition having a good balance between flexibility and viscosity can be obtained.

[0138] The content of the viscosity imparting agent in the total amount of the curable composition is not particularly limited, but is, for example, 0.1% by mass or more and 20.0% by mass or less, preferably 0.5% by mass or more and 15.0% by mass or less. A viscosity imparting agent content of, for example, 0.1% by mass or more can contribute to improving the adhesiveness of the polyurethane adhesive composition. A viscosity imparting agent content of, for example, 20.0% by mass or less is less likely to interfere with the effects of other raw materials such as hydrophilic components.

[0139] 2-3-4. Catalyst

[0140] The other raw material may be, for example, a catalyst. The mixture used in this embodiment and its cured product (polyurethane) may preferably further contain a catalyst. The catalyst can efficiently induce a polymer polymerization reaction of an isocyanate-terminated prepolymer or the like.

[0141] The catalyst may be, for example, a metal carboxylate, a bismuth carboxylate, a modified silicone, bis(2-ethylhexanoyloxy)zinc, an acrylic polymer, an acrylic silicone polymer, or a metal carbonate.

[0142] The content of the catalyst in the total amount of the curable composition may be, for example, 0.01% by mass or more and 5.0% by mass or less. Note that, in the case of a cured product, the total amount of the curable composition may be the total amount of the cured product. The content ratio of the catalyst relative to 100 parts by mass of the total amount of the component (A) and the component (B) may be, for example, 0.02 parts by mass or more and 10 parts by mass or less.

[0143] 2-3-5. Additives

[0144] The polyurethane adhesive composition according to the present embodiment may contain various additives other than those described above, such as plasticizers, fillers, pH adjusters, colorants, antibacterial agents, and pharmaceuticals (medicinal components), as long as the effects of the present invention are not impaired.

[0145] The plasticizer is not particularly limited, but examples thereof include ester-based plasticizers (dibutyl phthalate, dioctyl phthalate, dioctyl adipate, polyethylene glycol (molecular weight: 200) diadipate, etc.), phosphate ester-based plasticizers (triethyl phosphate, triisopropyl phosphate, etc.), and petroleum resin-based plasticizers.

[0146] The adhesive composition of this embodiment can be applied without using a plasticizer, and for example, the content of the plasticizer in the total amount of the curable composition is not particularly limited, but is preferably not more than 15% by mass, more preferably not more than 10% by mass, and even more preferably not more than 0% by mass. Furthermore, the blending ratio of the plasticizer relative to 100 parts by mass of the total amount of the polyurethane resin is preferably not more than 15 parts by mass, more preferably not more than 10 parts by mass, and even more preferably not more than 5 parts by mass.

[0147] 2-4. Method for producing polyurethane adhesive composition

[0148] The adhesive composition according to the present embodiment can be obtained by mixing at least the above-described (A) polypropylene glycol component and (B) polyisocyanate component (preferably diisocyanate component) and curing the resulting curable composition. During the production, optional components may be used or blended into the curable composition or mixture, as appropriate. The mixing and curing reaction may be carried out by means known in the art. The polyurethane adhesive composition may be for use on skin, wounds, or mucous membranes.

[0149] The curable composition or mixture containing the component (A) and the component (B) may be gradually cured over time. In order to promote the curing of the curable composition or mixture, the mixture may be heat-treated. The heat treatment may be heat drying. In the heat treatment, the heating temperature is, for example, from 50°C to 130°C, and preferably from 50°C to 100°C. The heating time is, for example, from 1 minute to 20 minutes, and preferably from 3 minutes to 10 minutes. For example, when producing a patch containing the pressure-sensitive adhesive composition, the contents of the description regarding "Patch according to this embodiment" in "2-6." described below and the [Manufacturing Procedure] described in [Examples] may be appropriately adopted.

[0150] Suitable curable compositions for use in this embodiment are as follows. Suitable examples of the contents, weight average molecular weights, hydroxyl values, NCO%, etc. of the (a1) monool-type propylene glycol component and (b1) diisocyanate component (preferably a diisocyanate-terminated prepolymer) used as raw materials for the polyurethane can be appropriately selected from the contents of the suitable curable compositions in "2-2. Polyurethane" above. In this case, the contents of the optional components used can be appropriately selected from the contents of the suitable curable compositions in "2-3. Optional Components" above.

[0151] In a more preferred embodiment, the present invention is directed to a curable composition containing at least polyurethane, which is a cured product of a composition containing (a1) a mono-ol polypropylene glycol component and (b1) a diisocyanate component. The curable composition may be cured by a polyurethane reaction, and the cured product may be a polyurethane adhesive composition.

[0152] The content of the monool-type polypropylene glycol component (a1) in the total amount of the curable composition is not particularly limited, and a suitable lower limit is not particularly limited, but is preferably 10% or more, more preferably 15% or more, even more preferably 18% or more, more preferably 20% or more, and more preferably 22% or more. Also, a suitable upper limit is not particularly limited, but is preferably 70% or less, more preferably 65% ​​or less, even more preferably 60% or less, and more preferably 58% or less.

[0153] The content of (a2) the triol or higher ol type (preferably triol type) polypropylene glycol component in the total amount of the curable composition is not particularly limited, and a suitable lower limit is not particularly limited, but is preferably 10% or more, more preferably 15% or more, even more preferably 20% or more, and more preferably 23% or more. Also, a suitable upper limit is not particularly limited, but is preferably 70% or less, more preferably 65% ​​or less, even more preferably 60% or less, and more preferably 58% or less.

[0154] The content of the diol-type polypropylene glycol component (a3) ​​in the total amount of the curable composition is not particularly limited, and a suitable upper limit is not particularly limited, but is preferably 20% or less, more preferably 15% or less, even more preferably 10% or less, more preferably 5% or less, 3% or less, 1% or less, or 0.5% or less, and may be substantially zero (0.25%, 0.1%, 0.05% or less, 0%).

[0155] The content of the diisocyanate component (b1) in the total amount of the curable composition is not particularly limited, but a suitable lower limit is not particularly limited, but is preferably 0.5% or more, more preferably 1% or more, and even more preferably 1.5% or more, and a suitable upper limit is not particularly limited, but is preferably 20% or less, more preferably 18% or less, and even more preferably 15% or less.

[0156] The content of the diisocyanate group-terminated prepolymer (b1) in the total amount of the curable composition is not particularly limited, and a suitable lower limit is not particularly limited, but is preferably 2% or more, more preferably 2.5% or more, even more preferably 3% or more, more preferably 3.5% or more, and more preferably 4% or more; and a suitable upper limit is not particularly limited, but is preferably 20% or less, more preferably 18% or less, even more preferably 15% or less, and more preferably 14% or less.

[0157] As for optional components in the total amount of the curable composition, the contents described above in "2-3. Optional Components" can be appropriately adopted as desired.

[0158] 2-5. Characteristics of polyurethane adhesive composition

[0159] The adhesive composition according to the present embodiment may be a polyurethane adhesive composition since it contains the polyurethane resin as an adhesive component. The polyurethane adhesive composition can penetrate into the skin grooves and adhere to both the skin ridges and the skin grooves. The polyurethane adhesive composition has a large contact area with the skin, so it has good adhesiveness over the entire contact surface, is easy to apply to uneven body surfaces, and is resistant to peeling. The polyurethane adhesive composition has a sufficient adhesive area and good adhesiveness even on uneven body surfaces, so there is no need to set the adhesive strength high during design, and skin irritation can be reduced. The polyurethane adhesive composition is less likely to cause skin troubles even when applied to the skin for a long period of time. The polyurethane adhesive composition is less likely to damage the stratum corneum when peeled from the skin. Furthermore, the polyurethane adhesive composition is less likely to cohere and peel, so it is less likely to leave adhesive residue when peeled from the skin.

[0160] The adhesive strength (N) of the polyurethane adhesive composition is not particularly limited, but a suitable lower limit is, although not particularly limited, preferably 0.1 N or more, more preferably 0.5 N or more, and even more preferably 1.0 N or more; a suitable upper limit is, although not particularly limited, preferably 15.0 N or less, more preferably 12.0 N or less, and even more preferably 10.0 N or less; and a suitable numerical range is, although not particularly limited, preferably 0.1 to 15.0 N, more preferably 0.5 to 12.0 N, and even more preferably 1.0 to 10.0 N. The skin adhesive strength (N) of the polyurethane adhesive composition is not particularly limited, but a suitable lower limit is, but is not particularly limited, preferably 0.1 N or more, more preferably 0.2 N or more, and even more preferably 0.4 N or more; a suitable upper limit is, but is not particularly limited, preferably 16.0 N or less, more preferably 14.0 N or less, and even more preferably 12.0 N or less or 11.0 N or less; and a suitable numerical range is, but is not particularly limited, preferably 0.1 to 16.0 N, more preferably 0.2 to 14.0 N, and even more preferably 0.4 to 12.0 N. The ratio (100%) of [skin adhesion / adhesive strength] of the polyurethane adhesive composition is not particularly limited, but a suitable lower limit is, although not particularly limited, preferably 30% or more, more preferably 40% or more, and a suitable upper limit is, although not particularly limited, preferably 200% or less, more preferably 150% or less, and a suitable numerical range is, although not particularly limited, preferably 30 to 200%, and even more preferably 40 to 150%. Approaching or exceeding 100% has the advantage of providing good adhesion to skin, wounds or mucous membranes and causing less irritation thereto (for example, contact irritation, peeling irritation, etc.). The ratio (100%) of [(skin adhesion - adhesion) / adhesive strength] of the polyurethane adhesive composition is not particularly limited, but a suitable lower limit is not particularly limited, but is preferably -70% or more, more preferably -65% or more, and a suitable upper limit is not particularly limited, but is 60% or less, more preferably 50% or less, and a suitable numerical range is not particularly limited, but is more preferably -70% to 60%.

[0161] 2-6. Uses of Polyurethane Adhesive Composition The uses of the polyurethane adhesive composition according to this embodiment are not particularly limited, and may be, for example, one or more uses selected from skin, wounds, and mucous membranes. In this specification, "for skin, wounds, or mucous membranes" means that the composition has at least one use selected from skin, wounds, and mucous membranes. Therefore, the term "for skin, wounds, or mucous membranes" also includes, for example, a composition having two uses, such as skin and wounds, and a composition having three uses, such as skin, wounds, and mucous membranes. In this embodiment, the polyurethane adhesive composition described above may be used on skin, wounds, or mucous membranes.

[0162] The present embodiment can provide a mono-ol type polypropylene glycol component and an isocyanate component or use thereof, or a composition containing a mono-ol type polypropylene glycol component and an isocyanate component or use thereof, for producing or for use in producing a polyurethane adhesive composition (preferably for skin, wounds, or mucous membranes).

[0163] This embodiment may be a method for preventing, treating, or ameliorating skin diseases, wounds, or mucosal diseases using the above-described polyurethane adhesive composition containing an active ingredient. This embodiment may be used for either therapeutic or non-therapeutic purposes. In this embodiment, "prevention" refers to preventing or delaying the onset of symptoms or diseases in a subject, or reducing the risk of developing symptoms or diseases in a subject. In this embodiment, "amelioration" refers to improving or maintaining the disease, symptoms, or condition in a subject; preventing or delaying deterioration; or reversing, preventing, or delaying progression. "Treatment" encompasses not only complete cure of a disease, but also ameliorating symptoms.

[0164] 3. Patches

[0165] The polyurethane adhesive composition is suitable for adhesive materials for skin, etc. Therefore, the present invention can also provide an adhesive material for skin, etc., comprising the polyurethane adhesive composition for skin, etc.

[0166] The polyurethane adhesive composition used in the adhesive material for skin etc. according to one embodiment of the present invention is as explained in "2." above, and this explanation also applies to this embodiment.

[0167] The adhesive patch according to the present embodiment can be produced, for example, by a known method of combining a substrate and a pressure-sensitive adhesive to obtain a patch. The adhesive patch according to the present embodiment can be produced, for example, by at least performing the steps of dropping or applying a mixture containing the (A) polypropylene glycol component and the (B) isocyanate component onto the surface of the substrate, and curing the mixture. Alternatively, the adhesive patch according to the present embodiment can be produced, for example, by at least performing the steps of dropping or applying a mixture containing the (A) component and the (B) component onto the surface of a release material (release sheet), curing the mixture, and laminating a substrate to the pressure-sensitive adhesive surface after curing.

[0168] The adhesive material of the present embodiment may have a pressure-sensitive adhesive layer on at least one side of a substrate, or may have substrates on both sides of the pressure-sensitive adhesive layer, or one or both may be release materials.

[0169] As the substrate, a film, a foam (foam), a fiber substrate (nonwoven fabric, woven fabric, knitted fabric), etc. can be used. Of these, a film substrate is preferred from the viewpoints of flexibility, stretchability, appropriate water vapor permeability, bacterial barrier properties, ease of wiping off dirt, etc. Furthermore, in the case of a patch in the form of a roll or a tape-like patch, a film substrate, a fiber substrate, or a laminate thereof is preferred, and among these, when a fiber substrate is used, a nonwoven fabric is preferred because a uniform film layer is easily formed when melted.

[0170] The material of the film substrate or fiber substrate is not particularly limited, but examples thereof include thermoplastic resins. Examples of such materials include polyurethane, polyester (polyethylene terephthalate, polybutylene terephthalate, etc.), polyamide (nylon 6, nylon 66, etc.), polyethylene, polypropylene, acrylic polymers, and olefin copolymers. One or more selected from these materials can be used. Among these, polyethylene and PET are preferred.

[0171] When a film substrate is used, the thickness of the substrate is preferably 1 to 200 μm, more preferably 10 to 100 μm, and when a fiber substrate is used, the thickness is preferably 15 to 1000 μm, more preferably 20 to 500 μm.

[0172] The thickness of the adhesive layer composed of the adhesive composition is not particularly limited, but is, for example, 0.01 mm or more, preferably 0.015 to 5 mm, and more preferably 0.02 to 3 mm. The thickness of the adhesive material obtained by laminating a substrate and an adhesive layer is not particularly limited, but is, for example, 0.02 mm or more, preferably 0.03 to 5 mm, and more preferably 0.04 to 3 mm.

[0173] The shape of the patch may be selected appropriately depending on the intended use. Specific shapes include circles, ellipses, and polygons such as triangles, rectangles, and diamonds. Furthermore, these shapes may be combined appropriately, or the patch may be formed into a roll.

[0174] Examples of adhesive patches according to the present embodiment include wound dressings, surgical tapes, tapes for fixing catheters and infusion tubes, patches for fixing electrocardiogram electrodes and magnetic therapy devices, skin protective agents for ostomy appliances, patches (cataplasms and tapes), and patches for skin care and beauty. Among these, the adhesive patches according to the present embodiment are particularly suitable for skin protective compositions and wound dressings for ostomy appliances. Therefore, the present embodiment can also provide a skin protective agent for ostomy appliances containing the polyurethane adhesive composition for skin, etc., and a wound dressing containing the polyurethane adhesive composition for skin, etc. The present embodiment can also provide an ostomy appliance comprising at least the polyurethane adhesive composition described above, which may optionally comprise one or more components selected from a base plate having an opening for inserting a stoma, a pouch, and a discharge fitting. The polyurethane adhesive composition may be disposed on the surface of the base plate that comes into contact with the skin. It is also preferred that the base plate and the fitting are bonded to the pouch.

[0175] The present technology can be embodied in the following aspects. [1] A pressure-sensitive adhesive composition comprising at least a polyurethane that is a cured product of a composition comprising (a1) a mono-ol type polypropylene glycol component, and (b) an isocyanate component. Preferably, the composition further comprises (a) a polyol type polypropylene glycol component, more preferably (a2) a tri- or higher polyol type polypropylene glycol component. The cured product may be formed from the composition, and in this case, a polyurethane reaction is preferably used. The composition may be a curable composition. [2] The pressure-sensitive adhesive composition according to [1], wherein the weight-average molecular weight of the (a1) mono-ol type polypropylene glycol component is 3000 or more, and / or the weight-average molecular weight of the (a2) tri- or higher polyol type polypropylene glycol component is 2000 or more. [3] The pressure-sensitive adhesive composition according to [1] or [2], wherein the hydroxyl value (mg KOH / g) of the (a1) monool-type polypropylene glycol component is 25 or less and / or the hydroxyl value (mg KOH / g) of the (a2) tri- or higher polyol-type polypropylene glycol component is 85 or less. [4] The pressure-sensitive adhesive composition according to any one of [1] to [3], wherein the (b) isocyanate component is a diisocyanate component. The diisocyanate component is preferably a diisocyanate-terminated prepolymer, more preferably a diisocyanate-terminated prepolymer having both ends derived from the same or different aliphatic diisocyanate monomers. [5] The pressure-sensitive adhesive composition according to any one of [1] to [4], wherein the (b) isocyanate component has a weight-average molecular weight of 400 or more, 500 or more, or 600 or more. [6] The adhesive composition according to any one of [1] to [5] above, wherein the isocyanate group content (NCO%) of the (b) isocyanate component is 5 to 60%, 10 to 20%, or 10 to 18%. [7] The adhesive composition according to any one of [1] to [6] above, wherein the adhesive composition is for skin, wounds, or mucous membranes. [8] A patch comprising the polyurethane or adhesive composition according to any one of [1] to [7] above.[9] A polyurethane comprising at least (a1) a structural unit derived from a monool-type polypropylene glycol, and (b) a structural unit derived from an isocyanate component.

[10] A polyurethane comprising (a1) a structural unit derived from a monool-type polypropylene glycol, (a) a structural unit derived from a polyol-type polypropylene glycol, and (b) a structural unit derived from a diisocyanate component.

[11] The polyurethane according to

[10] above, wherein the component (a) comprises (a2) a structural unit derived from a tri- or higher polyol-type polypropylene glycol.

[12] A pressure-sensitive adhesive composition or adhesive material comprising the polyurethane according to any one of [9] to

[11] above.

[0176] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0177] I. Test Example 1 [Examples 1 to 13 and Comparative Examples 1 to 5]

[0178] Test pieces of Examples 1 to 13 and Comparative Examples 1 to 5 made of a polyurethane adhesive for skin, etc. were prepared using the following raw materials and according to the following preparation procedure.

[0179] [Manufacturing Procedure] The materials listed in the table (except the catalyst) were mixed by stirring for 2 minutes. Next, the catalyst was added, mixed by stirring for 2 minutes, and degassed. These mixtures were coated on release paper in an amount that would result in a predetermined thickness of adhesive layer after drying, and the mixture was dried by heating at 80°C for 10 minutes, followed by laminating a substrate to obtain a patch containing an adhesive composition. The thicknesses of the substrate and adhesive layer were as listed in the table. In the case of a mixture containing a hydrophilic component, the mixture was sandwiched between a polyethylene film substrate and release paper, passed through a roll gap so that the predetermined thickness of the adhesive layer after drying was obtained, and then dried by heating at 80°C for 10 minutes to obtain a patch containing an adhesive composition.

[0180] <Adhesive Strength (Peel Strength)> Adhesive strength is measured in accordance with JIS Z 0237 "180-degree peel adhesive strength." A test piece was prepared by cutting a piece 10 mm wide and 60 mm or longer from the tape of the example, and laminating a non-elastic tape to the substrate side of the tape. A 1.5 mm thick PET plate (made of polyethylene terephthalate) was used as the adherend. The surface of the PET plate was smooth. The test piece was attached to the PET plate and pressed with a 2 kg roller twice, and then the adhesive strength was measured 5 minutes later. The measurement was performed using a tensile tester (Shimadzu Corporation, EZ-SX) at a temperature of 23°C and humidity of 65%, at a pulling speed of 300 mm / min and a peel angle of 180°. The adhesive strength was defined as the average value over a 50 to 100 mm peel displacement range.

[0181] <Skin Adhesion (Peeling Force)> A test specimen was prepared by cutting a 10 mm wide, 60 mm long or longer piece from the example tape, and attaching a non-elastic tape to the substrate side of the tape. The test piece was the inner forearm of a person who had thoroughly wiped and dried the skin with ethanol. After applying the test piece to the inner forearm, the test piece was pressed with a 2 kg roller twice, and the adhesive strength was measured 120 minutes later. The measurement was performed using a tensile tester (Shimadzu Corporation, EZ-SX) at a temperature of 23°C and humidity of 65%, at a pulling speed of 300 mm / min and a peel angle of 180°. The adhesive strength to the skin was measured as the average value of the peel displacement from 50 to 100 mm.

[0182] <Comparative Evaluation of Skin Adhesion> The above-mentioned <Adhesive Strength (Peeling Strength)> and <Skin Adhesion Strength (Peeling Strength)> were compared to evaluate the degree to which the skin adhesive strength decreased or increased when the adhesive strength was used as a reference. The skin adhesive strength test was conducted on skin with minute irregularities, and the adhesive strength test was considered as the adhesive strength at the time of basic design. When the ratio of [Skin Adhesion Strength / Adhesive Strength] is low, it is necessary to set the adhesive strength higher to ensure sufficient adhesive strength when applied to the skin, taking into account the decrease in adhesive strength upon application to the skin. However, setting the adhesive strength higher in this way may increase skin irritation. Alternatively, when the ratio of [Skin Adhesion Strength / Adhesive Strength] is low, the adhesive strength may decrease significantly after application to the skin, leading to peeling from the skin. Furthermore, when the adhesive strength (smooth PET plate) is high, the ratio of [(Skin Adhesion Strength - Adhesive Strength) / Adhesive Strength] tends to have a higher negative increase / decrease rate (stronger negative), and skin irritation also tends to be higher. Furthermore, when the skin adhesive strength is high, the rate of increase or decrease increases in the positive direction, preferably becomes positive, and it is therefore considered that the contact area increases while skin irritation is suppressed.

[0183] <Ratio (%) of Skin Adhesion to Adhesive Strength> Ratio (%) of Skin Adhesion to Adhesive Strength = [Skin Adhesion Strength / Adhesive Strength] × 100 The pass standard for the ratio (%) of Skin Adhesion to Adhesive Strength was set to 30% or more.

[0184] <Increase / Decrease Rate (%) of Skin Adhesion to Adhesive Force> Increase / Decrease Rate (%) of Skin Adhesion to Adhesive Force = [(Skin Adhesion - Adhesive Force) / Adhesive Force] x 100

[0185] (1) Raw materials

[0186] <Diisocyanate Reactant (Diisocyanate-Terminated Prepolymers 1-3)> <Diisocyanate-Terminated Prepolymer 1> The following raw polyol and raw diisocyanate were mixed and subjected to a thermal curing reaction to obtain diisocyanate-terminated prepolymer 1. Specifically, the polyol and the diisocyanate were subjected to a thermal curing reaction (80°C for 10 minutes) in the absence of a solvent so that the [NCO / OH] ratio was 1.0 or less, thereby obtaining isocyanate-terminated prepolymer 1. Since this prepolymer is an isocyanate-terminated prepolymer having NCO groups at at least both ends, it is also referred to as a "diisocyanate reactant." <Method for Calculating the [NCO / OH] Ratio> The [NCO / OH] ratio is calculated using the following formula. [NCO / OH] = (compound ratio of component (A) ÷ NCO equivalent of component (A)) ÷ (compound ratio of component (B) ÷ OH equivalent of component (B)) The NCO equivalent of the (A) isocyanate component is calculated by: NCO equivalent of (A) = molecular weight of NCO (42) ÷ NCO content of A (%) The OH equivalent of the (B) polyol component is calculated by: OH equivalent of (B) = molecular weight of KOH (56.1 ÷ (hydroxyl value of (B) (unit is mgKOH / g, so divide the hydroxyl value by 1000) ÷ 1000)

[0187] The following raw materials were used in the table. <Isocyanate> <Diisocyanate-Terminated Prepolymer 1> Diisocyanate-terminated prepolymer 1 was an isocyanate-terminated prepolymer (isocyanate group content 12.8%, Covestro), which is an aliphatic polyisocyanate-based prepolymer. The aliphatic polyisocyanate contained HDI. The weight-average molecular weight of diisocyanate-terminated prepolymer 1 according to GPC analysis was 656.

[0188] <Diisocyanate Group-Terminated Prepolymer 2> For diisocyanate group-terminated prepolymer 2, a diisocyanate-terminated prepolymer (isocyanate group content 11.2%; Tosoh Corporation), which is an HDI-based polyisocyanate-modified product, was used. GPC analysis of diisocyanate group-terminated prepolymer 2 revealed that it had a weight-average molecular weight of 1,366. Note that prepolymer 2 can also be obtained by subjecting the polyol and the diisocyanate to a thermal curing reaction (80°C for 10 minutes) in the absence of a solvent so that the [NCO / OH] ratio becomes 0.5 to 1.5.

[0189] <Diisocyanate Group-Terminated Prepolymer 3> Diisocyanate group-terminated prepolymer 3 was a diisocyanate-terminated prepolymer (isocyanate group content 19.5%; Tosoh Corporation), which is an HDI-based polyisocyanate-modified product. GPC analysis of diisocyanate group-terminated prepolymer 3 revealed that it had a weight-average molecular weight of 431. Note that prepolymer 3 can also be obtained by subjecting the polyol and the diisocyanate to a thermal curing reaction (80°C for 10 minutes) in the absence of a solvent so that the [NCO / OH] ratio becomes 0.5 to 1.5.

[0190] <Isocyanate Oligomer> HDI trimer (isocyanate group content 21.6%; Tosoh Corporation) having a polyisocyanurate structure and three NCO terminals was used. The weight average molecular weight of the HDI trimer was 680 according to GPC analysis. <Diisocyanate Monomer> HDI (diisocyanate monomer / two NCO terminals) (isocyanate group content 50%; Tosoh Corporation) was used. The weight average molecular weight of the HDI was 168 according to GPC analysis.

[0191] <Polypropylene glycol triol type> The following polypropylene glycol triols were used for the polypropylene glycol triol type. Polypropylene glycol triol type 1: Hydroxyl value 55.7 (mgKOH / g); weight average molecular weight by GPC analysis: approximately 3,000. Polypropylene glycol triol type 2: Hydroxyl value 34.4 (mgKOH / g); weight average molecular weight by GPC analysis: approximately 4,900. Polypropylene glycol triol type 3: Hydroxyl value 18.3 (mgKOH / g); weight average molecular weight by GPC analysis: approximately 9,200.

[0192] <Polypropylene glycol diol type> The following polypropylene diol was used as the polypropylene glycol diol type: Polypropylene glycol diol type: Hydroxyl value: 29.3 (mgKOH / g); weight average molecular weight by GPC analysis: about 3,800.

[0193] <Polypropylene glycol mono-type> A polypropylene glycol mono-ol type having a hydroxyl value of 11.2 (mgKOH / g) was used. The R moiety (R in the formula (1)) is an alkyl group. The weight average molecular weight by GPC analysis was about 5,000.

[0194] <Skin care ingredients> ・Ceramide 2 (Takasago International Corporation's "Ceramide 2")

[0195] <Hydrophilic component> A mixture of the following three components was used as the hydrophilic component: sodium carboxymethylcellulose ("Sunrose" manufactured by Nippon Paper Industries Co., Ltd.), pectin ("Genupectin" manufactured by Sansho Co., Ltd.), and sodium polyacrylate ("Junron" manufactured by Toagosei Co., Ltd.).

[0196] <Catalyst> Metal carboxylate ("Borchi Kat" manufactured by Borchers)

[0197] <Base material> PE: polyethylene PU: polyurethane PET: polyethylene terephthalate

[0198]

[0199]

[0200]

[0201] The results shown in Tables 1 to 3 reveal the following: In the examples, the ratio [skin adhesive strength / adhesive strength] remains at approximately 40% or more, meaning that adhesive strength, which is a basic adhesive property, is maintained to a certain extent even when the adherend is skin. In the comparative examples, the ratio [skin adhesive strength / adhesive strength] falls to approximately 25% or less, meaning that adhesive strength, which is a basic adhesive property, drops sharply when the adherend is skin. Furthermore, with respect to [(skin adhesive strength - adhesive strength) / adhesive strength], when the smooth adhesive strength is high, the negative rate of increase / decrease becomes larger (stronger) and skin irritation increases, while when the skin adhesive strength is high, the rate of increase / decrease increases in the positive direction, preferably to a positive value, suggesting that skin irritation is suppressed while the contact area increases.

[0202] Furthermore, considering Examples 1 to 9, it was considered preferable to use at least a mono-ol type polypropylene glycol component, and to combine a mono-ol type with a triol type. Furthermore, considering Examples 1 and 10 to 13, it was preferable to combine, as the polyisocyanate component, diisocyanate group-terminated prepolymers 1 to 3, diisocyanate monomers, and isocyanate oligomers with a mono-ol type polypropylene glycol component, and among these, polyisocyanate components having two NCO terminals (diisocyanate group-terminated prepolymers 1 to 3, diisocyanate components of diisocyanate monomers) were preferred, and diisocyanate group-terminated prepolymers were more preferred.

[0203] Therefore, taking into consideration Examples 1 to 9 and Comparative Examples 1 to 5, by using a mono-ol type polypropylene glycol component, more preferably a polyurethane that uses a mono-ol type polypropylene glycol component and an isocyanate component in combination, and an adhesive composition containing the polyurethane, it was possible to provide an adhesive composition that has good adhesiveness while causing little irritation to the area that comes into contact with the adhesive.

[0204] In the case of conventional polyurethane adhesives, those with a low ratio of skin adhesion to adhesive strength will experience a significant decrease in adhesive strength when applied to the skin. Taking this into consideration, the basic adhesive design was to set high adhesive strength by using adhesives with high polarity and intermolecular forces. This results in high adhesion at the interface between the skin and the adhesive, potentially increasing skin irritation. If the adhesive strength is set low to reduce irritation, this could lead to peeling. Thus, adjusting skin adhesion is extremely difficult.

[0205] In contrast, the polyurethane adhesive composition of the present invention has been prepared by focusing on achieving both wettability and cohesiveness, and therefore penetrates into the micro-irregularities of the skin and ensures a sufficient adhesive area, thereby allowing the composition to firmly adhere to the skin even though the adhesive strength at the skin interface is low, without cohesive failure (leaving no adhesive residue), and since the basic adhesive strength does not need to be set high, it is also less irritating to the skin. Thus, rather than focusing on adjusting the skin adhesive strength of conventional polyurethane adhesive compositions, the present inventors have reviewed the polyurethane resin raw materials to achieve the physical properties characteristic of polyurethane adhesive compositions, obtained a new polyurethane, and by using this in the composition, have been able to provide a new polyurethane adhesive composition that demonstrates extremely excellent effects.

[0206] Furthermore, even if conventional adhesive compositions are applied to a recipient (e.g., skin) underwater, they peel off from the recipient when removed from the water. However, the adhesive composition of the present invention did not peel off from the recipient even when applied to a recipient underwater and removed from the water. Furthermore, adhesives that can maintain their adhesion even when immersed in water while still adhering to skin have been known, but the adhesive composition of the present invention was able to adhere to the contact area of ​​a wetted recipient. Furthermore, when the recipient applied the adhesive composition of the present invention, the tape coated with the adhesive composition was less likely to become distorted in shape, and was able to adhere to the contact area while maintaining its tape shape and cohesiveness.

[0207] Furthermore, the adhesive composition of the present invention was able to maintain its adhesiveness to the adherend even after repositioning in water. The adhesive article of the present invention was able to maintain its adhesiveness to the adherend even without wiping off the water after being taken out of water. Furthermore, repositioning was possible even when the adhesive composition of the present invention did not contain a predetermined amount of hydrophilic component.

[0208] The adhesive composition of the present invention has overall soft properties, and therefore maintains its overall softness even when blended with powders such as hydrophilic components. Furthermore, by using the polyurethane resin of the present invention in, for example, an adhesive composition or a patch containing the same, the adhesive composition can exhibit a pH adjusting function in a short period of time. Furthermore, in general adhesive compositions, the performance of the adhesive composition is improved or enhanced by adding a plasticizer. However, the adhesive composition of the present invention was able to maintain its adhesiveness without the use of a plasticizer. Furthermore, the present invention also possessed water resistance and water sealing properties.

[0209] Thus, the polyurethane of the present invention and the adhesive composition containing it have various advantages in addition to having good adhesiveness and causing little irritation to the skin.

Claims

1. An adhesive composition comprising at least a polyurethane that is a cured product of a composition containing a mono-ol type polypropylene glycol component and an isocyanate component.

2. The adhesive composition according to claim 1, wherein the composition further comprises a tri- or higher polyol type polypropylene glycol component.

3. The adhesive composition according to claim 1, wherein the mono-ol type polypropylene glycol component has a hydroxyl value (mgKOH / g) of 25 or less.

4. The adhesive composition described in claim 2, wherein the hydroxyl value (mg KOH / g) of the monool-type polypropylene glycol component is 25 or less, and / or the hydroxyl value (mg KOH / g) of the tri- or higher polyol-type polypropylene glycol component is 85 or less.

5. The adhesive composition according to claim 1 or 2, wherein the isocyanate component is a diisocyanate component.

6. The adhesive composition according to claim 1 or 2, which is for use on skin, wounds, or mucous membranes.

7. A patch comprising the adhesive composition according to claim 1 or 2.

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