JP6680111B2 - Pressure sensitive adhesive and adhesive sheet - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a pressure-sensitive adhesive which is preferably used for sticking to the skin, a method for producing the same, a pressure-sensitive adhesive sheet using the same, and a medical laminate. More specifically, when it is applied to the skin surface using an adhesive sheet, it has conformability to the skin surface (flexibility), and has good drug stability in the adhesive layer and drug release from the adhesive layer, Further, the present invention relates to a pressure-sensitive adhesive that can be used for medical purposes, has no stuffiness or rash during application, and does not cause contamination of the skin or exfoliation of keratin when peeling, a method for producing the same, and an adhesive sheet using the same.

  BACKGROUND ART Conventionally, in the medical field and the like, patches that are directly applied to the skin have been frequently used. A patch that is directly applied to the skin generally has a structure in which a pressure-sensitive adhesive mixed with a drug or the like is applied to one side of a base material made of non-woven fabric, paper, a plastic sheet or the like. For example, in the case of a patch-type transdermal absorption preparation that is applied to the skin for the purpose of administering a drug into the body through the skin (for example, a transdermal absorption sheet preparation), it has sufficient adhesive force when sticking to the skin, In addition, it is required to have the property of being able to be peeled and removed after use without contamination of the skin surface (residual residue, stickiness, etc.) or damage to the skin (peeling of keratin, stuffiness or rash).

Adhesive transdermal preparations need to be firmly fixed to the skin surface in order to improve drug transfer to the skin, but if the adhesive strength to the skin is too large, the preparation will peel off from the skin surface after use. It causes pain and exfoliation due to physical irritation, and sometimes causes significant skin irritation, which often causes dermatitis. In addition, a transdermal absorption preparation may be used in combination with a transdermal absorption enhancer in order to administer the drug transdermally. In general, many transdermal absorption enhancers are in liquid form, and it is possible to enhance the penetration of the drug into the skin by including a large amount of a liquid component as an absorption enhancer in the adhesive layer. Has become. However, if the content of the liquid component in the adhesive layer is increased, the cohesive force required as a characteristic of the percutaneous absorption preparation will be low, and not only the fixing of the skin surface as described above will be insufficient but also peeling In some cases, adhesive residue will occur. Further, when the patch is used for a long period of time, if the water vapor permeability or the water absorbency of the adhesive layer is poor, the skin will become damp, stuffy, or the skin will be damaged.
The pressure-sensitive adhesive used as a method for maintaining removability by suppressing the decrease in cohesive strength of the adhesive layer, maintaining adhesive strength to the skin, or suppressing damage to the skin during peeling or long-term application. Various attempts have been made in the past.

  Acrylic resins and rubber resins are often used as pressure-sensitive adhesives used in patches, and silicone resins are used depending on the affected area. To these resins, generally, a suitable amount of rosin, rosin ester, or a tackifier (also known as tackifier) composed of a synthetic hydrocarbon resin, and a compounding agent such as a plasticizer and a stabilizer is added, While it is easy to control the characteristics, the compatibility with liquid components such as chemicals is insufficient, so the adhesive strength may decrease or the internal cohesive force may be insufficient depending on the compounding ratio, causing the adherend to adhere during use or peeling. Adhesive residue of pressure sensitive adhesive on certain skin surfaces is produced. Further, since the compounding agent is a low molecular weight component, it is strongly stimulated by these chemical components, penetrates into the skin and causes inflammation. Further, since it has high hydrophobicity, it has poor water absorbency and water vapor permeability, and there is a problem that the skin is easily damaged such as stuffiness, swelling, or rash.

  Therefore, a pressure-sensitive adhesive is disclosed in which an acrylic ester resin is mixed with a liquid component having good compatibility (a drug, a compounding agent, etc.) and metal cross-linking is performed (see Patent Document 1). Since this pressure-sensitive adhesive can contain a large amount of liquid components, it is possible to balance adhesive strength and removability as compared with conventional non-crosslinked pressure-sensitive adhesives. Unreacted acrylic acid remaining in the resin causes a great deal of damage to the skin, and the water vapor permeability of the resin is poor, causing damage to the skin such as stuffiness, swelling, or rashes.

  Further, in recent years, in order to compensate for these drawbacks, a pressure-sensitive adhesive obtained by mixing an alkylene oxide compound having a hydroxyl group with a polyurethane resin (see Patent Document 2) or a polyether urethane resin having an increased hydroxyl group concentration is used. A pressure sensitive adhesive has been disclosed (see Patent Document 3). However, the improvement of water vapor permeability and water absorption suppresses damage such as stuffiness, swelling, or rash on the skin, but due to lack of internal cohesive force, the adhesive force is too high, or the skin to be adhered when peeled off. There is a problem in removability, such as adhesive residue on the surface of the pressure-sensitive adhesive.

  In addition, a pressure-sensitive adhesive containing a biocompatible tackifying resin and a plasticizer in a polyurethane resin is disclosed (see Patent Document 4). However, the polyurethane resin used for this pressure-sensitive adhesive has a problem that it is difficult to suppress damage to the skin because it is made of a catalyst having cytotoxicity.

  In view of such a situation, adhesion to the skin (adhesion), conformability to the skin surface (flexibility), drug stability in the adhesive layer, drug release from the adhesive layer, stuffiness during application, There is no swelling or rash, and when peeling the transdermal absorbable adhesive sheet, it satisfies various characteristics such as maintaining re-peeling property that does not contaminate the skin and does not peel keratin, but pressure sensitive adhesive is desired. It was

JP, 03-220120, A JP, 11-290444, A JP, 07-310066, A JP, 2014-522259, A

  The problem to be solved by the present invention is to solve the above problems, when used in an adhesive sheet, the ability to retain a transdermal absorption enhancer, the adhesiveness to the skin, and the release performance of the transdermal drug. (EN) Provided is a pressure-sensitive adhesive which is excellent in skin irritation and is capable of forming a percutaneously absorbable adhesive sheet which is not irritating to the skin and does not leave a pressure-sensitive adhesive on the skin when peeled from the skin.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned object can be achieved by the pressure-sensitive adhesive shown below, and have completed the present invention.

That is, an embodiment of the present invention is a pressure-sensitive adhesive containing a polyurethane urea resin (A) and a reactive compound (B) having a functional group capable of reacting with a hydroxyl group,
As a monomer unit constituting the polyurethane urea resin (A), a polyol (a1) unit, a polyisocyanate (a2) unit and an amine compound (a3) unit are contained,
The polyurethane urea resin (A) has no aromatic ring, has an alkylene oxide unit and a hydroxyl group in its side chain, and has a weight average molecular weight of 10,000 to 500,000,
It is a pressure-sensitive adhesive containing 0.1 to 50 parts by weight of a reactive compound (B) having a functional group capable of reacting with a hydroxyl group with respect to 100 parts by weight of a polyurethane urea resin (A).

In addition, the embodiment of the present invention is based on a total of 100% by weight of the monomer units constituting the polyurethane urea resin (A),
45 to 94% by weight of the polyol (a1) unit,
5 to 30% by weight of polyisocyanate (a2) unit,
Amine compound (a3) unit is 1 to 25% by weight
The pressure-sensitive adhesive is included.

  Further, an embodiment of the present invention is the above pressure-sensitive adhesive, in which the polyol (a1) contains a polyether diol having no aromatic ring.

  Further, in the embodiment of the present invention, the content of the alkylene oxide unit in the polyurethane urea resin (A) is 25 to 80% by weight, and the pressure-sensitive formula according to any one of claims 1 to 3, It is an adhesive.

  Also, an embodiment of the present invention is the above pressure-sensitive adhesive, wherein the amine compound (a3) contains a diamine compound (a3-1) having two iminopropionic acid ester structures.

  Further, an embodiment of the present invention is the pressure-sensitive adhesive, wherein the diamine compound (a3-1) having two iminopropionic acid ester structures has a hydroxyl group.

  Further, an embodiment of the present invention is the above pressure-sensitive adhesive, wherein the amine compound (a3-1) having two iminopropionic acid ester structures has an alkylene oxide unit having a hydroxyl group or an alkoxy group at a terminal.

  Further, an embodiment of the present invention is the pressure-sensitive adhesive, wherein the reactive compound (B) contains the polyisocyanate (b1).

  Further, an embodiment of the present invention is the above pressure-sensitive adhesive which further contains an ester compound (C).

  Further, an embodiment of the present invention is the pressure-sensitive adhesive as described above, further containing at least one of the transdermal drug (d1) and the transdermal absorption enhancer (d2).

  Further, an embodiment of the present invention is an adhesive sheet in which an adhesive layer formed of the pressure-sensitive adhesive is laminated on at least one surface of the base material (G).

Further, in the embodiment of the present invention, the urethane prepolymer (X) obtained by reacting the polyol (a1) and the polyisocyanate (a2) has a diamine compound (a3-1) having two iminopropionic acid ester structures. The first step of producing a urethane urea resin (Y) having an isocyanate group at the end by reacting
The urethane urea resin (Y) is reacted with the reaction-terminating amine compound (a3-2-1) to have an alkylene oxide bond group and a hydroxyl group in the side chain and having a weight average molecular weight of 10,000 to 500,000. The second step of producing the polyurethane urea resin (A),
And a third step of mixing 0.1 to 50 parts by weight of the reactive compound (B) having a functional group capable of reacting with a hydroxyl group with 100 parts by weight of the polyurethane urea resin (A). This is a method for producing a pressure-sensitive adhesive.

  By using the pressure-sensitive adhesive of the present invention, it has excellent performance of holding a percutaneous absorption enhancer in a state before being attached to the skin, is hypoallergenic to the skin, has adhesiveness to the skin, and percutaneous absorption. It has become possible to provide a percutaneously absorbable adhesive sheet which is excellent in the release performance of a sexual drug and does not leave a pressure-sensitive adhesive on the skin when peeled from the skin.

Hereinafter, embodiments of the present invention will be described.
The pressure-sensitive adhesive of the present invention is a pressure-sensitive adhesive containing 0.1 to 50 parts by weight of a reactive compound (B) having a functional group capable of reacting with the hydroxyl group, relative to 100 parts by weight of a polyurethane urea resin (A). The feature is that it is an adhesive. The components of the pressure sensitive adhesive will be specifically described below.

<Polyurethane urea resin (A)>
The polyurethane urea resin (A) is a resin containing, as constituent monomer units, a polyol (a1) unit, a polyisocyanate (a2) unit and an amine compound (a3) unit, and these monomer mixtures are polymerized. It is a resin manufactured by

The components of the pressure sensitive adhesive will be specifically described below.
<< Polyol (a1) >>
First, the polyol (a1) unit, which is a monomer unit constituting the polyurethane urea resin (A), will be described.
The polyol (a1) is a compound having two or more hydroxyl groups in its structure, a low molecular weight polyol (a1-1) and a polyether polyol (a1-2) having a repeating unit having a degree of polymerization of 2 or more. ), Polyester polyols (a1-3), polyamide polyols (a1-4), polycarbonate polyols (a1-5), and other polyols other than (a1-1) to (a1-5) ( a1-6) and the like.

Among the polyols (a1), the low molecular weight polyols (a1-1) are the minimum units constituting the polyols (a1-2) to (a1-6) having a repeating unit having a polymerization degree of 2 or more, which will be described later. It is a compound that can be a monomer.
As the low molecular weight polyols (a1-1), known polyols can be used, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-butyl -3-ethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl -1,3-hexanediol, 3,3'-dimethylolheptane, 1, 8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-tetracosanediol, 1,6-tetra Aliphatic diols such as cosandiol, 1,4-hexacosanediol, 1,6-octacosanediol;

  For example, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, tricyclodecanediethanol, cyclopentadienedimethanol, 2,5-norbornanediol, 1,3-adamantanediol, dimerdiol. Alicyclic diols such as;

  For example, o-, m-, and p-dihydroxybenzene, 1,2-indanediol, benzene-1,2-dimethanol (alias: phthalyl alcohol), benzene-1,3-dimethanol (alias: isophthalyl) Alcohol), benzene-1,4-dimethanol (also known as terephthalyl alcohol), 1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-Hydroxyethoxy) benzene, (3,4-dihydroxyphenyl) methanol (alias: protocatechuyl alcohol), (4-hydroxy-3-methoxyphenyl) methanol (alias: vanillyl alcohol), 2- (4- Hydroxy-3-methoxyphenyl) ethan-1-ol (also known as homovanillyl alcohol), 3 (4-Hydroxy-3-methoxyphenyl) prop-2-en-1-ol (also known as coniferyl alcohol), 3- (4-hydroxy-3,5-dimethoxyphenyl) prop-2-en-1-ol (Alias: synapyl alcohol), 1,2-diphenylethane-1,2-diol (alias: hydrobenzoin), hydroquinone, resorcin, 4-chlororesorcin, 4-methylresorcin, 5-methylbenzene-1,3- Diol (alias: orcinol), 2-methylbenzene-1,4-diol (alias: tolhydroquinone), 2,3-dimethylbenzene-1,4-diol (alias: o-xylohydroquinone), 2,6-dimethyl Benzene-1,4-diol (alias: m-xylohydroquinone), 2,5-dimethylbenzene-1,4-di (Other name: p-xylohydroquinone), 2,3,5-trimethylbenzene-1,4-diol (other name: pseudocumohydroquinone), 2-isopropyl-5-methylbenzene-1,4-diol (other name) : Thymohydroquinone), 2,3,5,6-tetramethylbenzene-1,4-diol (alias: jurohydroquinone), 5-pentylbenzene-1,3-diol (alias: olivetol), 4,4′- Methylenediphenol (also known as p, p-bisphenol F), 4,4 '-(2-norbornylidene) diphenol, 4,4'-dihydroxymethylbiphenyl, 4,4'-biphenyldiol, 2,3-dihydroxybutene Phenyl, tetranitrobiphenyl diol, 5,5'-dipropyl-biphenyl-2,2'-diol, 3,3'-dia Minobiphenyl-4,4'-diol, 5,5'-tetramethylbiphenyl-4,4'-diol, diphenylsilanediol, (E) -4,4 '-(hex-3-ene-3,4- Diyl) diphenol (alias: diethylstilbestrol), 2,2-bis (4-hydroxyphenyl) sulfone (alias: bisphenol S), 4,4'-isopropylidenephenol, 4,4'-dihydroxydiphenyl ether (alias) : 4,4′-oxydiphenol), 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A), 1,3-naphthalene diol, 1,5-naphthalene diol, 1,7-naphthalene diol , 1,7-dihydroxymethylnaphthalene, 1,4-dihydroxy-2-naphthalene ammonium sulfonate, Aromatic diols such as 9,9′-bis (4-hydroxyphenyl) fluorene and 9,9′-bis (3-methyl-4-hydroxyphenyl) fluorene 1,4-dihydro-9,10-anthracenediol Can be mentioned.

Here, the dimer diol is an unsaturated fatty acid such as linoleic acid, oleic acid and linolenic acid, a carboxylic acid having 18 carbon atoms such as a dry oil fatty acid or a semi-dry oil fatty acid obtained from tall oil, cottonseed oil, soybean oil and the like. Is a 36-carbon aliphatic diol obtained by further completely hydrogenating a dimer acid obtained by thermal polymerization of a dimer acid, and is obtained as a mixture of geometric isomers of a dimer diol having a branched structure or a cyclohexane ring. It is a compound. Examples of commercially available products include PRIPOL-2030 and 2033 (manufactured by CRODA Coating & Polymers) and Sovermol-908 (manufactured by BASF).
The term "aliphatic" used herein means an acyclic carbon compound, and a cyclic carbon compound having no aromatic ring is defined as an alicyclic group.

  The formula weight (Mn, also referred to as number average molecular weight) of the low molecular weight polyols (a1-1) is preferably 50 to 1,000, more preferably 60 to 800. When the formula weight (Mn) is in this range, pseudo-crystals of the polyether polyol (a1-2), polyester polyol (a1-3), polyamide polyol (a1-4), or polycarbonate polyol (a1-5) described later. Since the properties are lost, the viscosity of the polyurethane urea resin can be reduced and the coating processability becomes good. In addition, since the flexibility is further increased, tackiness (tack) and conformability to the skin are easily exhibited. As the formula weight (Mn), the literature value described in the Chemical Handbook, Basic Edition, Revised 5th Edition (2004, Chemical Society of Japan) and the like was used.

  Among these, aliphatic diols having an alkyl group in the side chain among aliphatic diols and alicyclic diols, in view of the fact that flexibility can be imparted along with the reduction of density in order to improve the ability to follow the skin. And alicyclic diols are preferably used in combination, and for example, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, neopentyl glycol, 2,4- Particularly preferred are diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,12-dodecanediol and dimerdiol.

  As the polyether polyols (a1-2), known polyether polyols can be used. The polyether polyols (a1-2) are polyoxyalkylene polyols obtained by ring-opening addition polymerization of alkylene oxide with an initiator having 2 to 4 active hydrogen atoms. Examples of the initiator include the above-mentioned short chain polyols (a1-1) and aliphatic amines (for example, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, alkylenediamine such as neopentyldiamine, monoethanolamine, and the like. Examples thereof include alkanolamines such as diethanolamine). In consideration of the skin-following property of the pressure-sensitive adhesive, the water vapor permeability, the compatibility with the drug (D) described later, etc., the above-mentioned low molecular weight polyols (a1 It is particularly preferable to use the aliphatic diols described in -1) as an initiator to prepare a polyether diol. These may be used alone or in combination of two or more.

Examples of the alkylene oxide include those having a polyoxyalkylene skeleton obtained by ring-opening addition polymerization of ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, oxetane, tetrahydrofuran and the like.
Examples of the polyether polyol having an alkylene oxide skeleton include polyethylene glycol, polyethylene propylene glycol (ethylene oxide / propylene oxide copolymer), polyethylene tetramethylene glycol (ethylene oxide / tetramethylene oxide copolymer), polypropylene glycol, and poly (ethylene glycol). Tetramethylene glycol, alkyl polyalkylene glycol obtained by ring-opening polymerization of alkylene oxide using the above low molecular weight polyols (a1-1), cycloalkyl polyalkylene glycol, or bisphenols such as bisphenol A and bisphenol F with ethylene oxide ( Abbreviation: EO), propylene oxide (abbreviation: PO) and other aromatic rings formed by addition of alkylene oxides Polyarylalkylenes glycol having like.

Among these, considering water absorbency and water vapor permeability, it is preferable to use polyetherol having an ethylene oxide skeleton or a propylene oxide skeleton. When the polyurethane urea resin (A) has an ethylene oxide skeleton or a propylene oxide skeleton, sufficient water vapor permeability can be imparted to the produced adhesive film. It is possible to prevent damage. Further, since the compatibility with the drug (D) described later becomes high, it becomes possible to control the sustained release property of the drug (D) from the adhesive film. It is particularly preferable to have an ethylene oxide skeleton that is effective in preventing skin damage in addition to maintaining water vapor permeability and water absorption.
As such a polyether polyol having an ethylene oxide skeleton, for example, polyethylene glycol, polyethylene propylene glycol (ethylene oxide / propylene oxide copolymer), polyethylene tetramethylene glycol (ethylene oxide / tetramethylene oxide copolymer), Examples thereof include alkyl polyethylene glycols and cycloalkyl polyethylene glycols obtained by ring-opening polymerization of ethylene oxide using the low molecular weight polyols (a1-1) as an initiator, and preferably have no aromatic ring. These ethylene oxide skeletons are preferably contained in at least 3 to 80% by weight in 100% by weight of the polyether polyol having an ethylene oxide skeleton. When the ethylene oxide skeleton is in the above range, when used as a pressure-sensitive adhesive, it exhibits favorable water vapor permeability and water absorption, and the whitening of the adhesive layer and water resistance are favorable, which is preferable.

  As the polyether polyols (a1-2), commercially available products may be used, and for example, PEG400 (Mn = 400, hydroxyl value = 275, acid value <0.5, linear liquid type), PEG600 (Mn = 600, hydroxyl group). Value = 180, acid value <0.5, linear liquid type), PEG1000 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear wax type), PEG2000 (Mn = 2,000, Hydroxyl value = 56, acid value <0.5, linear wax type), PEG4000N (Mn = 3,000, hydroxyl value = 37, acid value <0.5, linear wax type), PEG10000 (Mn = 10, 000, hydroxyl value = 11, acid value <0.5, linear solid type), Newpol PP-400 (Mn = 400, hydroxyl value = 275, acid value <0.5, linear liquid tie ), Newpol PP-1000 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type), Newpol PP-2000 (Mn = 2,000, hydroxyl value = 56, acid) Value <0.5, linear liquid type), Newpol PP-4000 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid type), Newpol 50HB-260 (Mn = 880, Hydroxyl value = 128, acid value <0.5, linear liquid type), Newpol 50HB-400 (Mn = 1,340, hydroxyl value = 84, acid value <0.5, linear liquid type), Newpol 50HB- 660 (Mn = 1,800, hydroxyl value = 62, acid value <0.5, linear liquid type), Newpol 50HB-2000 (Mn = 2,300, hydroxyl value = 49, acid value <0.5, linear) liquid Type), Primepol FF-3550 (Mn = 5,000, hydroxyl value = 34, acid value <0.5, linear liquid trifunctional type), Primepol FF-3320 (Mn = 3,000, hydroxyl value =) 56, acid value <0.5, linear liquid trifunctional type), Primepol FH-2200 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type), Primepol PX-1000 (Mn = 1,000, hydroxyl value = 115, acid value <0.5, linear liquid type) [above, Sanyo Chemical Industry Co., Ltd.];

  Adeka polyether P-700 (Mn = 700, hydroxyl value = 270, acid value <0.1, linear liquid type), Adeka polyether P-1000 (Mn = 1,000, hydroxyl value = 110, acid value <0 .1, linear liquid type), Adeka polyether P-2000 (Mn = 2,000, hydroxyl value = 56, acid value <0.1, linear liquid type), Adeca polyether P-3000 (Mn = 3,000) , Hydroxyl value = 37, acid value <0.1, linear liquid type), Adeca polyether BPX-1000 (Mn = 1,000, hydroxyl value = 113, acid value <0.1, aromatic ring-containing linear liquid type) , ADEKA polyether BPX-2000 (Mn = 2,000, hydroxyl value = 56, acid value <0.1, aromatic ring-containing linear liquid type) [above, manufactured by ADEKA];

  EXCENOL 420 (Mn = 400, hydroxyl value = 280, acid value <0.03, linear liquid type), EXCENOL 720 (Mn = 700, hydroxyl value = 160, acid value <0.03, linear liquid type), EXCENOL 1020 (Mn = 1,000, hydroxyl value = 112, acid value <0.05, linear liquid type), EXCENOL 2020 (Mn = 2,000, hydroxyl value = 56, acid value <0.05, linear liquid type), EXCENOL 3020 (Mn = 3,200, hydroxyl value = 35, acid value <0.03, linear liquid type), EXCENOL 3021 (Mn = 3,300, hydroxyl value = 34, acid value <0.03, linear liquid type) ), EXCENOL 510 (Mn = 4,000, hydroxyl value = 28, acid value <0.05, linear liquid type), EXCENOL 530 (M = 3,000, hydroxyl value = 37, acid value <0.05, linear liquid type), EXCENOL 540 (Mn = 2,000, hydroxyl value = 56, acid value <0.05, linear liquid type) [above, Asahi Glass Co., Ltd.];

  PTG 1000 (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear wax type), PTG 2000 (Mn = 2,000, hydroxyl value = 56, acid value <0.05, linear wax) Type), PTG 3000 (Mn = 3,000, hydroxyl value = 36, acid value <0.05, linear wax type) [above, Hodogaya Chemical Co., Ltd.];

  PTMG850 (Mn = 850, hydroxyl value = 130, acid value <0.05, linear liquid type), PTMG1000 (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear wax type), PTMG1500 (Mn = 1,500, hydroxyl value = 75, acid value <0.05, linear wax type), PTMG1800 (Mn = 1,800, hydroxyl value = 62, acid value <0.05, linear wax type) , PTMG 2000 (Mn = 2,000, hydroxyl value = 56, acid value <0.05, linear wax type), PTMG 3000 (Mn = 3,000, hydroxyl value = 38, acid value <0.05, linear Wax type) [above, manufactured by Mitsubishi Chemical Corporation];

  HQ-20 (Mn = 200, hydroxyl value = 565, acid value <0.1, aromatic ring-containing linear solid type), BA-4 glycol (Mn = 400, hydroxyl value = 280, acid value <0.1, Aromatic ring-containing linear liquid type), BA-6 glycol (Mn = 500, hydroxyl value = 225, acid value <0.1, aromatic ring-containing linear liquid type), BA-10 glycol (Mn = 660, hydroxyl value = 170) , Acid value <0.1, aromatic ring-containing linear liquid type), BA-17 glycol (Mn = 950, hydroxyl value = 170, acid value <0.1, aromatic ring-containing linear liquid type), BA-P2 glycol ( Mn = 360, hydroxyl value = 312, acid value <0.1, aromatic ring-containing linear liquid type), BA-P4 glycol (Mn = 450, hydroxyl value = 250, acid value <0.1, aromatic ring-containing linear liquid) Type), BA-P Glycol (Mn = 660, hydroxyl value = 170, acid value <0.5, aromatic ring-containing linear liquid type), BPF4 (Mn = 380, hydroxyl value = 300, acid value <0.1, aromatic ring-containing linear liquid type) ) [Above, manufactured by Nippon Emulsifier] and the like.

The polyester polyols (a1-3) can be obtained by the condensation reaction of the above-mentioned low molecular weight polyols (a1-1) and polycarboxylic acids.
Known polycarboxylic acids used to obtain the polyester polyols (a1-3) include, for example, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, and chloromaleic acid. Acids, fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, glutaric acid, itaconic acid, succinic anhydride, maleic anhydride and other aliphatic dicarboxylic acids and their anhydrides;

  For example, alicyclic dicarboxylic acids such as dimer acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and anhydrides thereof;

  For example, o-phthalic acid, isophthalic acid, terephthalic acid, 2,5-dimethylterephthalic acid, 4,4-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, norbornenedicarboxylic acid, diphenylmethane. -4,4'-dicarboxylic acid, phenylindanedicarboxylic acid, aromatic dicarboxylic acid such as phthalic anhydride, and anhydrides thereof;

  In addition, polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly (β-methyl-γ-valerolactone), and polyvalerolactone can also be used. Taking into consideration moisture permeability, water absorption, affinity with drugs, and skin conformability of the adhesive film, aliphatic or alicyclic compounds using the above aliphatic or alicyclic dicarboxylic acids and their anhydrides. A group polyester polyol may be used in combination. These may be used alone or in combination of two or more.

  As the polyester polyols (a1-3), commercially available products can be used, and Kuraray polyol P510 (Mn = 500, hydroxyl value = 224, acid value <0.5, linear liquid type), Kuraray polyol P1010 (Mn = 1). 2,000, hydroxyl value = 112, acid value <0.5, linear liquid type), Kuraray polyol P2010 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type), Kuraray polyol P3010 (Mn = 3,000, hydroxyl value = 37, acid value <0.5, linear liquid type), Kuraray polyol P4010 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid type) , Kuraray polyol P5010 (Mn = 5,000, hydroxyl value = 22, acid value <0.5, linear liquid type), Kuraray polyol P6010 (Mn = 6, 00, hydroxyl value = 19, acid value <0.5, linear liquid type), Kuraray polyol P2050 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type), Kuraray polyol P3050 ( Mn = 3,000, hydroxyl value = 37, acid value <0.5, linear liquid type), Kuraray polyol P4050 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid type), Kuraray Polyol N2010 (Mn = 2,000, Hydroxyl Value = 56, Acid Value <0.5, Linear Liquid Type), Kuraray Polyol N4010 (Mn = 4,000, Hydroxyl Value = 28, Acid Value <0.5, Linear Liquid type), Kuraray polyol PNOA1010 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type), Kuraray polyol PNOA2014 (Mn 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type), Kuraray polyol P1012 (Mn = 1,000, hydroxyl value = 112, acid value <1, aromatic ring-containing linear liquid type), Kuraray Polyol P2012 (Mn = 2,000, hydroxyl value = 56, acid value <1, aromatic ring-containing linear liquid type), Kuraray polyol P1013 (Mn = 1,000, hydroxyl value = 112, acid value <1, aromatic ring-containing Linear liquid type), Kuraray polyol P2013 (Mn = 2,000, hydroxyl value = 56, acid value <1, aromatic ring-containing linear liquid type), Kuraray polyol P1020 (Mn = 1,000, hydroxyl value = 112, acid value <1, aromatic ring-containing linear liquid type), Kuraray polyol P2020 (Mn = 2,000, hydroxyl value = 56, acid value <1, aromatic ring-containing linear liquid type), Kuraray polyol P530 (Mn = 500, hydroxyl value = 224, acid value <0.5, aromatic ring-containing linear liquid type), Kuraray polyol P1030 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, Aromatic ring-containing linear liquid type), Kuraray Polyol P2030 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, aromatic ring-containing linear liquid type) [above, manufactured by Kuraray Co., Ltd.];

  For example, URIC H-62 (Mn = 430, hydroxyl value = 260, acid value <4.0, linear liquid type), URIC Y-202 (Mn = 980, hydroxyl value = 115, acid value <1.0, linear Liquid type), URIC Y-332 (Mn = 910, hydroxyl value = 123, acid value <1.0, linear liquid type), URIC SE-3506 (Mn = 3,500, hydroxyl value = 32, acid value <1 .0, white solid type), URIC H-52 (Mn = 840, hydroxyl value = 200, acid value <3.0, white solid trifunctional type), URIC AC-005 (Mn = 550, hydroxyl value = 205, acid value <4.0, aromatic ring-containing linear liquid type), URIC AC-006 (Mn = 650, hydroxyl value = 178, acid value <5.0, aromatic ring-containing linear liquid type) [above, Ito Oil Manufactured by the company];

  For example, PLACCEL 205 (Mn = 530, hydroxyl value = 212, acid value <1.0, linear liquid type), PLACCEL 208 (Mn = 830, hydroxyl value = 135, acid value <1.0, linear wax type) , PLACCEL 210 (Mn = 1,000, hydroxyl value = 114, acid value <1.0, linear wax type), PLACCEL 220 (Mn = 2,000, hydroxyl value = 56, acid value <1.0, linear Wax type), PLACCEL 230 (Mn = 3,000, hydroxyl value = 37, acid value <1.0, linear wax type), PLACCEL 240 (Mn = 4,000, hydroxyl value = 28, acid value <1. 0, linear wax type) [above, manufactured by Daicel];

  For example, Kyowapol 2000BA (Mn = 2,000, hydroxyl value = 58, acid value <0.5, linear liquid type), Kyowapol 5000PA (Mn = 5,000, hydroxyl value = 22, acid value <0.5 , Linear liquid type) [above, Kyowa Hakko Chemical Co., Ltd.];

    For example, Polylite OD-X-221 (Mn = 2,000, hydroxyl value = 56, acid value <0.3, linear liquid type), Polylite OD-X-2586 (Mn = 850, hydroxyl value = 200, acid value) = 0.4, linear liquid type), Polylite OD-X-2420 (Mn = 2,000, hydroxyl value = 56, acid value = 0.4, linear liquid type), Polylite OD-X-2523 (Mn = 3) , 500, hydroxyl value = 32, acid value = 0.5, linear solid type), Polylite OD-X-2547 (Mn = 4,500, hydroxyl value = 25, acid value = 0.3, linear solid type), Polylite OD-X-102 (Mn = 2,000, hydroxyl value = 56, acid value = 1.3, linear solid type), Polylite OD-X-2420 (Mn = 2,000, hydroxyl value = 56, acid value) = 0.3, linear liquid type ), Polylite OD-X-2155 (Mn = 1,000, hydroxyl value = 115, acid value = 0.2, linear solid type), Polylite OD-X-2722 (Mn = 2,000, hydroxyl value = 58). , Acid value = 0.3, linear liquid type) [above, manufactured by DIC];

  For example, Nipporan 4002 (Mn = 1,000, hydroxyl value = 110, acid value <2, linear solid type), Nipporan 4040 (Mn = 2,000, hydroxyl value = 56, acid value <2, linear solid type), Nipporan 4009 (Mn = 1,000, hydroxyl value = 110, acid value <2, linear solid type), Nipporan 4010 (Mn = 2,000, hydroxyl value = 56, acid value <2, linear solid type), Nipporan 164 (Mn = 1,000, hydroxyl value = 110, acid value <1, linear solid type), Nipolan 4073 (Mn = 2,000, hydroxyl value = 56, acid value <1, linear solid type), Nipolan 152 (Mn = 1,000, hydroxyl value = 110, acid value <1, linear liquid type), Nipporan 1004 (Mn = 2,600, hydroxyl value = 42, acid value <2, linear liquid type) Nippolan 5018 (Mn = 2,000, hydroxyl value = 56, acid number <1, the linear solid type) [above, Tosoh - made Company]

  For example, MAXMOL RDK-133 (Mn = 360, hydroxyl value = 315, acid value = 0.5, linear liquid type), MAXMOL RDK-142 (Mn = 280, hydroxyl value = 400, acid value = 0.5, linear) Liquid type) [above, Kawasaki Kasei Co., Ltd.];

  For example, Phantol SV-298 (Mn = 450, hydroxyl value = 250, acid value <1, linear liquid type), Phantol SV-208 (Mn = 480, hydroxyl value = 235, acid value <1, linear liquid type) ), Phantoor TA22-735A (Mn = 1,400, hydroxyl value = 80, acid value <1, linear liquid type), Phantol TA22-735C (Mn = 1,450, hydroxyl value = 79, acid value <1 , Linear liquid type) [above, Hitachi Chemical Co., Ltd.];

  For example, ADEKA NEWACE F18-62 (Mn = 1,000, hydroxyl value = 112, acid value <1, linear liquid type), ADEKA NEWACE F7-67 (Mn = 2,000, hydroxyl value = 56, acid value) <1, linear liquid type), ADEKA NEW ACE YT-101 (Mn = 680, hydroxyl value = 165, acid value <0.3, linear liquid type), ADEKA NEW ACE Y9-10 (Mn = 1,000, hydroxyl group) Value = 110, acid value <1, linear liquid type), ADEKA NEWACE F13-35 (Mn = 1,000, hydroxyl value = 112, acid value <1, linear solid type), ADEKA NEWACE F52-21 (Mn = 2,000, hydroxyl value = 56, acid value <1, linear liquid type), ADEKA NEWACE YG-108 (Mn = 900, hydroxyl value = 110, acid value <1, linear solid type) , Adeka New Ace NS2400 (Mn = 2,000, hydroxyl value = 56, acid value <1, linear liquid type), Adeka New Ace V14-90 (Mn = 2,000, hydroxyl value = 56, acid value <0. 3, linear solid type) [above, manufactured by Adeka];

  For example, HS2H-200S (Mn = 2,000, hydroxyl value = 56, acid value <0.3, linear liquid type), HS2H-350S (Mn = 3,500, hydroxyl value = 32, acid value <0.3 , Linear liquid type), HS2H-500S (Mn = 5,000, hydroxyl value = 22, acid value <0.3, linear liquid type), HS2H-179A (Mn = 1,750, hydroxyl value = 64, acid value) <0.3, aromatic ring-containing linear liquid type), HS2H-458T (Mn = 4,500, hydroxyl value = 25, acid value <0.3, aromatic ring-containing linear solid type), HS2F-237P (Mn = 2) 1,000, hydroxyl value = 56, acid value <0.3, aromatic ring-containing linear solid type) [above, manufactured by Toyokuni Oil Co., Ltd.];

  For example, Teslac 2460 (Mn = 2,000, hydroxyl value = 56, acid value <1, linear liquid type), for example, Teslac 2450 (Mn = 2,000, hydroxyl value = 56, acid value <1.5, linear Liquid type), Teslac 2462 (Mn = 2,000, hydroxyl value = 56, acid value <1, linear liquid type), Teslac 2464 (Mn = 1,000, hydroxyl value = 115, acid value <1, linear liquid type) ), Teslac 2469 (Mn = 3,000, hydroxyl value = 37, acid value <1, linear liquid type), Teslac 2471 (Mn = 2,000, hydroxyl value = 56, acid value <1, linear liquid type), Teslac 2477 (Mn = 1,750, hydroxyl value = 65, acid value <1, linear liquid type), Teslac TA22-558 (Mn = 2,000, hydroxyl value = 72, acid value <1 Linear liquid type), Tesrack TA22-559 (Mn = 2,500, hydroxyl value = 80, acid number <1, the linear liquid type) [manufactured by Hitachi Chemical Co.];

  For example, MAXMOL RDK-133 (Mn = 360, hydroxyl value = 315, acid value = 0.5, linear liquid type), MAXMOL RDK-142 (Mn = 280, hydroxyl value = 400, acid value = 0.5, linear) Liquid type) [above, Kawasaki Kasei Co., Ltd.];

  For example, preplast 1900 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type), preplast 1838 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear Liquid type), preplast 3186 (Mn = 1,700, hydroxyl value = 71, acid value <0.5, linear liquid type), preplast 3162 (Mn = 1,000, hydroxyl value = 110, acid value <0.5 , Linear solid type), preplast 3172 (Mn = 3,000, hydroxyl value = 38, acid value <0.5, linear solid type), preplast 3199 (Mn = 2,000, hydroxyl value = 55, acid value <0 .5, linear liquid type) [above, CRODA company make] etc. can be mentioned.

The polyamide polyols (a1-4) can be obtained by forming a polyamide by a condensation reaction with the above-mentioned polycarboxylic acids and polyamines, and subjecting the above-mentioned low-molecular weight polyols (a1-1) to a condensation reaction. .
As the known polyamines used to obtain the polyamide polyols (a1-4), polyamines having two or more amino groups can be used without particular limitation. For example, ethylenediamine, propylenediamine, butylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, bis- (3-aminopropyl) ether, 1,2-bis- (3-aminopropoxy) ethane, 1, 3-bis- (3-aminopropoxy) -2,2-dimethylpropane, α, ω-bis- (3-aminopropyl) polyethylene glycol ether, neopentyldiamine, 1,2-diaminobutane, 1,4-diamino Aliphatic diamines such as butane, hexamethylenediamine, trimethylhexamethylenediamine;

  For example, messendiamine, isophoronediamine, 1,3- (bisaminomethyl) cyclohexane, 1,4- (bisaminopropyl) cyclohexane, 4,4′-methylenebis (2-methylcyclohexylamine), norbornanediamine and other fats Cyclic diamines;

  Examples thereof include polyamines having three or more amino groups such as methanetriamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, butane-1,1,4,4-tetraamine.

  Ketimines, which are reaction products of these polyamines and ketones, are also included in the polyamines.

Among these, aliphatic polyamines and alicyclic diamines are preferable as polyamines in consideration of the solubility of the pressure-sensitive adhesive in an organic solvent described below, the adhesiveness to the skin, and the high carcinogenicity.
The polyamines may be used alone or in combination of two or more, but the polyamide polyol (a1-4) is preferably used in combination with other polyols from the viewpoint of solubility in an organic solvent.

  As the polyamide polyols (a1-4), commercially available products can also be used, and specifically, TPAE617 (Mn = 15,000, Tg = 90 ° C., hydroxyl value = 16, acid value = 1, linear type). [The above are manufactured by Fuji Kasei Kogyo Co., Ltd.] and the like.

  The polycarbonate polyols (a1-5) have a structure represented by the following general formula [I] in the molecule, and known polycarbonate polyols can be used.

General formula [I]
-[-OR- ^l- O-CO-] _m-
(In the formula, R ¹ represents a divalent organic residue, and m represents an integer of 1 or more.)

The polycarbonate polyols (a1-5) are (1) the reaction of the low molecular weight polyols (a1-1) with a carbonic acid ester, or (2) the presence of an alkali in the low molecular weight polyols (a1-1). It can be obtained by a reaction in which phosgene is caused to act below.
Examples of the carbonic acid ester used in the above case (1) include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate and propylene carbonate.

  Since the polycarbonate polyol (a1-5) has a carbonate structure as a linking group, the cohesive force of the polyurethane resin (A) is increased, and sufficient adhesion to the skin can be exhibited.

  As the polycarbonate polyols (a1-5), commercially available products can be used, and for example, oximer N112 (Mn = 1,000, Tg = 60 ° C., hydroxyl value = 112, acid value <0.5, linear type) [ Made by Perstorp];

  Duranol T5651 (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear liquid type), Duranol T5652 (Mn = 2,000, hydroxyl value = 56, acid value <0.05, linear liquid type) ), Duranol T4671 (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear liquid type), Duranol T4672 (Mn = 2,000, hydroxyl value = 52, acid value <0.05, linear Liquid type) [above, manufactured by Asahi Kasei Chemicals];

  ETERNACOLL UH-100 (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear liquid type), ETERNACOLLUH-200 (Mn = 2,000, hydroxyl value = 56, acid value <0.05, Linear liquid type) [above, made by Ube Industries];

  BENEBiOL NL1010DB (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear solid type), BENEBiOL NL2010DB (Mn = 2,000, hydroxyl value = 56, acid value <0.05, linear solid type) ), BENEBiOLNL1010B (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear solid type), BENEBiOLNL2010B (Mn = 2,000, hydroxyl value = 56, acid value <0.05, linear solid type) ) [Above, manufactured by Mitsubishi Chemical Corporation];

  PLACCEL CD205 (Mn = 500, hydroxyl value = 225, acid value <0.1, linear liquid type), PLACCEL CD210 (Mn = 1,000, hydroxyl value = 116, acid value <0.1, linear wax type) , PLACCEL CD220 (Mn = 2,000, hydroxyl value = 56, acid value <0.1, linear wax type) [above, manufactured by Daicel Corporation];

Kuraray polyol C-1065N (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear wax type), Kuraray polyol C-2065N (Mn = 2,000, hydroxyl value = 56, acid value < 0.5, linear wax type), Kuraray polyol C-1090 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type), Kuraray polyol C-2090 (Mn = 2,000) , Hydroxyl value = 56, acid value <0.5, linear liquid type), Kuraray polyol C-3090 (Mn = 3,000, hydroxyl value = 37, acid value <0.5, linear liquid type), Kuraray polyol C -4090 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid type), Kuraray polyol C-5090 (Mn = 5,000, hydroxyl value = 22, acid value < 0.5, linear liquid type), Kuraray polyol C-1015N (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type), Kuraray polyol C-2015N (Mn = 2,000, Hydroxyl value = 56, acid value <0.5, linear liquid type) [above, manufactured by Kuraray Co., Ltd.];
Etc. can be mentioned.

  The other polyols (a1-6) are polyols that do not belong to the above polyols (a1-1) to (a1-5), and contain at least one ionic functional group, dimethylsiloxane diol. Typical examples thereof include polyols having a siloxane skeleton such as, and polyols having a diene skeleton such as polybutadiene diol and polyisoprene diol. However, hydrogenated diene in which the diene skeleton is saturated with hydrogen atoms is also defined to be included in the diene skeleton.

  Among the polyols containing at least one ionic functional group, the ionic functional group means a quaternary ammonium group, a tertiary amino group, a carboxylate group, a carboxyl group, a sulfonate group, a sulfonic acid group, a phosphonium group. And ionic groups such as phosphinic acid groups and sulfuric acid ester groups, or precursor groups thereof. Carboxyl groups, tertiary amino groups, etc. do not contain ionic groups, but since they can be easily converted into ionic groups by neutralization or quaternization reaction with ammonia, tertiary amine, acetic acid, etc., they are ionic functional groups. Shall be included in.

  Examples of the polyol containing at least one ionic functional group include 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butyric acid, and 2,2-bis (hydroxymethyl) kyl. Carboxyl group-containing polyol compounds such as herbic acid and 2,2-bis (hydroxymethyl) butanoic acid, and also hydrogen atoms of ammonia such as N, N-bis (2-hydroxypropyl) aniline and N-methyldiethanolamine are hydrocarbon groups. Examples of the substituent include a substituent-containing polyol and the like.

  Examples of commercially available polyols having a siloxane skeleton include KF6001 (Mn = 1,800, hydroxyl value = 62, acid value <0.5, linear liquid type), KF6002 (Mn = 3,000, hydroxyl value = 35). , Acid value <0.5, linear liquid type), KF6003 (Mn = 5,000, hydroxyl value = 22, acid value <0.5, linear liquid type) [above, manufactured by Shin-Etsu Chemical Co., Ltd.];

  XF42-B0970 (Mn = 1,850, hydroxyl value = 60, acid value <0.5, linear liquid type) [above, manufactured by Momentive Performance Materials, Inc.];

  SF8427 (Mn = 2,400, hydroxyl value = 46.8, acid value <0.1, linear liquid type), SF8428 (Mn = 3,200, hydroxyl value = 35, acid value <0.1, linear liquid type) ) [These are manufactured by Toray Dow Corning Co., Ltd.] and the like.

  Examples of commercially available polyols having a diene skeleton include GI-1000 (Mn = 1,500, hydroxyl value = 67, acid value <0.5, linear liquid type), GI-2000 (Mn = 2,100, Hydroxyl value = 47, acid value <0.5, linear liquid type), GI-3000 (Mn = 3,100, hydroxyl value = 26, acid value <0.5, linear liquid type) [above, Nippon Soda Co., Ltd. ];

  Epol (Mn = 2,500, hydroxyl value = 45, acid value <0.1, linear liquid type), Poly bd R45HT (Mn = 1,200, hydroxyl value = 93.5, acid value <0.1, linear Liquid type) [above, manufactured by Idemitsu Kosan Co., Ltd.] and the like. However, the olefin skeleton obtained by hydrogenating the diene skeleton is also included in the diene skeleton.

In the above-mentioned polyol (a1), polyether polyols (a1-2), polyester polyols (a1-3), polyamide polyols (a1-4), polycarbonate polyols (a1-5), or other polyols. As described above, (a-6) is preferably a diol having two hydroxyl groups and has a number average molecular weight (also referred to as Mn) ranging from a low molecular weight to a high molecular weight. The number average molecular weight (Mn) is preferably in the range of 200 to 50,000, though it is not particularly limited as long as it can be dissolved in a solvent. It is more preferably 400 to 30,000, and most preferably 500 to 10,000. As described above, when the number average molecular weight (Mn) is within the above range, the viscosity suitable for coating can be maintained, so that handling at the time of coating is excellent, and the polyurethane urea resin (A) described later is suitable for use. Cohesive force and sufficient flexibility can be imparted, and sufficient adhesiveness to the skin can be expressed. In addition, when an adhesive film made of a pressure-sensitive adhesive is laminated on a base material (G) described below, it does not float or peel even under severe conditions such as water or high temperature and high humidity, adhesion to the skin, A pressure-sensitive adhesive having excellent wettability can be obtained and can be applied to a transdermally absorbable adhesive sheet.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene conversion values measured by gel permeation chromatography (GPC) method. Details of the GPC measurement method are described in Examples.

Among the polyols (a1), polyether polyols (a1-2), polyester polyols (a1-3), polyamide polyols (a1-4), polycarbonate polyols (a1-5), or other polyols ( The hydroxyl value of a1-6) is preferably in the range of 2 to 560 mgKOH / g, more preferably in the range of 4 to 280 mgKOH / g, and most preferably in the range of 4 to 200 mgKOH / g. When the hydroxyl value is in the above range, a pressure-sensitive adhesive having excellent adhesion to skin and followability can be obtained as in the case of the number average molecular weight (Mn), and can be applied to a transdermal absorbent sheet. Becomes It is generally known that if the hydroxyl value of a polyol is determined, the number average molecular weight is also determined, and the hydroxyl value and the number average molecular weight are linked.
The hydroxyl value (OHV) is a value measured according to JIS K1557-1: 2007 and the acid value (AV) is a value measured according to JIS K0070: 1992, and the details of the measuring method are described in Examples. .

  When the above-mentioned polyol (a1) has a glass transition temperature (Tg), it is not particularly limited, but is preferably −80 to 80 ° C., more preferably −70 to 60 ° C. When the glass transition temperature (Tg) is within the above range, when the polyurethane urea resin (A) is used as a pressure-sensitive adhesive, it has sufficient adhesiveness and cohesive force, so that the adhesiveness is maintained and after lamination. It suppresses the cohesive failure of, and suppresses the floating and peeling after sticking to the skin as an adhesive sheet. The glass transition temperature (Tg) can be adjusted by appropriately selecting the types of the polyol (a1) and the amine compound (a3) described later as the constituent components. Further, it is also possible to adjust to an appropriate glass transition temperature by using two or more kinds of polyols (a1) having different glass transition temperatures. Details of the measuring method will be described in Examples.

  Adhesive layer using pressure-sensitive adhesive Stability of drug in the adhesive layer, drug release from the adhesive layer, transdermal absorbability Adhesive sheet does not contaminate the skin, keeps removability, exfoliates keratin It is preferable to use diols having no aromatic ring from the viewpoints such as not to do so. From the viewpoint of water vapor permeability that suppresses stuffiness, swelling, or rash during application and maintenance of water absorption, polyether polyols (a1- 2) is preferably used, and polyethylene glycol is particularly preferably used. Also, in terms of adhesion (adhesion) to the skin and conformability to the skin surface (flexibility), use in combination with low molecular weight polyols that do not have an aromatic ring and have an alkyl group on the side chain. Is preferred.

  The content of the polyether polyols (a1-2) contained in the polyurethane urea resin (A) is preferably 20 to 100% by weight, and more preferably 50 to 90% by weight based on the total amount of the polyol (a1). When the content of the polyether polyols (a1-2) is within the above range, when used as a pressure-sensitive adhesive, it does not adversely affect high adhesiveness to the skin and is in an environment with large temperature changes. Not only can the adhesive strength after being left for a long time and the solubility for the drug (D) (transdermal drug (d1) or transdermal absorption enhancer (d2)) described below be improved, but also high water vapor can be obtained. Since it exhibits permeability and water absorption, it becomes possible to suppress whitening of the coating film, water resistance, or prevent stuffiness, swelling, or rash during sticking.

<< Polyisocyanate (a2) >>
Next, the polyisocyanate (a2) unit, which is a monomer unit constituting the polyurethane urea resin (A), will be described.
As the polyisocyanate (a2), conventionally known ones can be used, and examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates, which are carcinogenic even when decomposed. Aliphatic polyisocyanates or alicyclic polyisocyanates that do not generate high aromatic diamines are preferable.
The term "aliphatic" used herein means an acyclic carbon compound, and a cyclic carbon compound having no aromatic ring is defined as an alicyclic group.
Further, the polyisocyanate (a2) may have three or more isocyanate groups, but a diisocyanate having two isocyanate groups is preferable from the viewpoint of imparting flexibility with the decrease in density of the polyurethane urea resin.

  Examples of the polyisocyanate (a2) include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene. Aliphatic diisocyanates such as diisocyanate, dodecamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate;

  For example, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4- Cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane, norbornene diisocyanate, dimer acid diisocyanate, octahydro-4,7-methano-1H Alicyclic diisocyanates such as indene dimethyl diisocyanate;

  For example, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (alias: 2,4-TDI), 2,6-tolylene diisocyanate (alias) : 2,6-TDI), 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4′-diphenyl ether diisocyanate, 4,4 ′, 4 ″ -triphenyl Methane triisocyanate, 1,3-phenylene bismethylene diisocyanate (alias: m-XDI), 1,4-phenylene bismethylene diisocyanate (alias: p-XDI), 2,2'-diphenylmethane diisocyanate (alias: 2,2-MDI), 4,4'-diphenyl Tandiisocyanate (alias: 4,4-MDI), 1,3-naphthalenediyl diisocyanate (alias: 1,3-NDI), 1,5-naphthalenediyl diisocyanate (alias: 1,5-NDI), ω, ω ' -Diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3 -Aromatic diisocyanates such as tetramethylxylylene diisocyanate;

  Examples thereof include polyisocyanates having three or more isocyanate groups such as lysine triisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate, and methylsilanetriyltrisisocyanate.

The polyisocyanate (a2) may have three or more isocyanate groups as described above, but the diisocyanates having two isocyanate groups may give flexibility as the density of the polyurethane resin (A) decreases. It is preferable in terms.
Among these, aliphatic polyisocyanates such as hexamethylene diisocyanate (alias: HDI), alicyclic polyisocyanates such as isophorone diisocyanate (alias: IPDI), 4,4′-methylenebis (cyclohexyl isocyanate) (alias: hydrogenated MDI) It is preferable to use diisocyanates having no aromatic ring such as isocyanates.

<< amine compound (a3) >>
Next, the amine compound (a3) unit, which is a monomer unit constituting the polyurethane urea resin (A), will be described.
The amine compound (a3) is used for introducing and forming a urea bond into the polyurethane resin (X) synthesized with the polyol (a1) and the polyisocyanate (a2). When the polyurethane urea resin (A) containing the amine compound (a3) as a monomer unit is used as a pressure-sensitive adhesive, not only the water absorption is improved, but also the durability and the adhesive strength accompanying the introduction of the urea bond are improved. It becomes possible to achieve both.

As the amine compound (a3), it is important to include the diamine compound (a3-1) having two iminopropionic acid ester structures, and it is also possible to include the amine compound (a3-2) other than the diamine compound (a3-1). good.
Here, the amino group, ammonium, a monovalent atomic group obtained by removing hydrogen from primary or secondary amine _{(-NH 3, -NHR, -NRR '} ) refers to the respective substituents second It is called a primary amino group, a secondary amino group, or a tertiary amino group.

Here, the iminopropionic acid ester structure is a structure represented by the following general formula [II] in which a nitrogen atom having one hydrogen atom is bonded to an ester bonding group via ethylene, It is a structure formed from 1 molar equivalent of an amino group and 1 molar equivalent of a double bond group.
By having a substituent having an ester bond group in the amine compound, it becomes possible to give the polyurethane urea resin (A) with durability associated with the urea bond, and appropriate polarity and flexibility, which is preferable. .

[In the general formula [II], each R ₁ independently represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aralkyl group, an aryl group, a hydroxyalkyl group, a hydroxyalkylene oxide group, an alkoxyalkylene oxide group, It is a hydroxyalkylcarbonyloxyalkyl group. R ₂ is independently a hydroxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, a hydroxyalkyl group, a hydroxyalkylene oxide group, or an alkoxyalkylene oxide group. ]

Here, the monovalent substituents (R ₁ , R ₂ ) represented by the iminopropionic acid ester structure represented by the general formula [II] will be described.
The hydroxyl group is a hydroxyl group.
The alkyl group may be linear or branched and preferably has 1 to 26 carbon atoms, and more preferably 1 to 22 carbon atoms.
The cycloalkyl group is alicyclic and preferably has 2 to 26 carbon atoms, and more preferably 2 to 22 carbon atoms.
The alkenyl group may be linear or branched and preferably has 2 to 26 carbon atoms, more preferably 2 to 22 carbon atoms.
The cycloalkenyl group is alicyclic and preferably has 2 to 26 carbon atoms, and more preferably 2 to 22 carbon atoms.
The aryl group is a substituent having a substituted or unsubstituted aromatic ring having 6 to 30 carbon atoms.
The alkyl portion of the aralkyl group is the same as the above alkyl group, and the aryl portion is the same as the above aryl group.
The hydroxyalkyl group is preferably a C1-C30 alkyl group having a hydroxyl group at the terminal.
The hydroxyalkylene oxide group preferably has a hydroxyl group at the terminal, has 1 to 16 repeating units, and has 2 to 5 carbon atoms.
The alkoxyalkylene oxide group has an alkoxy group having an alkyl group having 1 to 30 carbon atoms at the terminal, has 1 to 16 repeating units, and preferably has 2 to 5 carbon atoms.
The hydroxyalkylcarbonyloxyalkyl group preferably has a hydroxyl group at the terminal, has 1 to 10 repeating units, and preferably has 2 to 8 carbon atoms. For example, ethyl 6-hydroxyhexanoate group, 6-ethoxy-6-oxohexyl 6-hydroxyhexanoate group, 6-ethoxy-6-oxohexyl 6-{(6-hydroxyhexanoyl) oxy} hexanoate group, etc. Is mentioned.

<< Diamine compound having two iminopropionic acid ester structures (a3-1) >>
First, the diamine compound (a3-1) having two iminopropionic acid ester structures will be described.
The diamine compound (a3-1) having two iminopropionic acid ester structures represented by the general formula [II] is (1) a primary amine compound (a3-1-1-1) having one amino group. A diamine compound (a3-1-1) formed from 2 molar equivalents and 1 molar equivalent of an ethylenically unsaturated compound (a3-1-1-2) having two double bond groups, and (2) amino. 1 molar equivalent of a primary diamine compound (a3-1-2-1) having two groups and 2 molar equivalents of an ethylenically unsaturated compound (a3-1-2-2) having one double bond group Can be classified as a diamine compound (a3-1-2).
Here, the primary amine compound (a3-1-1-1) having one amino group and the ethylenically unsaturated compound (a3-1-2-2) having one double bond group are polyurethane urea. It is used for forming a side chain in the resin (A), and the amine compound (a3-1-1-1) and the ethylenically unsaturated compound (a3-1-2-2) are used to reduce heat yellowing and It is preferable that the aromatic ring is not contained from the viewpoint of ensuring adhesion to the skin due to the decrease in density or suppressing carcinogenicity.

The primary amine compound (a3-1-1-1) having one amino group includes a primary amine compound (a3-1-1-1-1) having a hydroxyl group and a primary amine having no hydroxyl group. It can be classified as an amine compound (a3-1-1-1-2).
Moreover, the ethylenically unsaturated compound (a3-1-2-2) having one double bond group does not have a hydroxyl group and the ethylenically unsaturated compound (a3-1-2-2-1) having a hydroxyl group. It can be classified as an ethylenically unsaturated compound (a3-1-2-2-2).

  The hydroxyl group of the side chain of the polyurethane urea resin is a primary amine compound having a hydroxyl group (a3-1-1-1-1) or an ethylenically unsaturated compound having a hydroxyl group (a3-1-2-2-1). Is formed by. The polyurethane urea resin (A) having a hydroxyl group-containing primary amine compound (a3-1-1-1-1) and a hydroxyl group-containing ethylenically unsaturated compound (a3-1-2-2-1) will be described later. It is preferable because it can be used as a reaction point with the reactive compound (B) having a functional group capable of reacting with the hydroxyl group.

  Further, the primary amine compound (a3-1-1-1-2) having no hydroxyl group and the ethylenically unsaturated compound (a3-1-2--2-2) having no hydroxyl group have 4 to 4 carbon atoms. It is preferable to use a primary amine compound having 22 alkyl groups or an ethylenically unsaturated compound in combination. These alkyl groups having 4 to 22 carbon atoms form side chains of the polyurethane urea resin, and improve adhesion (adhesion) to the skin and followability (flexibility) to the skin surface, and further improve water resistance. Show the effect.

  Further, the primary amine compound (a3-1-1-1) having one amino group and the ethylenic unsaturated compound (a3-1-2-) having one double bond group regardless of the presence or absence of a hydroxyl group. In 2), it is preferable to have an alkylene oxide unit. Having an alkylene oxide unit forms the side chain of the polyurethane urea resin and not only suppresses the whitening of the adhesive layer, but also improves the water vapor permeability and water absorption, which can prevent damage to the skin. Become. Of the alkylene oxide units, it is particularly preferable to have an ethylene oxide skeleton in terms of water vapor permeability, water absorption, suppression of damage to the skin, drug stability in the adhesive layer, and drug release from the adhesive layer. preferable

(1) 2 mole equivalents of a primary amine compound (a3-1-1-1) having one amino group and an ethylenically unsaturated compound (a3-1-1-2) 1 having two double bond groups The diamine compound (a3-1-1) formed from the molar equivalent will be described.
Of the primary amine compound (a3-1-1-1) having one amino group, the primary amine compound (a3-1-1-1-1) having a hydroxyl group is, for example, hydroxyamine, Methanolamine, 2-aminoethanol, 2-aminopropanol, 3-aminopropanol, 4-aminobutanol, 2-aminobutanol, 6-aminohexanol, 8-aminooctanol, 6-amino-2-methyl-2-heptanol ( Alias: heptamyl), 2-amino-3-hydroxypropionic acid (alias: serine), rac- (R *)-2-amino-3-methylbutan-1-ol (alias: valinol), 2-amino-4-. Methyl-1-pentanol (also known as leucinol), 2-amino-1-propanol, 2-amino-2-methyl-1-propanol , 1-amino-2-methyl-2-propanol, 2-amino-3-methyl-1-butanol, 2-amino-4-methyl-1-pentanol, and other alkanolamines having one hydroxyl group. ;

  For example, 2-amino-4- (methylthio) -1-butanol (alias: methioninol) and other alkanolamines having a sulfur atom and one hydroxyl group;

  For example, polyether monoamines having a hydroxyl group at the end formed by adding 1 to 40 moles of alkylene oxide such as ethylene oxide (abbreviation: EO) and propylene oxide (abbreviation: PO) to the above alkanolamines;

  For example, 2-aminopropane-1,3-diol (alias: serinol), rel- (2R *, 3R *)-2-amino-1,3-butanediol (alias: threoninol), 2-amino-4-. Octadecene-1,3-diol (also known as sphingosine), 2-amino-2-ethyl-1,3-propanediol, 2,2-bis (hydroxymethyl) -2-aminoethanol, trishydroxymethylaminomethane, etc. Examples thereof include amines having two or more long chain alkyl groups and two or more hydroxyl groups.

Each of these may be used alone or in combination of two or more, but it is preferable to use an alkanolamine having one aromatic group, which does not have an aromatic group and which can reduce the density of the polyurethane urea resin. preferable. When an alkanolamine having two or more hydroxyl groups is used, the cross-linking points arranged on the side chains of the polyurethane urea resin (A) are too close and the density may increase, so caution is required. .
In particular, 2-aminoethanol, 2-aminopropanol, 3-aminopropanol, 4-aminobutanol, 6-amino-2-methyl-2-heptanol, 2- (2-aminoethoxy) ethan-1-ol, 2- {2- (2-Aminoethoxy) ethoxy} ethane-1-ol, 2- [2- {2- (2-aminoethoxy) ethoxy} ethoxy] ethane-1-ol, 2- (2-aminopropoxy) ethane -1-ol, 2- {2- (2-aminopropoxypropoxy) propoxy} ethane-1-ol, 2- [2- {2- (2-aminopropoxy) propoxy} propoxy] ethane-1-ol, 2 -Amino-4-methyl-1-pentanol is preferred.

Examples of the primary amine compound (a3-1-1-1-2) having no hydroxyl group include conventionally known compounds having no hydroxyl group, and amine compounds having an alkyl group having 4 to 22 carbon atoms. (A3-1-1-1-2-1), an amine compound (a3-1-1-1-2-2) having an alkylene oxide unit and a terminal being an alkoxy group, and a C4 to C22 It can be classified as an amine compound (a3-1-1-1-2-3) having no alkyl group or alkylene oxide unit. However, none of these have an aromatic ring.
The C4-C22 alkyl group contained in the polyurethane urea resin (A) is also formed from an amine compound (a3-1-1-1-2-1) having a C4-C22 alkyl group. Since the hydrogen bonding property and the crystallinity of the resin are destroyed, not only the viscosity can be lowered, but also the effect of improving the conformability to the skin is exhibited.
In addition, the alkylene oxide unit contained in the side chain of the polyurethane urea resin (A) has an alkylene oxide unit, and an amine compound (a3-1-1-1-2-2) whose terminal is an alkoxy group is used. Since it is formed and water vapor permeability and water absorption are improved, it is effective in suppressing damage to the skin. As described above, it is particularly preferable to have an ethylene oxide skeleton from the viewpoints of water vapor permeability, water absorption, suppression of damage to the skin, drug stability in the adhesive layer, and drug release from the adhesive layer. .

  Examples of the amine compound (a3-1-1-1-2-1) having an alkyl group having 4 to 22 carbon atoms include n-butylamine, sec-butylamine, isobutylamine, tert-butylamine, 2-methylbutylamine, 3-methylbutylamine, 1-amino-2-methyl-n-pentane, 1-amino-3-methyl-n-pentane, 1-amino-2,2-dimethyl-n-butane, 1-amino-2,3 -Dimethyl-n-butane, 1-amino-2-ethyl-n-butane, 1-aminopentane, 1-aminohexane, 2-aminohexane, 1-aminoheptane, 1-aminooctane, 2-aminooctane, 2 -Ethylhexylamine, 1-aminononane, 1-aminodecane, 1-aminoundecane, 1-aminododecane (alias: laurylamine), -Aminotridecane, 1-aminotetradecane (alias: myristylamine), 1-aminopentadecane, 1-aminohexadecane (alias: cetylamine), 1-aminoheptadecane, 1-aminooctadecane (alias: stearylamine), 1- Alkyl amines such as aminononadecane, 1-icosylamine, 1-eicosylamine, 1-heneicosylamine, 1-docosylamine and the like can be mentioned.

  These may be used alone or in combination of two or more, but in view of the density reduction of the polyurethane urea resin (A) and the adhesiveness to the skin, 1-aminohexane, 1-amino-2, 2-dimethyl-n-butane, 2-aminooctane, 2-ethylhexylamine, 1-aminododecane (alias: laurylamine), 1-aminotetradecane (alias: myristylamine), 1-aminohexadecane (alias: cetylamine), 1-Aminooctadecane (also known as stearylamine) is preferred.

  Examples of the amine compound (a3-1-1-1-2-2) having an alkylene oxide unit and having an alkoxy group at the terminal include, for example, ethylene oxide (abbreviation: EO), propylene oxide ( Abbreviations: PO) and other alkylene oxides are added in an amount of about 1 to 40 mol, and polyether monoamines having an alkoxy group such as a methoxy group or an ethoxy group at the end are mentioned.

  These may be used alone or in combination of two or more, but in view of water vapor permeability and water absorption of the polyurethane urea resin (A), at least 6 mol or more of ethylene oxide (abbreviation: EO) skeleton is used. Addition of a polyether monoamine is preferred.

  Examples of the amine compound (a3-1-1-1-2-3) having no alkyl group having 4 to 22 carbon atoms and the alkylene oxide unit include methylamine, ethylamine, propylamine, tricosylamine, tetracosylamine, Alkylamines such as octacosylamine;

  For example, alkenylamines such as allylamine, methallylamine, propenylamine, butanylamine, hexanylamine, octanylamine, decenylamine, octadecenylamine (also known as oleylamine);

  For example, 1-methyl-cyclopropanamine, 2-methyl-cyclopropanamine, 1-amino-2,3-dimethyl-cyclopropane, 1-amino-2-ethyl-cyclopropane, 1-amino-2-isopropyl- Cyclopropane, cyclobutylamine, 1-amino-2-methyl-cyclobutane, 1-amino-2-ethyl-cyclobutane, 1-amino-3-ethyl-cyclobutane, 1-amino-2,2-dimethyl-cyclobutane, 1- Amino-2,3-dimethyl-cyclobutane, 1-amino-2,3,4-trimethyl-cyclobutane, cyclopentylamine, 1-amino-2-methyl-cyclopentane, 1-amino-3-methyl-cyclopentane, cyclohexyl Amine, 2-methylcyclohexylamine, 4-methylcyclohexylamine 2-propylcyclohexylamine, 2-isopropylcyclohexylamine, 2-hexylcyclohexylamine, cycloheptylamine, cyclooctylamine, cyclononylamine, cyclodecylamine, cycloundecylamine, cyclododecylamine, norbornane-2-amine, 2 , 3-dimethyl-2-norbornanamine, cycloalkylamines such as amantadine;

  For example, cycloalkenylamines such as (S) -3-aminocyclobutene, 3-aminocyclohexene, 5-norbornene-2-methylamine, 3-cyclohexenylmethylamine and 1-aminodicyclopentadiene.

  Alanine, cysteine, glycine, leucine, isoleucine, valine, 1,1-dimethylhydrazine, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, γ-aminopropyltri Other amines such as ethoxysilane may be mentioned.

The primary amine compound (a3-1-1-1) having one amino group may be used alone or in combination of two or more. As a constituent component of (A), a primary amine compound having a hydroxyl group (a3-1-1-1-1) and an amine compound having an alkyl group having 4 to 22 carbon atoms (a3-1-1-1-2). -1), and an amine compound (a3-1-1-1-2-2) having an alkylene oxide unit and having an alkoxy group at the end are preferably contained as an essential component.
Moreover, the content ratio of the amine compound (a3-1-1-1-1), the amine compound (a3-1-1-1-2-1), and the amine compound (a3-1-1-1-2-2). Is appropriately determined according to the number average molecular weight and the content ratio of the above-mentioned polyol (a1) and polyisocyanate (a2).

  In this way, by containing the amine compound (a3-1-1-1) in the polyurethane urea resin (A), a hydroxyl group can be introduced into the side chain, so that the crosslinking reaction with the reactive compound (B) described later It is a component of the polyurethane urea resin (A), which is effectively promoted and contains an amine compound (a3-1-1-1-2-1) having an alkyl group having 4 to 22 carbon atoms. It is possible to reduce the crystallinity and the resin density associated with the polyol (a1). Therefore, the resin can be softened, and not only the conformability to the skin can be improved, but also the adhesion to the skin can be improved. In addition, since it has an alkylene oxide unit and contains an amine compound (a3-1-1-1-2-2) in which the terminal is an alkoxy group, water vapor permeability and water absorption are improved, so It is possible to suppress damage. In particular, it is preferable to have an ethylene oxide skeleton from the viewpoints of water vapor permeability, water absorption, suppression of damage to the skin, drug stability in the adhesive layer, and drug release from the adhesive layer.

Next, the ethylenically unsaturated compound (a3-1-1-2) having two double bond groups may be a known compound as long as it is a compound containing two double bond groups. . By containing an ethylenically unsaturated compound having two double bond groups, a structure different from that of the polyol (a1) can be introduced into the main chain of the polyurethane urea resin (A). When the pressure-sensitive adhesive is used, the adhesiveness to the skin and the durability such as water resistance under severe conditions can be maintained.
In addition, when described as “(meth) acrylic”, “(meth) acryloyl”, “(meth) acrylic acid”, “(meth) acrylate”, “(meth) acryloyloxy”, and “(meth) allyl” Unless otherwise specified, each is "acrylic or methacrylic", "acryloyl or methacryloyl", "acrylic acid or methacrylic acid", "acrylate or methacrylate", "acryloyloxy or methacryloyloxy", and "allyl or methallyl". Is represented.

  Examples of the ethylenically unsaturated compound (a3-1-1-2) having two double bond groups include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and di (meth) acrylic. Acid 2-butyl-2-ethyl-1,3-propanediol, di (meth) acrylic acid 1,2-butanediol, di (meth) acrylic acid 1,3-butanediol, di (meth) acrylic acid 1, 4-butanediol, 1,5-pentanediol di (meth) acrylate, 3-butyl-3-ethyl-1,5-pentanediol di (meth) acrylate, 3-methyl-1 di (meth) acrylate , 5-pentanediol, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, di (meth) acrylic 1,6-hexanediol, 2-ethyl-1,3-hexanediol di (meth) acrylate, 3,3′-dimethylolheptane di (meth) acrylic acid, 1,8-octane di (meth) acrylic acid Diol, 2-methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylic acid, 1,10-decanediol di (meth) acrylic acid, di (meth) acrylic Acid alkyl (meth) acrylic acid diesters such as 1,12-dodecanediol;

  For example, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate (EO addition mole number: 4 to 23), propylene glycol di (meth) acrylate, di ( (Meth) acrylic acid dipropylene glycol, di (meth) acrylic acid polypropylene glycol (EO addition mole number: 3 to 23), di (meth) acrylic acid polytetramethylene glycol (tetramethylene addition mole number: 3 to 23), di (Meth) acrylic acid poly (ethylene glycol-propylene glycol) (EO addition mole number: 2 to 23, PO addition mole number: 2 to 23), di (meth) acrylic acid poly (ethylene glycol-tetramethylene glycol) (EO Addition mole number: 2 to 23, tetramethylene addition mole number: 2 23) having an alkylene oxide unit, such as (meth) acrylic acid diesters;

  For example, 1,4-cyclohexanediol di (meth) acrylic acid, 2,5-norbornanediol di (meth) acrylic acid, 1,4-cyclohexanedimethanol di (meth) acrylic acid, dimethylol di (meth) acrylic acid Tricyclodecane, epichlorohydrin modified hexahydrophthalic acid di (meth) acrylic acid ester, tricyclodecane dihydroxymethyl di (meth) acrylate, tricyclodecane dihydroxymethyl dicaprolactonate di (meth) acrylate 2-Methyl-1,1′-tricyclo [3,3,1,13,7] decane-1,3-diyl (meth) acrylate, 1,2-adamantanediol di (meth) acrylate, di (meth ) 1,3-adamantane diol acrylic acid, 1,4-adamantane diol di (meth) acrylic acid, (Meth) acrylic acid 1,2-adamantane dimethanol, di (meth) acrylic acid 1,3-adamantane dimethanol, di (meth) acrylic acid ethylene oxide-modified hydrogenated bisphenol A (EO addition mole number: 2 to 22) , Cycloalkyl having alicyclic structure such as propylene oxide di (meth) acrylic acid modified hydrogenated bisphenol A (PO addition mole number: 2 to 22), epichlorohydrin modified hexahydrophthalic acid di (meth) acrylic acid ester System (meth) acrylic acid diesters;

  For example, 1,4-cyclohexenediol di (meth) acrylate, 1,4-cyclohexene dimethanol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, dicyclopentenyloxyethyl di (meth) acrylate Cycloalkene-based (meth) acrylic acid diesters such as;

  For example, di (meth) acrylic acid ester of neopentyl glycol hydroxypivalate, ε-caprolactone adduct of neopentyl glycol di (meth) acrylic acid hydroxypivalate (ε-caprolactone addition mole number: 2 to 12), etc. (Meth) acrylic acid diesters having fatty acid esters;

  For example, glycerol di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, 1,3-bis {(meth) acryloyloxy} -2-propanol, di (meth) acrylic acid (Meth) acrylic acid diesters having a hydroxyl group such as trimethylolpropane, pentaglycerol di (meth) acrylate, pentaerythritol di (meth) acrylate, and tripentaerythritol di (meth) acrylate;

  For example, di {2- (meth) acryloyloxyethyl} acid phosphate, di {2- (meth) acryloyloxypropyl} acid phosphate, di {2- (meth) acryloyloxybutyl} acid phosphate, di {2- (meth ) Acryloyloxyhexyl} acid phosphate, di {2- (meth) acryloyloxyoctyl} acid phosphate, bis {(meth) acryloyloxymethyl} methylphosphonate, bis [2-{(meth) acryloyloxy) ethyl] methylphosphonate , Bis {2-((meth) acryloyloxy) propyl} methylphosphonate, bis [3-{(meth) acryloyloxy} propyl] methylphosphonate, bis [4-{(meth) acryloyloxy} butyl] methylphosphone Bis [5-{(meth) acryloyloxy} pentyl] methylphosphonate, bis [6-{(meth) acryloyloxy} hexyl] methylphosphonate, bis [7-{(meth) acryloyloxy} heptyl] methylphosphonate, Bis {8- (acryloyloxy) octyl} methylphosphonate, bis {(meth) acryloyloxyphenyl} methylphosphonate Bis {(meth) acryloyloxymethyl} ethylphosphonate, bis {(meth) acryloyloxy-di- (methyloxy) } Methylphosphine oxide, bis {(meth) acryloyloxy-di- (ethyloxy)} methylphosphine oxide, bis {(meth) acryloyloxy-di- (propyloxy)} methylphosphine oxide, bis {(meth) acryl Loyloxy-di- (propyloxy)} methylphosphine oxide, bis {(meth) acryloyloxy-di- (butyloxy)} methylphosphine oxide, bis {(meth) acryloyloxy-di- (pentyloxy)} methylphosphine oxide, (Meth) acrylic acid diesters having a phosphorus atom such as bis {(meth) acryloyloxy-di- (hexyloxy)} methylphosphine oxide;

  For example, (meth) acrylic acid diesters having a sulfur atom such as di (meth) acrylic acid mercaptoethyl sulfide;

  For example, 1,1-bis {(meth) acryloyloxymethyl} ethyl isocyanate, 1,1-bis {(meth) acryloyloxymethyl} propyl isocyanate, 1,1-bis {(meth) acryloyloxymethyl} butyl isocyanate, etc. (Meth) acrylic acid diesters having an isocyanate group of

  For example, unsaturated compounds having both a (meth) acryloyl group and a vinyl group such as 2-vinyloxyethyl (meth) acrylate and 2- (2′-vinyloxyethoxy) ethyl (meth) acrylate;

  For example, divinyl compounds such as divinyl adipate and divinyl sebacate;

  For example, ethylene glycol divinyl ether, diethylene glycol divinyl ether (DEGVE), triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, polypropylene glycol Divinyl ethers such as divinyl ether, butanediol divinyl ether, neopentyl glycol divinyl ether, hexanediol divinyl ether, nonanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether;

  For example, di (meth) allyl ether, di (meth) allyl adipate, di (meth) allyl sebacate, di (meth) allyl phthalate, di (meth) allyl hexahydrophthalate, di (meth) allyl disulfide, di Examples include di (meth) allyl compounds such as (meth) allyl trisulfide, 2,2-bis (allyloxymethyl) -1-butanol, diallyl phthalate and the like.

These may be used alone or in combination of two or more, but have chain alkyl (meth) acrylic acid diesters and alkylene oxide units (meth) capable of reducing the density of the polyurethane urea resin. Polyurethane urea is a compound having no aromatic ring, such as acrylic acid diesters, cycloalkyl (meth) acrylic acid diesters, (meth) acrylic acid diesters having a fatty acid ester, or (meth) acrylic acid diesters having a hydroxyl group. A chain alkyl type (meth) acrylic acid diester or a (meth) acrylic acid diester having an alkylene oxide unit, which is preferably used for reducing the density of the resin (A), is particularly preferable.
As described above, the (meth) acrylic acid diester having a hydroxyl group is preferable because it has a hydroxyl group and can serve as a crosslinking point with the reactive compound (B) described later. In addition, (meth) acrylic acid diesters having an alkylene oxide unit are preferable in terms of water vapor permeability and water absorption because damage to the skin can be suppressed.
Further, from the viewpoint of easy formation of the diamine compound (a3-1) and storage stability of the compound, the ethylenically unsaturated compound (a3-1-1-2) is more preferably a (meth) acrylic acid ester. Most preferred are acrylic acid esters.

  The diamine compound (a3-1-1) is an ethylenic compound having two double bond groups and two molar equivalents of the above-described primary amine compound (a3-1-1-1) having one amino group. 1 mole equivalent of the saturated compound (a3-1-1-2) is a compound formed of and, more specifically, a primary amine compound (a3-1-1) having no aromatic ring and having a hydroxyl group. -1-1), an amine compound (a3-1-1-1-2-1) having an alkyl group having 4 to 22 carbon atoms, and an amine compound (a3 having an alkylene oxide unit and an end being an alkoxy group). -1-1-1-2-2) is a diamine compound added to an ethylenically unsaturated compound (a3-1-1-2) having two double bond groups, and the diamine compound (a3-1 -1) has no aromatic ring in the side chain, hydroxyl group, carbon number To 22 alkyl group, and preferably form to have each alkylene oxide unit. The hydroxyl group contained in the diamine compound (a3-1-1) becomes a hydroxyl group contained in the polyurethane urea resin (A) and can be used as a reaction point with the reactive compound (B) described later. Further, the alkyl group having 4 to 22 carbon atoms contained in the diamine compound (a3-1-1) becomes a part of the alkyl group having 4 to 22 carbon atoms contained in the polyurethane urea resin (A), and hydrogen bond of the resin. Since the properties and crystallinity are destroyed, not only the viscosity can be reduced, but also the ability of the resin to follow the skin with the reduced density is exhibited. Moreover, since the alkylene oxide unit contained in the diamine compound (a3-1-1) can improve water vapor permeability and water absorption, damage to the skin can be suppressed.

Primary amine compound (a3-1-1-1-1) having a hydroxyl group, amine compound (a3-1-1-1-2-1) having an alkyl group having 4 to 22 carbon atoms, and alkylene oxide unit And the ratio of the amine compound (a3-1-1-1-2-2) having an alkoxy group at the terminal is such that the crosslinking reactivity of the polyurethane urea resin (A) depends on the purpose of use of the pressure-sensitive adhesive. It can be arbitrarily set depending on flexibility, flexibility, or water vapor permeability.
The diamine compound (a3-1-1) includes a primary amine compound (a3-1-1-1) having a hydroxyl group and an amine compound (a3-1-1) having an alkyl group having 4 to 22 carbon atoms. 1-2-1), and an amine compound (a3-1-1-1-2-2) having an alkylene oxide unit and an end being an alkoxy group, and a substituent having no other aromatic ring The amine compound (a3-1-1-1-2-3) having a group and the diamine compound added to the ethylenically unsaturated compound (a3-1-1-2) having two double bond groups are also used. It is possible.

(2) 1 molar equivalent of a primary diamine compound (a3-1-2-1) having two amino groups and an ethylenically unsaturated compound (a3-1-2-2) 2 having one double bond group The diamine compound (a3-1-2), which is composed of and the molar equivalents of and, will be described.
The primary diamine compound (a3-1-2-1) having two amino groups forms part of the main chain skeleton of the polyurethane urea resin (A), and has an ethylenic non-monomer having one double bond group. The saturated compound (a3-1-2-2) forms part of the side chain skeleton. However, it does not have an aromatic ring.
Examples of the primary diamine compound (a3-1-2-1) having two amino groups include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1, 5-diaminopentane, 2,2-dimethyl-1,3-diaminopropane, 1,6-diaminohexane, 2,2,4-trimethyl-1,6-hexamethylenediamine, 2,4,4-trimethyl-1 , 6-hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, dendrimer having an amino group at the end, etc. Aliphatic diamines of

  For example, a diamine having amino groups at both ends of an alkylene oxide unit such as polyoxyethylene, polyoxypropylene, or polyoxyethylene / polyoxypropylene, having propoxyamine at both ends, and represented by the following general formula (II) Polyether diamines having alkylene oxide units such as polyoxyalkylene diamines;

General formula (III)
_{H 2 N-CH 2 -CH 2} -CH 2 -O- (C p H 2p -O) q -CH 2 -CH 2 -CH 2 -NH 2
(In the formula, p represents an arbitrary integer of 2 to 4, and q represents an arbitrary integer of 2 to 50.)

  For example, diaminocyclohexane, 1,3-bisaminocyclohexane, isophoronediamine, dicyclohexylmethane-4,4′-diamine, 4,4′-methylenebis (cyclohexylamine), 4,4′-methylenebis (2-methylcyclohexylamine) , Norbornanediamine, adamantane-1,3-diamine, diaminoareonitrile, and alicyclic diamines such as dimerdiamine obtained by converting the carboxyl group of dimer acid into an amino group. These may be used alone or in combination of two or more.

As the primary diamine compound (a3-1-2-1) having two amino groups, it is preferable not to use an aromatic diamine having carcinogenicity. Compounds having no aromatic ring, such as aliphatic diamines, polyether amines or alicyclic diamines, which can reduce the density of the polyurethane urea resin, are preferably used for reducing the density of the polyurethane urea resin (A). Polyetherdiamines with polyalkylene oxide units are not only effective in improving water vapor permeability and maintaining water absorption, but also suppress damage to the skin when peeling the adhesive sheet from the skin or during long-term application. Since it is possible, it is particularly preferably used.
As described above, the alkylene oxide unit may be appropriately selected depending on the content of the alkylene oxide unit in the polyurethane urea resin (A) in order to maintain the balance between the water vapor permeability of the pressure-sensitive adhesive and the adhesive force to the skin.

  In addition, diamines having a hydroxyl group are preferable because they have a hydroxyl group and can serve as a crosslinking point with the reactive compound (B) described later. From the viewpoint of easy formation of the diamine compound (a3-1-2) and storage stability of the compound, the primary diamine compound (a3-1-2-1) having two amino groups is ethylenediamine. 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2,2-dimethyl-1,3-diaminopropane, 1,6-diaminohexane, 2,2,4-trimethyl- Aliphatic diamines such as 1,6-hexamethylenediamine, polyoxyethylene, polyoxypropylene, or polyetherdiamines such as diamines having amino groups at both ends of alkylene oxide units such as polyoxyethylene / polyoxypropylene. , Diaminocyclohexane, isophoronediamine, 4,4'-methylenebis (cyclohexylamine), 4 4'-methylenebis (2-methylcyclohexylamine) alicyclic diamines are preferably used.

  Among the ethylenically unsaturated compound (a3-1-2-2) having one double bond group, the ethylenically unsaturated compound (a3-1-2-2-1) having a hydroxyl group is, for example, ( 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, ( 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, cyclohexane Dimethanol mono (meth) acrylic acid ester, (meth) acrylic acid 10-hydroxydecyl, (meth 12-hydroxylauryl acrylate, ethyl (meth) acrylate-α- (hydroxymethyl), glycerol monofunctional (meth) acrylate, or glycidyl laurate (meth) acrylate, glycidyl oleate (meth) acrylate For a fatty acid ester-based (meth) acrylic acid ester such as glycidyl stearate (meth) acrylate, or the above-mentioned hydroxyl group-containing ethylenically unsaturated compound such as 2- (acryloyloxy) ethyl 6-hydroxyhexanonate. Hydroxyl group-containing aliphatic (meth) acrylic acid esters such as (meth) acrylic acid ester having a hydroxyl group at the terminal obtained by ring-opening addition of ε-caprolactone;

  For example, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyoctyl vinyl ether, hydroxydecyl vinyl ether, hydroxydodecyl vinyl ether, hydroxy octadecyl vinyl ether, glyceryl vinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, triethyl glycol Hydroxyl group-containing aliphatic vinyl ethers such as methylolpropane monovinyl ether and pentaerythritol monovinyl ether;

  For example, (meth) allyl alcohol, isopropenyl alcohol, dimethyl (meth) allyl alcohol, hydroxyethyl (meth) allyl ether, hydroxypropyl (meth) allyl ether, hydroxybutyl (meth) allyl ether, hydroxyhexyl (meth) allyl ether , Hydroxyoctyl (meth) allyl ether, hydroxydecyl (meth) allyl ether, hydroxydodecyl (meth) allyl ether, hydroxyoctadecyl (meth) allyl ether, glyceryl (meth) allyl ether, etc. Alcohols;

  For example, ethylenically unsaturated compounds having a plurality of hydroxyl groups, such as propene diol, butene diol, heptene diol, octene diol, and glycerol di (meth) acrylate;

  For example, containing a hydroxyl group such as N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, N-hydroxyoctyl (meth) acrylamide, etc. (Meth) acrylamides;

  For example, monomers having a hydroxyl group and a vinyl group such as vinyl alcohol;

  For example, the above-mentioned, containing both a hydroxyl group and an alkylene oxide unit such as an alkylene oxide-added ethylenically unsaturated compound obtained by repeatedly adding an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide to a hydroxyl group-containing ethylenically unsaturated compound. Examples thereof include ethylenically unsaturated compounds, but are not particularly limited thereto. These may be used alone or in combination of two or more.

  As the ethylenically unsaturated compound (a3-1-2-2-1) having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, from the viewpoint of improving the adhesiveness to the base material and the adhesiveness to the skin, 2-hydroxypropyl (meth) acrylic acid, 4-hydroxybutyl (meth) acrylic acid, and the like, fatty acid ester-based (meth) acrylic acid ester having 2 to 18 carbon atoms, and ε-caprolactone 1-2 mol addition (meth) acrylic acid (Meth) acrylic acid ester having a hydroxyl group at the terminal of 2 to 18 carbon atoms obtained by ring-opening addition of ε-caprolactone to a hydroxyl group-containing ethylenically unsaturated compound such as 2-hydroxyethyl, ethylene oxide or propylene Alkylene oxides such as oxides have a hydroxyl group-containing ethylenic property such as 2-hydroxyethyl (meth) acrylate. A (meth) acrylic acid ester having a hydroxyl group at the terminal obtained by adding 1 to 20 mol to a saturated compound, a hydroxyl group-containing aliphatic vinyl ether such as hydroxyethyl vinyl ether, and a hydroxyl group-containing (meth) acrylate such as N-hydroxyethyl acrylamide. ) C2-C18 ethylenically unsaturated compounds such as acrylamide are preferred. Among them, alkylene oxides such as ethylene oxide and propylene oxide have 1 to 20 mol of hydroxyl group-containing ethylenically unsaturated compounds such as 2-hydroxyethyl (meth) acrylate and hydroxyethyl vinyl ether in terms of water vapor permeability and water absorption. An ethylenically unsaturated compound containing both a hydroxyl group and an alkylene oxide unit, such as a (meth) acrylic acid ester having a hydroxyl group at the terminal and an alkylene oxide unit or a vinyl ether, which is obtained by the addition is particularly preferable.

Examples of the ethylenically unsaturated compound having no hydroxyl group (a3-1-2-2-2) include conventionally known compounds that do not have a hydroxyl group, and are ethylenic having an alkyl group having 4 to 22 carbon atoms. Unsaturated compound (a3-1-2-2-2-1), ethylenically unsaturated compound (a3-1-2-2-2-2) having an alkylene oxide unit and having an alkoxy group at the terminal, and It can be classified into an ethylenically unsaturated compound (a3-1-2-2-2-3) having no alkyl group having 4 to 22 carbon atoms and alkylene oxide unit. However, none of these have an aromatic ring.
The alkyl group having 4 to 22 carbon atoms contained in the polyurethane urea resin (A) is obtained from the ethylenically unsaturated compound (a3-1-2-2-2-1) having an alkyl group having 4 to 22 carbon atoms. Is also formed, and the hydrogen bondability and crystallinity of the resin are destroyed, so that not only can the viscosity be reduced, but it is also effective in improving the conformability to the skin and improving the water resistance.
Further, the alkylene oxide unit contained in the side chain of the polyurethane urea resin (A) has an alkylene oxide unit, and the terminal is an alkoxy group, an ethylenically unsaturated compound (a3-1-2-2-2-). It is formed by 2) and improves the water vapor permeability and the water absorption, and thus it is effective in suppressing damage to the skin. As described above, it is particularly preferable to have an ethylene oxide skeleton from the viewpoints of water vapor permeability, water absorption, suppression of damage to the skin, drug stability in the adhesive layer, and drug release from the adhesive layer. .

  Examples of the ethylenically unsaturated compound (a3-1-2-2-2-1) having an alkyl group having 4 to 22 carbon atoms include n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, and acrylic. Acid pentyl, isoamyl acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid 3 , 4-dimethylhexyl, nonyl (meth) acrylate, isononyl (meth) acrylate, 3,4-dimethylheptyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, (meth) Isostearyl acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, etc. Alkyl esters of acrylic acid;

  For example, N-butyl (meth) acrylamide, N-propyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-nonyl (meth). Acrylamide, N-tricosyl (meth) acrylamide, N-nonadecyl (meth) acrylamide, N-docosyl (meth) acrylamide, N-tridecyl (meth) acrylamide, N- (5,5-dimethylhexyl) (meth) acrylamide, N N-alkyl (meth) acrylamides such as-(dibutylaminomethyl) (meth) acrylamide;

  For example, n-butyl vinyl ether, isobutyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether, tert-pentyl vinyl ether, n-hexyl vinyl ether, isohexyl vinyl ether, 2-ethylbutyl vinyl ether, 2-ethylhexyl. Alkyl vinyl ethers such as vinyl ether, n-heptyl vinyl ether, n-octyl vinyl ether, isooctyl vinyl ether, nonyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, hexadecyl vinyl ether, octadecyl vinyl ether, docosyl vinyl ether;

  For example, n-butyl (meth) allyl ether, tert-butyl (meth) allyl ether, n-hexyl (meth) allyl ether, n-octyl (meth) allyl ether, n-nonyl (meth) allyl ether, n-tricosyl. (Meth) allyl ether, n-nonadecyl (meth) allyl ether, n-docosyl (meth) allyl ether, n-tridecyl (meth) allyl ether, (5,5-dimethylhexyl) (meth) allyl ether, (dibutylamino) Examples thereof include alkyl (meth) allyl ethers such as methyl) (meth) allyl ether, but are not particularly limited thereto. These may be used alone or in combination of two or more.

Examples of the ethylenically unsaturated compound (a3-1-2-2-2-2) having an alkylene oxide unit and having an alkoxy group at the terminal include, for example,


Examples of the ethylenically unsaturated compound (a3-1-1-1-2-2) having an alkylene oxide unit and having an alkoxy group at the terminal include (meth) acrylic acid having the above hydroxyl group, vinyl ethers, or In addition to allylic ethers, alkylene oxides such as ethylene oxide (abbreviation: EO) and propylene oxide (abbreviation: PO) are added in an amount of about 1 to 40 moles, and a group having an alkoxy group such as a methoxy group or an ethoxy group at the end, An ethylenically unsaturated compound having an alkoxy group such as a methoxy group or an ethoxy group at the end formed by adding 1 to 40 mol of alkylene oxide such as ethylene oxide (abbreviation: EO) or propylene oxide (abbreviation: PO) is exemplified. .

  These may be used alone or in combination of two or more, but in view of water vapor permeability and water absorption of the polyurethane urea resin (A), at least 6 mol or more of ethylene oxide (abbreviation: EO) skeleton is used. Addition ethylenically unsaturated compounds are preferred.

  Examples of the ethylenically unsaturated compound (a3-1-2-2-2-3) having no alkyl group having 4 to 22 carbon atoms and alkylene oxide unit include ethyl acrylate, n-propyl acrylate, acrylic acid. (Meth) acrylic acid alkyl esters such as isopropyl;

  For example, (meth) allyl (meth) acrylate, 1-butenyl (meth) acrylate, 2-butenyl (meth) acrylate, 3-butenyl (meth) acrylate, 3-methyl-3- (meth) acrylate. Butenyl, 2-chloro-2-propenyl (meth) acrylate, 3-chloro-2-propenyl (meth) acrylate, 2- (2-propenyloxy) ethyl (meth) acrylate, 2-propenyllac (meth) acrylate Chill, 3,7-dimethyloct-6-en-1-yl (meth) acrylate, (E) -3,7-dimethylocta-2,6-dien-1-yl (meth) acrylate, (meth ) Rhodenyl acrylate, cinnamyl (meth) acrylate, vinyl (meth) acrylate, and the like (meth) acrylates further containing an unsaturated double bond group;

  For example, perfluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate, perfluorooctyl (meth) acrylate, (meth) Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-permethacrylate Fluoromethyl-2-perfluoroethylmethyl, triphafluoromethylmethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate , (Meth) acrylic acid 2-perfluorode Ruechiru, (meth) (meth) acrylic acid perfluoroalkyl esters such as 2-perfluoro-hexadecyl acrylate;

  For example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 3-propoxyethyl (meth) acrylate, 2-butoxy (meth) acrylate. Ethyl, 3-butoxyethyl (meth) acrylate, 4-butoxyethyl (meth) acrylate, 6-hexyloxyethyl (meth) acrylate, 8-octyloxyethyl (meth) acrylate, (meth) acrylic acid 10 An alkoxy group-containing (meth) acrylic acid ester such as a (meth) acrylic acid ester having an alkyl at the terminal such as decyloxyethyl;

For example, cyclohexyl (meth) acrylate, 1-methyl-1-cyclopentyl (meth) acrylate, 1-ethyl-1-cyclopentyl (meth) acrylate, 1-isopropyl-1-cyclopentyl (meth) acrylate, (meth ) 1-Methyl-1-cyclohexyl acrylate, 1-ethyl-1-cyclohexyl (meth) acrylate, 1-isopropyl-1-cyclohexyl (meth) acrylate, 1-ethyl-1-cyclooctyl (meth) acrylate , (Meth) acrylic acid isobornyl, (meth) acrylic acid 2-methyladamantyl-2-yl, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid dicyclopentenyl, (meth) acrylic acid dicyclopentenyloxy Ethyl, 2-ethyladamantyl-2-yl (meth) acrylate, (Meth) acrylic acid 2-n-propyladamantyl-2-yl, (meth) acrylic acid 2-isopropyladamantyl-2-yl, (meth) acrylic acid 1- (adamantan-1-yl) -1-methylethyl, ( 1- (adamantan-1-yl) -1-ethylethyl (meth) acrylate, 1- (adamantan-1-yl) -1-methylpropyl (meth) acrylate, 1- (adamantan-1-meth) acrylate Yl) -1-ethylpropyl, (meth) acrylic acid-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] non-2-yl, (meth) acrylic acid-5-oxo 4-oxa - tricyclo [5.2.1.0 ^{3, 8]} dec-2-yl, (meth) acrylic acid-dihydro -α- Tapiniru, (meth) acrylic acid-6-oxo-7-oxa - bicyclo B) [3.2.1] oct-2-yl, (meth) acrylic acid-7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl, etc. do not have an aromatic ring ( (Meth) acrylic acid cyclic esters;

  For example, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltripropoxysilane, 3- (meth) acryloyloxypropyltributoxysilane. , 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropylbutyldimethoxysilane, 3- (meth) acryloyloxypropylethyldipropoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropyl trimethyl Kishishiran, 3- (meth) acryloyloxy propyl triethoxysilane, 3- (meth) acryloyl alkoxysilyl group-containing (meth) acrylic acid esters such as propyl tripropoxysilane;

  For example, tetrahydrofurfuryl (meth) acrylate, 2-oxotetrahydropyran-4-yl (meth) acrylate, 4-methyl-2-oxotetrahydropyran-4-yl (meth) acrylate, (meth) Acrylic acid-4-ethyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-propyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-5-oxotetrahydrofuran-3- Yl, (meth) acrylic acid-2,2-dimethyl-5-oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-5-oxotetrahydrofuran-3-yl, (meth) acrylic acid- 2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-2-oxotetrahydrofuran N-3-yl, (meth) acrylic acid-5,5-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5- Such as oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-3,3-dimethyl-5-oxotetrahydrofuran-2-ylmethyl, and (meth) acrylic acid-4,4-dimethyl-5-oxotetrahydrofuran-2-ylmethyl. 5-membered or higher cyclic ether group-containing (meth) acrylic acid esters having at least one oxygen atom in the ring;

  For example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, pentamethylpiperidinyl (meth) acrylate, 4- (pyrimidine (2-yl) piperazin-1-yl (meth) acrylate and other (meth) acrylic acid esters having a tertiary amine;

  For example, glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 9,10-epoxyoctadecanoic anhydride (meth) acrylic acid, 4-hydroxybutyl (meth) acrylate glycidyl ether, (Meth) acrylic acid 3,4-epoxycyclo [5.2.1.02,6] decane-1-yl ester, (meth) acrylic acid 2-{(1,2-epoxy-4,7-methanohide) (Meth) acrylic acid esters having an epoxy group such as lindan-5-yl) oxy} ethyl ester;

  For example, (3-methyl-3-oxetanyl) methyl (meth) acrylate, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, (3-n-propyl-3-oxetanyl) (meth) acrylate Methyl, (3-isopropyl-3-oxetanyl) methyl (meth) acrylate, (3-Methyl-3-oxetanyl) ethyl (meth) acrylate, (3-Ethyl-3-oxetanyl) ethyl (meth) acrylate, (3-n-Propyl-3-oxetanyl) ethyl (meth) acrylate, (3-Isopropyl-3-oxetanyl) ethyl (meth) acrylate, (2,4-Dimethyl-3-oxetanyl) acrylate (meth) Methyl, (meth) acrylic acid (2,3,4-trimethyl-3-oxetanyl) methyl, (meth) acrylic acid (3-ethyl-2- Cyl-3-oxetanyl) methyl, (meth) acrylic acid (3-ethyl-2,4-dimethyl-3-oxetanyl) methyl, (meth) acrylic acid (3-methyl-3-oxetanyl) ethoxymethyl, (meth) (Meth) acrylic acid esters having an oxetanyl group such as (3-ethyl-3-oxetanyl) ethoxymethyl acrylate;

  For example, (methoxycarbonyl) methyl (meth) acrylate, (methoxycarbonyl) ethyl (meth) acrylate, (methoxycarbonyl) propyl (meth) acrylate, (methoxycarbonyl) butyl (meth) acrylate, (meth) acrylic Acid (methoxycarbonyl) decyl, (meth) acrylic acid (ethoxycarbonyl) methyl, (meth) acrylic acid (ethoxycarbonyl) ethyl, (meth) acrylic acid (ethoxycarbonyl) propyl, (meth) acrylic acid (ethoxycarbonyl) butyl , (Meth) acrylic acid (ethoxycarbonyl) hexyl, (meth) acrylic acid (ethoxycarbonyl) octyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) ethyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) propyl , ( ) 2- (Ethoxycarbonyloxy) butyl acrylate, 2- (ethoxycarbonyloxy) hexyl (meth) acrylate, 2- (ethoxycarbonyloxy) octyl (meth) acrylate, 2- (propoxycarbonyl) (meth) acrylate (Oxy) ethyl, 2- (butoxycarbonyloxy) ethyl (meth) acrylate, 2- (butoxycarbonyloxy) butyl (meth) acrylate, 2- (octyloxycarbonyloxy) ethyl (meth) acrylate, (meth) Aliphatic (meth) acrylic acid esters having one carbonyl group such as 2- (octyloxycarbonyloxy) butyl acrylate;

  For example, 2-oxobutanoylethyl (meth) acrylate, 2-oxobutanoylpropyl (meth) acrylate, 2-oxobutanoylbutyl (meth) acrylate, 2-oxobutanoylhexyl (meth) acrylate, 2-Oxobutanoyloctyl (meth) acrylate, 2-oxobutanoyldecyl (meth) acrylate, 2-oxobutanoyldodecyl (meth) acrylate, 3-oxobutanoylethyl (meth) acrylate, (meth ) 3-oxobutanoylpropyl acrylate, 3-oxobutanoylbutyl (meth) acrylate, 3-oxobutanoylhexyl (meth) acrylate, 3-oxobutanoyloctyl (meth) acrylate, (meth) acrylic Acid 3-oxobutanoyldecyl, (meth) acrylic acid 3-oxobutanoyldodecyl 4-Cyanooxobutanoylethyl (meth) acrylate, 4-cyanooxobutanoylpropyl (meth) acrylate, 4-cyanooxobutanoylbutyl (meth) acrylate, 4-cyanooxobutanoyl (meth) acrylate Ruhexyl, 4-cyanooxobutanoyloctyl (meth) acrylate, 2,3-di (oxobutanoyl) propyl (meth) acrylate, 2,3-di (oxobutanoyl) butyl (meth) acrylate, ( Aliphatic (meth) acrylic acid ester having two carbonyl groups such as 2,3-di (oxobutanoyl) hexyl (meth) acrylate and 2,3-di (oxobutanoyl) octyl (meth) acrylate Kind;

For example, (meth) acrylic acid-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] non-2-yl, (meth) acrylic acid-10-methoxycarbonyl -5-oxo-4-oxa-tricyclo [5.2.1.0 ^3,8 ] non-2-yl, 4-methoxycarbonyl-6-oxo-7-oxa-bicyclo [3 (meth) acrylate] 2.1.2.1] octa-2-yl and a carbonyl group such as 4-methoxycarbonyl-7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl (meth) acrylate ( (Meth) acrylic acid cyclic esters;

  For example, N- (2-oxobutanoylethyl) (meth) acrylamide, N- (2-oxobutanoylpropyl) (meth) acrylamide, N- (2-oxobutanoylbutyl) (meth) acrylamide, N- ( Having a carbonyl group such as 2-oxobutanoylhexyl) (meth) acrylamide, N- (2-oxobutanoyloctyl) (meth) acrylamide, N- (1,1-dimethyl-3-oxobutyl) (meth) acrylamide (Meth) acrylamides;

  For example, vinyl acetoacetate, vinyl acetopropionate, vinyl acetoisobutyrate, vinyl acetobutyrate, vinyl acetovalerate, vinyl acetohexanoate, vinyl aceto-2-ethylhexanoate, vinyl aceto-n-octanoate, vinyl acetodecanoate, acetododecane. Vinyl acetate, vinyl acetooctadecanoate, vinyl acetopivalate, vinyl acetocaprate, vinyl acetocrotonate, vinyl acetosorbate, vinyl propanoyl acetate, vinyl butyryl acetate, vinyl isobutyryl acetate, vinyl palmitoyl acetate, vinyl stearoyl acetate, vinyl pyrvoyl acetate. , Vinyl propanoyl valerate, vinyl butyryl valerate, vinyl isobutyryl valerate, vinyl palmitoyl valerate, vinyl stearoyl valerate, pyruvoyl Vinyl ester compounds such aceto fatty acids having a carbonyl group of vinyl Rerin acid, and the like;

  For example, vinyl ether compounds of aceto fatty acid having a carbonyl group such as 2-acetoacetoxyethyl vinyl ether, 2-acetoacetoxybutyl vinyl ether, 2-acetoacetoxyhexyl vinyl ether, and 2-acetoacetoxyoctyl vinyl ether;

  For example, (meth) allyl acetoacetate, (meth) allyl acetopropionate, (meth) allyl acetoisobutyrate, (meth) allyl acetobutyrate, (meth) allyl acetovalerate, (meth) allyl acetohexanoate, aceto 2- Ethylhexanoic acid (meth) allyl, aceto n-octanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetododecanoic acid (meth) allyl, acetooctadecanoic acid (meth) allyl, acetopivalic acid (meth) allyl, acetocaprin Acid (meth) allyl, acetocrotonic acid (meth) allyl, acetosorbic acid (meth) allyl, propanoyl acetate (meth) allyl, butyryl acetate (meth) allyl, isobutyryl acetate (meth) allyl, palmitoyl acetate (meth) allyl, Stearoyl acetate (meth) allyl, (meth) allyl Aliphatic (meth) allyl compounds having an acyl group such as hydrin;

  For example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, 2-methylprop-2-enoylamine, N, N -N-alkyl-substituted (meta) such as -dimethyl (meth) acrylamide, N, N-diethyl- (meth) acrylamide, N- [3- (N ', N'-dimethylamino) propyl]-(meth) acrylamide, ) Acrylamides;

  For example, N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N-methoxybutyl (meth) acrylamide, N-methoxyhexyl (meth) acrylamide, N-methoxy Octyl (meth) acrylamide, N-methoxydecyl (meth) acrylamide, N-methoxydodecyl (meth) acrylamide, N-methoxyoctadecyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide , N-ethoxypropyl (meth) acrylamide, N-ethoxybutyl (meth) acrylamide, N-ethoxyhexyl (meth) acrylamide, N-ethoxyoctyl (meth) acrylamide, N-iso Ropoxymethyl (meth) acrylamide, N-isopropoxyethyl (meth) acrylamide, N-isopropoxypropyl (meth) acrylamide, N-isopropoxybutyl (meth) acrylamide, N-isopropoxyhexyl (meth) acrylamide, N-isopropoxy Octyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide, N-butoxypropyl (meth) acrylamide, N-butoxybutyl (meth) acrylamide, N-butoxyhexyl (meth) acrylamide , N-butoxyoctyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-isobutoxyethyl (meth) acrylamide, N-isobutoxypropyl (meth Acrylamide, N-isobutoxybutyl (meth) acrylamide, N-isobutoxyhexyl (meth) acrylamide, N-isobutoxyoctyl (meth) acrylamide, N- (pentoxymethyl) (meth) acrylamide, N-1-methyl- N-alkoxy group-containing (meth) acrylamides such as 2-methoxyethyl (meth) acrylamide, N, N-di (methoxymethyl) (meth) acrylamide, N, N-di (ethoxymethyl) (meth) acrylamide;

  For example, (meth) acrylamides having a tertiary amine such as dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide;

  For example, an amide group-containing ethylenically unsaturated compound such as crotonamide, maleamide, fumaramide, mesaconamide, citracone amide, itacone amide;

  For example, heterocyclic acrylamides such as 4-acryloylmorpholine, N- (oxetan-3-ylmethoxymethyl) (meth) acrylamide, N- (oxetan-2-ylmethoxymethyl) (meth) acrylamide;

    For example, sulfonyl group-containing (meth) acrylamides such as (meth) acrylamidesulfonic acid, tert-butyl- (meth) acrylamidesulfonic acid, (meth) acrylamide-2-methyl-1-propanesulfonic acid;

  For example, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, allyl vinyl ether, isopropyl vinyl ether, ethoxymethyl vinyl ether, 2-methoxyethyl vinyl ether, 2-ethoxyethyl vinyl ether, 2-butoxyethyl vinyl ether, acetoxymethyl vinyl ether, 2-acetoxyethyl vinyl ether. Aliphatic vinyl ethers such as 3-acetoxypropyl vinyl ether, 4-acetoxybutyl vinyl ether and 4-ethoxybutyl vinyl ether;

  For example, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, cyclohexyl ethyl vinyl ether, menthyl vinyl ether, 5-vinyl bicyclo [2.2.1] hept-2-ene, 2,5-bis (allyloxy) norbornane, norbornenyl vinyl ether, 1- Alicyclic vinyl ethers such as adamantyl vinyl ether and 2-adamantyl vinyl ether;

  For example, 5-vinyl-2-norbornane, 2- (2-propenyl) bicyclo [2.2.1] heptane, 5-vinylbicyclo [2.2.1] hept-2-ene, 2-ethenylidene adamantane, Alicyclic vinyl compounds such as 1-allyl adamantane;

  For example, 2-vinyloxetane, 3-vinyloxetane, 4-vinyloxetane-2-one, 3,3-bis (vinyloxymethyl) oxetane, 3-ethyl-3- (4-vinyloxycyclohexyloxymethyl) oxetane, Vinyl compounds having an oxetanyl group such as 3-ethyl-3- (vinyloxymethyl) oxetane;

  For example, 2-vinylfuran, 3-vinylfuran, 5-vinylfuran-2-methanol, 5-vinylfuran-2-carbaldehyde, 2- {2- (2,4,6-trinitrophenyl) vinyl} furan. , 2-{(E) -2- (2-thienyl) vinyl} furan, 4,5-dihydro-4β-tert-butyl-3β-vinylfuran-2 (3H) -one, 2-vinyloxytetrahydropyran, (3S) -3α-Vinyltetrahydro-2H-pyran-4α-ol, 4-vinyltetrahydro-2H-pyran-2-one, (2S) -2-vinyltetrahydro-2H-pyran, 4-methoxy-6- { (E) -2-Phenylvinyl} -2H-pyran-2-one and the like, and cyclic ether group-containing vinyl compounds having one or more oxygen atoms in the ring, and the like. The present invention is not limited to.

The ethylenically unsaturated compound (a3-1-2-2) having one double bond group may be used alone or in combination of two or more, but polyurethane may be used. As a constituent of the urea resin (A), an ethylenically unsaturated compound having a hydroxyl group (a3-1-2-2-1) and an ethylenically unsaturated compound having an alkyl group having 4 to 22 carbon atoms (a3-1). 2-2-2-1), and 3 types of ethylenically unsaturated compound (a3-1-2-2-2-2) having an alkylene oxide unit and having an alkoxy group at the end are essential. Is preferred.
Moreover, the ethylenically unsaturated compound (a3-1-2-2-1), the ethylenically unsaturated compound (a3-1-2-2-2-1), and the ethylenically unsaturated compound (a3-1-2). The content ratio of (2-2-2) is appropriately determined depending on the number average molecular weight and the content ratio of the above-mentioned polyol (a1) and polyisocyanate (a2).

  Moreover, the diamine compound (a3-1-2) includes an ethylenically unsaturated compound (a3-1-2-2-1) having a hydroxyl group and an ethylenically unsaturated compound (a3-4) having an alkyl group having 4 to 22 carbon atoms. a3-1-2-2-2-1), and an alkylene oxide unit, and in addition to the ethylenically unsaturated compound (a3-1-2-2-2-2) whose terminal is an alkoxy group, The ethylenically unsaturated compound having a substituent having no other aromatic ring (a3-1-2-2-2-3) is also a primary diamine compound having two amino groups (a3-1-2-1). It is also possible to use a diamine compound added to ().

In this way, by containing the ethylenically unsaturated compound (a3-1-2-2-1) in the polyurethane urea resin (A), a hydroxyl group can be introduced into the side chain, and thus the reactive compound (B ) Is effectively promoted, and by containing an ethylenically unsaturated compound (a3-1-2-2-2-1) having an alkyl group having 4 to 22 carbon atoms, a polyurethane urea is obtained. It is possible to reduce the crystallinity and the resin density associated with the polyol (a1), which is a component of the resin (A). Therefore, the resin can be softened, and not only the conformability to the skin can be improved, but also the adhesion to the skin can be improved. Further, since it has an alkylene oxide unit and contains an ethylenically unsaturated compound (a3-1-2-2-2-2) whose terminal is an alkoxy group, water vapor permeability and water absorption are improved, It is possible to suppress damage to the skin.
In addition, in view of the ease of forming the diamine compound (a3-1-2) and the storage stability of the compound, as the ethylenically unsaturated compound (a3-1-2-2), a (meth) acrylic acid ester is More preferably, acrylic acid ester is most preferable.

The diamine compound (a3-1) is the above-mentioned (1) 2 molar equivalents of the primary amine compound (a3-1-1-1) having one amino group and the ethylenic non-compound having two double bond groups. A diamine compound (a3-1-1) formed from 1 mol equivalent of a saturated compound (a3-1-1-2) and a primary diamine compound (a3-1) having (2) two amino groups. 2-1) A diamine compound (a3-1-2) formed from 1 molar equivalent and 2 molar equivalents of an ethylenically unsaturated compound (a3-1-2-2) having one double bond group. is there. However, neither contains an aromatic ring.
More specifically, a primary amine compound (a3-1-1-1-1) having no aromatic ring and having a hydroxyl group, and an amine having no aromatic ring and having an alkyl group having 4 to 22 carbon atoms The compound (a3-1-1-1-2-1) and the amine compound (a3-1-1-1-2-2), which has an alkylene oxide unit and whose terminal is an alkoxy group, form an aromatic ring. Diamine compound (a3-1-1) which is not added and is added to the ethylenically unsaturated compound (a3-1-1-2) having two double bond groups, and which does not have an aromatic ring and has a hydroxyl group. Ethylenically unsaturated compound (a3-1-2-2-1) and ethylenically unsaturated compound (a3-1-2-2-2) having no aromatic ring and having an alkyl group having 4 to 22 carbon atoms. -1) and an ethylene having an alkylene oxide unit and an alkoxy group at the end Diamine compound (a3-1-) in which the unsaturated unsaturated compound (a3-1-2-2-2-2) is added to the primary diamine compound (a3-1-2-1) having two amino groups. 2).

  A preferred form of the diamine compound (a3-1) is that it does not have an aromatic ring, and has three kinds of a hydroxyl group, an alkyl group having 4 to 22 carbon atoms, and an alkylene oxide unit. The hydroxyl group contained in the diamine compound (a3-1) becomes a hydroxyl group contained in the polyurethane urea resin (A) and can be used as a reaction point with the reactive compound (B) described later. In addition, the alkyl group having 4 to 22 carbon atoms contained in the diamine compound (a3-1) becomes the alkyl group having 4 to 22 carbon atoms contained in the polyurethane urea resin (A), thereby improving the hydrogen bonding property and the crystallinity of the resin. As it breaks down, it not only lowers the viscosity but also has an effect on the ability to follow the skin. Further, the alkylene oxide unit contained in the diamine compound (a3-1) becomes a side chain alkylene oxide unit of the polyurethane urea resin (A), improves water vapor permeability and water absorption, and prevents damage to the skin. It will be possible.

  Moreover, among the diamine compounds (a3-1), the diamine compound (a3-1-1) has a primary amine compound (a3-1-1-1-1) having a hydroxyl group and an aromatic ring. , An amine compound having an alkyl group having 4 to 22 carbon atoms (a3-1-1-1-2-1), and an amine compound having an alkylene oxide unit and having an alkoxy group at the end (a3-1-1). -1-2-2), an amine compound (a3-1-1-1-2-3) having an amino group having 4 to 22 carbon atoms or a substituent having no aromatic ring other than the alkylene oxide chain. Also, a diamine compound added to an ethylenically unsaturated compound (a3-1-1-2) having two double bond groups can be used.

  In the diamine compound (a3-1), the diamine compound (a3-1-2) has no aromatic ring and has an ethylenically unsaturated compound (a3-having one double bond group having a hydroxyl group). 1-2-1-2) and an ethylenically unsaturated compound (a3-1-2-2-2-1) having a substituent having 4 to 22 carbon atoms and not having an aromatic ring, and an alkylene oxide unit. In addition to the ethylenically unsaturated compound (a3-1-2-2-2-2) whose terminal is an alkoxy group, it does not have an alkyl group having 4 to 22 carbon atoms or an aromatic ring other than the alkylene oxide chain. The amine compound (a3-1-2-2-2-3) having a substituent and the diamine compound added to the primary diamine compound (a3-1-2-1) having two amino groups should be used. Is possible.

<< Amine compound (a3-2) other than diamine compound (a3-1) >>
Next, among the amine compounds (a3), the amine compounds (a3-2) other than the diamine compounds (a3-1) will be described.
Of the amine compound (a3), the amine compound (a3-2) other than the diamine compound (a3-1) is disposed at the terminal of the polyurethane urea resin (A) and reacts with the unreacted residual isocyanate group to form a resin of the resin. It is used as a reaction terminator to stabilize the reaction activity. At this time, if a primary amine compound is used to stabilize the reaction activity of the resin, the amino group represented by (-NHR) having one active hydrogen at the terminal of the polyurethane urea resin (A) may remain. When a polyisocyanate (b1), which is a reactive compound (B) described later, is used as a crosslinking agent, pot life (also referred to as pot life) may be shortened. Requires attention. Therefore, if the polyurethane urea resin (A) contains the amine compound (a3-2) as a reaction terminator, it is preferable to use secondary amines, which can be used as a reaction terminator. It is defined as an amine compound (a3-2-1).

  Among the amine compounds (a3-2), examples of the reaction-terminating amine compound (a3-2-1) that is a secondary amine that can be used as a reaction terminator include, for example, dimethylamine, diethylamine, dipropylamine and diamine. Chains of butylamine, methylethylamine, methylisopropylamine, diisopropylamine, ethylbutylamine, propylbutylamine, methylisobutylamine, methyl tert-butylamine, dihexylamine, butylhexylamine, dioctylamine, diisononylamine, butyldecylamine, dilaurylamine, etc. Secondary amines having a linear alkyl group;

  For example, secondary amines having a cycloalkyl group such as N-isopropylcyclohexylamine, dicyclohexylamine, N-methylcyclohexylamine, 1-cyclohexylethylamine, 2-methylcyclohexylamine and 4-methylcyclohexylamine;

  For example, diethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methylbutanolamine, N-ethylbutalamine, 2- (methylaminomethyl) cyclohexanol, 4-N-acetyl- Secondary amines having a hydroxyl group such as aminohexanol;

For example, butyl 3- (ethylamino) propanoate _{"R 1 = C 4 H 9} , R 2 = C 2 H 5", butyl 3- (propylamino) propanoate _{"R 1 = C 4 H 9} , R 2 = C 3 H ₇ ", butyl 3- (butylamino) _{propanoate" R 1 = C 4 H 9} , R 2 = C 4 H 9 ", butyl 3- (hexylamino) _{propanoate" R 1 = C 4 H 9} , R 2 = C ₆ H ₁₃ ", butyl 3- (hexylamino) _{propanoate" R 1 = C 4 H 9} , R 2 = C 6 H 13 ", butyl 3 - {(2-ethylhexyl) amino} propanoate" R ₁ = C _{4 H 9, R 2 = C 8} H 17 ", butyl 3- (octylamino) _{propanoate" R 1 = C 4 H 9} , R 2 = C 8 H 17 ", butyl 3- (laurylamino) propanoate" R ₁ = _{C 4 H 9, R 2 =} C 12 H 25 ", butyl 3 (Stearyl amino) propanoate _{"R 1 = C 4 H 9} , R 2 = C 18 H 37",

2-ethylhexyl 3- (ethylamino) propanoate _{"R 1 = C 8 H 17} , R 2 = C 2 H 5", 2- ethylhexyl 3- (propylamino) propanoate _{"R 1 = C 8 H 17} , R 2 = C ₃ H ₇ ", 2- ethylhexyl 3- (butylamino) _{propanoate" = R 1 = C 8 H} 17, R 2 C 4 H 9 ", 2- ethylhexyl 3- (hexylamino) propanoate" R ₁ = C ₈ H ₁₇ , R ₂ = C ₆ H ₁₃ >>, 2-ethylhexyl 3- (hexylamino) propanoate << R ₁ = C ₈ H ₁₇ , R ₂ = C ₆ H ₁₃ >>, 2-ethylhexyl 3-{(2-ethylhexyl ) amino} propanoate _{"R 1 = C 8 H 17} , R 2 = C 8 H 17", 2- ethylhexyl 3- (octylamino) propanoate _{"R 1 = C 8 H 17} , R 2 = C 8 H 17", 2-ethyl Hexyl 3- (laurylamino) propanoate _{"R 1 = C 8 H 17} , R 2 = C 12 H 25", 2- ethylhexyl 3- (stearyl amino) propanoate _{"R 1 = C 8 H 17} , R 2 = C 18 H ₃₇ >>,

Dodecyl 3- (ethylamino) propanoate _{"R 1 = C 12 H 25} , R 2 = C 2 H 5",
Dodecyl 3- (propylamino) propanoate _{"R 1 = C 12 H 25} , R 2 = C 3 H 7", dodecyl 3- (butylamino) propanoate _{"R 1 = C 12 H 25} , R 2 = C 4 H 9 >>,
Dodecyl 3- (hexylamino) propanoate _{"R 1 = C 12 H 25} , R 2 = C 6 H 13", dodecyl 3- (hexylamino) propanoate _{"R 1 = C 12 H 25} , R 2 = C 6 H 13 ", dodecyl 3 - {(2-ethylhexyl) amino} _{propanoate" R 1 = C 12 H 25} , R 2 = C 8 H 17 ", dodecyl 3- (octylamino) _{propanoate" R 1 = C 12 H 25} , R ₂ = C ₈ H ₁₇ ", dodecyl 3- (laurylamino) _{propanoate" R 1 = C 12 H 25} , R 2 = C 12 H 25 ", dodecyl 3- (stearyl amino) propanoate" R ₁ = C ₁₂ H ₂₅ , R ₂ ═C ₁₈ H ₃₇ >> and the like, among the monoamine compounds having one iminopropionic acid ester structure represented by the above general formula [II], both R ₁ and R ₂ are monoamine compounds having an alkyl group. Things.

  Examples of the amines (a3-2-2) other than the reaction-terminating amine compound (a3-2-1) include chain forms of methylamine, ethylamine, propylamine, tricosylamine, tetracosylamine, octacosylamine, and the like. Primary amines having an alkyl group;

  For example, alanine, cysteine, glycine, leucine, isoleucine, valine, 1,1-dimethylhydrazine, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, γ-amino. Other amines such as propyltriethoxysilane may be mentioned.

  These may be used alone or in combination of two or more, but are secondary amines capable of reducing the density of the polyurethane urea resin, such as dibutylamine, butylhexylamine, methylisobutylamine, dioctylamine, Chain alkylamines such as dilaurylamine are preferred. In order to form a hydroxyl group at the molecular end of the polyurethane urea resin (A) from the viewpoint of introducing some crosslinking points, it has a hydroxyl group such as diethanolamine, N-methylethanolamine, 4-N-acetyl-aminohexanol. It is also possible to use primary amines. Further, depending on the intended use, the amines (a3-2-2) other than the above reaction-terminating amine compound (a3-2-1) may be contained in the polyurethane urea resin (A) as a reaction terminator. However, as described above, there is a possibility that the pot life may be shortened, so caution is required when using.

  The polyurethane urea resin (A) is a resin obtained by polymerizing the above polyol (a1), polyisocyanate (a2), and amine compound (a3), and the weight average molecular weight (Mw) of the polyurethane urea resin (A). ), When the polyurethane urea resin (A) is used as a pressure-sensitive adhesive, the coating aptitude of the pressure-sensitive adhesive and the cohesive strength of the coating film are both 10,000 to 500, It is preferably 000, more preferably 40,000 to 300,000. When the Mw is less than 10,000, the cohesive force of the polyurethane urea resin (A) is insufficient, and when it is used as a pressure-sensitive adhesive, floating and peeling are likely to occur. On the other hand, when it exceeds 500,000, the viscosity of the polyurethane urea resin (A) becomes high, so that the coating property of the pressure-sensitive adhesive may be deteriorated. When Mw is in the above range, cohesive force and the like are further improved, so that floating and peeling can be further suppressed, and wettability and spreadability are further improved. The above weight average molecular weight and number average molecular weight are polystyrene conversion values measured by gel permeation chromatography (GPC). Details of the GPC measurement method are described in Examples.

  The hydroxyl value (OHV) of the polyurethane urea resin (A) is preferably 0.1 to 50 mgKOH / g, more preferably 0.5 to 30 mgKOH / g. When the hydroxyl value (OHV) is in the above range, an efficient crosslinking reaction with the reactive compound (B) described later can be carried out, so that when used as a pressure-sensitive adhesive, it is sufficient. While maintaining the cohesive force, it becomes easy to develop the adhesive force in the slightly viscous region. In addition, it is easy to maintain durability such as heat resistance and moist heat resistance even under severe conditions such as high temperature and high humidity after aging.

Further, all the alkylene oxide units contained in the polyurethane urea resin (A) are derived from the polyol (a1) and the amine compound (a3), and the side chain alkylene oxide unit is particularly composed of the diamine compound (a3-1). It is particularly preferable that it is introduced and has an ethylene oxide skeleton.
The content of all alkylene oxide units is preferably 25 to 80% by weight, and more preferably 30 to 70% by weight, based on the total amount of the polyurethane urea resin (A). The content of alkylene oxide units in the side chain is preferably 0.5 to 5.0% by weight in the total amount of polyurethane urea resin (A). Further, the ethylene oxide skeleton in the side chain alkylene oxide units is preferably 25 to 95% by weight in the total amount of the side chain alkylene oxide units. When the content of the alkylene oxide unit is in the above range, the water vapor permeability of the polyurethane urea resin (A) is 500 to 5,000 [g / (m ² · 24h)]], and therefore, the pressure-sensitive adhesive is used. When used, it becomes possible to suppress stuffiness, stuffiness, or skin damage. The method for evaluating the water vapor transmission rate will be described in Examples.

  The solution viscosity of the polyurethane urea resin (A) is not particularly limited and is selected depending on the use of the resin, but preferably, the nonvolatile content concentration is 3,000 to 25,000 mPa · s (25 ° C.) at a concentration of 50% by weight. is there. When the viscosity is within this range, the coating processability is improved while maintaining a sufficient cohesive force, which is preferable.

  In the above-mentioned aromatic polyol (a1), polyisocyanate (a2) and amine compound (a3), which are the monomer units constituting the polyurethane urea resin (A), the weight ratio of all the monomers constituting the polyurethane urea resin is It is preferably contained as a monomer mixture containing 45 to 94 parts by weight of the polyol (a1), 5 to 30 parts by weight of the polyisocyanate (a2), and 1 to 25 parts by weight of the amino compound (a3). More preferably, it is contained in the range of 60 to 94 parts by weight of the polyol (a1), 5 to 25 parts by weight of the polyisocyanate (a2), and 1 to 15 parts by weight of the amino compound (a3).

  When the polyol (a1), polyisocyanate (a2), and amine compound (a3) are in the above ranges, the viscosity suitable for coating is maintained, and therefore the polyurethane urea resin (A) is excellent in handling during coating. Becomes Further, when this polyurethane urea resin (A) is used as a pressure-sensitive adhesive, it becomes possible to impart an appropriate cohesive force and sufficient flexibility, so the prepared adhesive sheet was attached to the skin. At the same time, it has excellent adhesive strength and removability, and it does not come off or peel off even after aging, even under severe conditions such as high temperature and high humidity. It is possible to apply to a pressure sensitive adhesive for medical use which can form

<Reactive compound (B) having functional group capable of reacting with hydroxyl group>
Next, the reactive compound (B) having a functional group capable of reacting with a hydroxyl group will be described.
The reactive compound (B) having a functional group capable of reacting with a hydroxyl group is characterized by containing 0.1 to 50 parts by weight of the reactive compound (B) with respect to 100 parts by weight of the polyurethane urea resin (A). To do. More preferably, it is in the range of 1 to 30 parts by weight. When the reactive compound (B) is in this range, the hydroxyl group contained in the polyurethane urea resin (A) is effectively cross-linked, so that heat resistance, moist heat resistance or water resistance is improved. In addition, the coating film can be prevented from floating, peeling, or foaming in a harsh environment, and can be applied to a transdermal absorbent adhesive sheet.

Moreover, since the polyurethane urea resin (A) has a hydroxyl group, examples of the reactive functional group capable of reacting with the hydroxyl group in the reactive compound (B) include an isocyanate group, an alkoxysilyl group, and a methylol group. .
Examples of the reactive compound (B) include polyisocyanate (b1), silane compound (b2), and methylolmelamine compound (b3). Among them, compounds having two or more functional groups capable of reacting with the hydroxyl groups of the polyurethane urea resin (A) are preferably used as the reactive compound (B) in order to impart crosslinkability.
In particular, the polyisocyanate (b1) is preferably used because it is excellent in the adhesiveness after the crosslinking reaction and the adhesiveness to the base material (G) described later.

  The polyisocyanate (b1) is not particularly limited as long as it is a compound having a plurality of isocyanate groups in the molecule, and is not particularly limited, but aliphatic polyisocyanates, alicyclic polyisocyanates, or aromatic polyisocyanates. Can be classified into As the aliphatic polyisocyanates and the alicyclic polyisocyanates, compounds equivalent to the aliphatic polyisocyanates and the alicyclic polyisocyanates shown in the above polyisocyanate (a2) can be used. Note that aromatic polyisocyanates are not preferable to be used because they may decompose to form carcinogenic aromatic amines.

  The polyisocyanate (b1) is preferably a compound having 3 or more isocyanate groups. Such polyisocyanate (b1) is used in addition to the above-described polyisocyanates having three or more isocyanate groups, and various polyisocyanates such as 2-methylpentane-2,4-diol and trimethylolpropane. An adduct, a trimer having an isocyanurate ring, or the like can be preferably used. Further, polyphenylmethane polyisocyanate (also known as PAPI), and modified products of these polyisocyanates are also preferable. The polyisocyanate modified product may be a carbodiimide group, a uretdione group, a uretonimine group, a buret group reacted with water, an isocyanurate group, or a modified product having two or more of these groups. Reaction products of polyols and diisocyanates can also be used as compounds having at least two isocyanate groups. As the polyisocyanate (b1), a blocked isocyanate having an isocyanate group blocked by using a blocking agent can also be used.

  When the polyisocyanate (b1) is used, a known catalyst can be used if necessary in order to accelerate the reaction between the hydroxyl group of the polyurethane urea resin (A) and the isocyanate group. Examples of the catalyst include tertiary amine compounds and organometallic compounds.

  Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (alias: DBU) and the like.

Examples of the organometallic compound include tin compounds and non-tin compounds.
Examples of the tin compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (also known as DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide. , Tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate and the like.
Examples of the non-tin compound include titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate and butoxy titanium trichloride, lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate. -Iron-type iron such as iron hexanoate, iron 2,4-pentadionate, cobalt type such as cobalt benzoate and cobalt 2-ethylhexanoate, zinc type naphthenate, zinc type such as zinc 2-ethylhexanoate, naphthene Examples thereof include zirconium acid.

    Among the above catalysts, diazabicycloundecene (alias: DBU), dibutyltin dilaurate (alias: DBTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene. The catalyst may be used alone or in combination of two or more kinds.

  Particularly, as the polyisocyanate (b1), from the viewpoint of crosslinking reactivity, an adduct of diisocyanate such as HDI, TDI, MDI and IPDI with trimethylolpropane, a buret body reacted with water, and an isocyanurate ring formed 3 Polymers are preferably used, but from the viewpoints of maintaining the adhesive strength in the slightly viscous region and reducing the density, HDI and IPDI adducts with trimethylolpropane that do not have an aromatic ring, burettes that react with water, and isocyanates are used. A trimer having a nurate ring is particularly preferable.

  As the silane compound (b2), a known silane compound can be used, and examples thereof include an alkyl alkoxysilane, an aryl alkoxysilane, a carbamate alkoxysilane, a vinyl alkoxysilane, a halogen alkoxysilane, and (meth). Examples thereof include alkoxysilanes having an alkoxyl group such as acryloyl-based alkoxysilane, mercapto-based alkoxysilane, imidazole-based alkoxysilane, isocyanate-based alkoxysilane, epoxy-based alkoxysilane, and amino-based alkoxysilane.

  For example, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltriacetoxysilane, methyltris (methoxyethoxy) silane, methyltris (methoxypropoxy) silane, Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriisopropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxy Silane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, silane Chlohexyltrimethoxysilane, cyclohexyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldiacetoxysilane, dimethylbis (methoxyethoxy) silane, dimethylbis (methoxypropoxy) silane, diethyldimethoxysilane , Diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldiacetoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methylethyldiisopropoxysilane, methylethyldiacetoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxy Alkyl-based alkoxysilanes such as silane, methylpropyldiisopropoxysilane, and methylpropyldiacetoxysilane. ;

  For example, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltriacetoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropoxysilane, diphenyldiphenylsilane. Aryl-based alkoxysilanes such as acetoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylphenyldiisopropoxysilane, and methylphenyldiacetoxysilane;

For example, (3-carbamateethyl) propyltriethoxysilane, (3-carbamateethyl) propyltrimethoxysilane, (3-carbamateethyl) propyltripropoxysilane, (3-carbamatepropyl) propyltriethoxysilane, (3-carbamatepropyl) ) Propyltrimethoxysilane, (3-carbamatepropyl) propyltripropoxysilane, (3-carbamatebutyl) propyltriethoxysilane, (3-carbamatebutyl) propyltrimethoxysilane, (3-carbamatebutyl) propyltripropoxysilane, (3-carbamatebutyl) butyltripropoxysilane, (3-carbamatebutyl) propylmethyldiethoxysilane, (3-carbamatepentyl) propyltriethoxysilane , (3-carbamatehexyl) propyltriethoxysilane, (3-carbamateoctyl) pentyltributoxysilane, (3-carbamateethyl) propylsilyltrichloride, (3-carbamateethyl) propyltrimethylsilane, (3-carbamateethyl) ) Carbamate-based alkoxysilanes such as propyldimethylsilane, 3-carbamateethyl) propyltributylsilane, (3-carbamateethyl) ethyl-p-xylenetriethoxysilane, and (3-carbamateethyl) -p-phenylenetriethoxysilane;

  For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltriacetoxysilane, vinyltris (methoxyethoxy) silane, vinyltris (methoxypropoxy) silane, allyltrimethoxysilane, allyltriethoxysilane, divinyldimethoxysilane. , Divinyldiethoxysilane, divinyldiisopropoxysilane, divinyldiacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldiisopropoxysilane, methylvinyldiacetoxysilane, diallyldimethoxysilane, diallyldiethoxysilane, Diallyldiisopropoxysilane, methylallyldimethoxysilane, methylallyldiethoxysilane, methylallyldiisopropoxy Orchids, vinyl and allylic alkoxysilanes such as methyl allyl diacetoxy silane;

  For example, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, 3-chloropropylmethyldiethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane. Halogen-based alkoxysilanes such as silane, 3,3,3-trifluoropropyltriethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, and 3,3,3-trifluoropropylmethyldimethoxysilane. Kind;

  For example, 3-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ- (Meth) acryloyl-based alkoxysilanes such as acryloxypropylmethyldimethoxysilane;

  For example, mercapto-based alkoxysilanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldiethoxysilane;

  For example, imidazole-based alkoxysilanes such as 3- (2-imidazolin-1-yl) propyltrimethoxysilane and 3- (2-imidazolin-1-yl) propyltriethoxysilane;

  For example, isocyanate-based alkoxysilanes such as 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and 3-isocyanatepropyltripropoxysilane;

  For example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- ( Epoxy alkoxysilanes such as 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane;

  For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylethyldiethoxysilane, 3-aminopropyldimethylethoxy. Silane, N- (2-aminomethyl) 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3- (2-aminoethylaminopropyl) trimethoxysilane, N- (2-Aminoethyl) 3-aminopropylmethyldimethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 3- [2- (2-aminoethylaminoethylamino) propyl] trimethoxysilane, methyltris (2-aminoethoxy) ) Silane Butylaminomethyltrimethoxysilane, 2- (2-aminoethylthioethyl) trimethylsilane, 2- (2-aminoethylthioethyl) methyldiethoxysilane, 3-allylaminopropyltrimethoxysilane, 3-cyclohexylaminopropyltrisilane Methoxysilane, 2-cyclohexylaminoethylthiomethyltrimethoxysilane, 3- (N-phenyl) aminopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, N- [2- (vinylbenzylamino) ethyl] -3 -Aminopropyltrimethoxysilane, 2- (2-aminoethylthioethyl) triethoxysilane, 3-piperazinopropylmethyldimethoxysilane, 3-piperazinopropyltrimethoxysilane, 3-ureidopropyltriethoxysila Amino-based alkoxysilane, etc. and the like.

  Further, as the silane compound (b2), it is possible to use a commercially available product, or it is possible to use an oligomer silane obtained by hydrolyzing and condensing a mixture of two or more kinds of silanes to form an oligomer. The silane compound (b2) may be used alone or in combination of two or more kinds, but a silane compound having no aromatic ring is preferable from the viewpoint of wettability and spreadability to an adherend. In addition, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane are preferred in terms of condensation reaction with hydroxyl groups contained in the polyurethane urea resin (A) and improvement of adhesion to the surface of the substrate. Alkyl-based alkoxysilanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane and other mercapto-based alkoxysilanes, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane Epoxy alkoxysilanes such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, imidazole alkoxysilanes such as 3- (2-imidazolin-1-yl) propyltriethoxysilane, 3-aminopropyl Trimethoxy 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, 2-cyclohexylaminoethylthio Amino-based alkoxysilanes such as methyltrimethoxysilane and trimethylsilyldimethylamine, and isocyanate-based alkoxysilanes such as 3-isocyanatepropyltriethoxysilane are preferably used. The silane compound (b2) can be used alone or in combination of two or more kinds.

  As the methylolmelamine-based compound (b3), a methylolmelamine derivative obtained by condensing melamine and formaldehyde, and a lower alcohol such as methyl alcohol, ethyl alcohol, or isopropyl alcohol, etc. are reacted to be etherified. Examples thereof include compounds such as monomethylolmelamine, dimethylolmelamine, trimethylolmelamine (also known as cearicin), tetramethylolmelamine, pentamethylolmelamine, pentamethoxymethylolmelamine, hexamethylolmelamine, hexamethoxymethylolmelamine, hexaethoxymethylmelamine. , Hexakis- (methoxymethyl) melamine, N, N ', N "-trimethyl-N, N', N" -trimethylolmelamine, N, N ', N "-tri Ji melamine, N, N ', N "- tributyl -N, N', N" - trimethylolmelamine, (hydroxymethyl) pentakis (methoxymethyl) melamine, hexamethylol melamine pentamethyl ether.

  The methylol melamine compound (b3) may be used alone or in combination of two or more kinds. Of these, pentamethoxymethylolmelamine and hexamethoxymethylmelamine are preferable from the viewpoint of condensation reaction with hydroxyl groups contained in the polyurethane urea resin (A) and improvement of adhesion to the surface of the substrate.

  As the reactive compound (B) having a functional group capable of reacting with a hydroxyl group, a polyisocyanate (b1), a silane compound (b2), a methylolmelamine compound (b3), etc. are used. In addition to excellent adhesion to the base material (G) described below, suppression of reduction of cohesive force associated with the inclusion of the adhesive agent (D) described below, maintenance of flexibility by control of crosslinking density, or re-peel The polyisocyanate (b1) is preferably used from the viewpoint of maintaining the property.

<Ester compound (C)>
Next, the ester compound (C) will be described.
In one embodiment of the pressure-sensitive adhesive of the present invention, the pressure-sensitive adhesive may further contain an ester compound (C) in addition to the above essential components.
The ester compound (C) imparts a plasticizing effect to the adhesive layer after coating,
The adhesiveness of the adhesive sheet to the skin can be further improved. Further, after the adhesive sheet is attached to the skin, peeling at the time of peeling can be lightened, so that workability is improved. Further, it is possible to suppress contamination such as adhesive residue on the adherend. Components other than the polyurethane urea resin (A) and the reactive compound (B) having a functional group capable of reacting with a hydroxyl group are referred to as optional components.

  The ester compound (C) is an esterified product of a fatty acid such as an aliphatic carboxylic acid, an aliphatic phosphoric acid, and an aliphatic boric acid and a hydroxyl group-containing aliphatic alcohol, and an epoxy-modified ester obtained by further epoxy-modifying these esterified products. It is a compound. The ester compound (C) does not include an ethylenically unsaturated double bond-containing compound and an organic solvent. The ester compound (C) is roughly classified into a fatty acid ester (c1), a phosphoric acid ester (c2), and a boric acid ester (c3).

  The fatty acid ester (c1) is (1) an ester of a monobasic acid or polybasic acid having 4 to 22 carbon atoms and a monohydric alcohol having 22 or less carbon atoms, (2) one having 18 to 22 carbon atoms. An ester of a basic acid and a tetravalent or less alcohol having 22 or less carbon atoms, and an epoxy-modified ester obtained by further modifying the ester of (3) (1) or (2) with epoxy are preferable.

  The saturated monobasic acid having 4 to 22 carbon atoms is, for example, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, 2-ethylcaproic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecyl acid, Examples thereof include palmitic acid, margaric acid, stearic acid, isostearic acid, arachidic acid, behenic acid and the like.

  Unsaturated monobasic acids having 4 to 22 carbon atoms include crotonic acid, palmitoleic acid, sabienoic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, pinolenic acid, eleostearic acid, stearidonic acid, boseopentaene. Acid, gadoleic acid, icosadienoic acid, icosatrienoic acid, eicosenoic acid, eicosadienoic acid, eicosatrienoic acid, eicosatetraenoic acid, eicosapentaenoic acid, mead acid, arachidonic acid, erucic acid, docosadienoic acid, adrenic acid, ozbondic acid, Examples include sardine acid and docosahexaenoic acid.

  Examples of the saturated dibasic acid having 4 to 22 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,10-decanedioic acid and 1,12-dodecanedioic acid. Acid, 1,12-octadecanedioic acid, eicosanedioic acid and the like can be mentioned.

  Examples of the unsaturated dibasic acid having 4 to 22 carbon atoms include maleic acid, fumaric acid, mesaconic acid, muconic acid and the like.

  The polybasic acids having 4 to 22 carbon atoms include isocitric acid, aconitic acid, 1,2,3-propanetricarboxylic acid, 1,2,3-propenetricarboxylic acid, camphoronic acid, isocamphoronic acid, ethanetetracarboxylic acid, butane. Examples thereof include tetracarboxylic acid, octane tetracarboxylic acid, ethylene tetracarboxylic acid, butene tetracarboxylic acid and the like.

  Monovalent saturated alcohols having 22 or less carbon atoms include, for example, methanol, ethanol, propanol, butanol, hexanol, 2-ethylhexanol, april alcohol, pelargone alcohol, caprin alcohol, undecyl alcohol, 2-butyloctanol, and lauryl. Alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetanol (also known as palmityl alcohol), isocetyl alcohol, heptadecanol, stearyl alcohol, isostearyl alcohol, nonadecyl alcohol, eicosanol (also known as arachidyl alcohol) Also called), octyldodecyl alcohol, heneicosanol, behenyl alcohol, 2- (2-butoxyethoxy) ethyl alcohol, 2- 2-methoxyethoxy) ethyl alcohol, and or alkylene oxide adducts thereof, and the like.

  Monovalent unsaturated alcohols having 22 or less carbon atoms include, for example, palmitolyl alcohol, elaidyl alcohol, oleyl alcohol, linoleyl alcohol, elide linoleyl alcohol, linolenyl alcohol, erucyl alcohol, or the like. The alkylene oxide adduct of

  Examples of the dihydric or tetrahydric alcohol having 18 or less carbon atoms include, for example, the diols having 22 or less carbon atoms, ricinoleyl alcohol, glycerin, diglycerin, polyglycerin, and trimethylolpropane which are mentioned in the polyol (a1). , Pentaerythritol, sorbitol and the like, or alkylene oxide adducts thereof.

  In the fatty acid ester (c1), (1) the ester of a monobasic acid or polybasic acid having 4 to 22 carbon atoms and a monohydric alcohol having 22 or less carbon atoms includes, for example, isopropyl caproate and lauryl caproate. , Stearyl caproate, cetyl caprylate, stearyl caprylate, cetyl 2-ethylcaproate, isocetyl 2-ethylcaproate, stearyl 2-ethylcaproate, stearyl caprate, hexyldecyl dimethyloctanoate, methyl laurate, laurate Butyl, hexyl laurate, cetyl laurate, stearyl laurate, isopropyl myristate, isocetyl myristate, stearyl myristate, myristyl myristate, octyldodecyl myristate, isopropyl palmitate, 2-ethyl palmitate Ruhexyl, lauryl palmitate, isostearyl palmitate, methyl stearate, butyl stearate, 2-ethylhexyl stearate, isocetyl stearate, stearyl stearate, octyldodecyl stearate, isotridecyl stearate, isocesyl isostearate, isopropyl isostearate, Saturated fatty acid monoesters of monobasic acids and monohydric alcohols such as cholesteryl isostearate, isostearyl behenate, polyoxyethylene lauric acid methyl ester, polyoxyethylene lauric acid stearyl ester, polyoxyethylene stearic acid isopropyl ester;

  For example, lauryl methacrylate, methyl crotonate, butyl crotonate, methyl palmitoleate, octyldodecyl palmitoleate, methyl sabienate, methyl oleate, methyl oleate, isopropyl oleate, butyl oleate, octyl oleate, octyl oleate. Dodecyl, methyl elaidate, methyl vaccenate, methyl linoleate, ethyl linoleate, isopropyl linoleate, butyl linoleate, octyldodecyl linoleate, ethyl linolenate, octyldodecyl linolenate, methyl pinolenate, methyl pinolenate, eleo. Methyl stearate, Methyl stearidate, Butyl stearidate, Methyl boseopentaenoate, Methyl gadoleate, Methyl icosadienoate, Methyl icosatrienoate, Eicosene Methyl, ethyl eicosenoate, isopropyl eicosenoate, methyl eicosadienate, methyl eicosatrienoate, methyl eicosatetraenoate, methyl eicosapentaenoate, methyl meadate, methyl arachidonic acid, methyl erucate, methyl docosadienoate, adrenate Unsaturated fatty acid monoesters of monobasic acids such as methyl, methyl ozbondate, methyl sardine, and methyl docosahexaenoate with monohydric alcohols;

  For example, diethyl succinate, diisopropyl succinate, dibutyl succinate, dimyristyl succinate, diethyl glutarate, diethyl 3-methylglutarate, dibutyl glutarate, diethyl adipate, diisopropyl adipate, bis (2-butoxyethyl adipate). , Bis {2- (2-butoxyethoxy) ethyl adipate}, bis (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, diisostearyl adipate, diethyl pimelate, dibutyl pimelate, diethyl suberate , Diethyl azelate, diethyl sebacate, diisopropyl sebacate, dibutyl sebacate, diisocetyl sebacate, dibutyloctyl sebacate, diisostearyl sebacate, dibutyl 1,10-decanedioate. Saturated fatty acid diester of a dibasic acid and a monohydric alcohol and the like;

  For example, dimethyl maleate, diethyl maleate, diisopropyl maleate, dibutyl maleate, dimethyl fumarate, diisopropyl fumarate, dimethyl mesaconate, diethyl mesaconate, diisopropyl mesaconate, dibutyl meconate, dimethyl muconate, diethyl muconate, etc. Unsaturated fatty acid diesters of dibasic acids with monohydric alcohols;

Trimethyl isocitrate, trimethyl aconitate, trimethoxy polyoxyethylene aconitate, trimethyl 1,2,3-propane tricarboxylate, trimethyl 1,2,3-propene tricarboxylate, trimethyl camphoroneate, trimethoxy polyoxyethylene camphoroneate, Trimethyl isocampholone, tetramethyl ethanetetracarboxylate, dimethyl butanetetracarboxylate, trimethyl butanetetracarboxylate, tetramethyl butanetetracarboxylate, tetramethyl octanetetracarboxylate, tetramethyl ethylenetetracarboxylate, tetramethyl butenetetracarboxylate Unsaturated fatty acid polyhydric esters of polybasic acids such as and monohydric alcohols;

  For example, polybasic acids such as monoisopropyl succinate, monoethyl adipate, monoisodecyl adipate, monoisopropyl sebacate, monoisostearyl sebacate, monoethyl mesaconate, monoisopropyl mesaconate, dimethyl aconitate, dimethyl camphoronate and monovalent Unsaturated fatty acid monoesters with alcohols are mentioned.

  In the fatty acid ester (c1), (2) an ester of a monobasic acid having 4 to 22 carbon atoms and a tetravalent or less alcohol having 22 or less carbon atoms includes, for example, diethylene glycol dibutyrate and divaleric acid. Diethylene glycol, neopentyl glycol dicaproate, diethylene glycol dicaproate, triethylene glycol dicaproate, oxyethylene dicaproate, dipropylene glycol dicaproate, polyoxypropylene dicaproate, dienanthate diethylene glycol, neopentyl glycol dicaprylate, ethylene glycol dicaprylate, Propylene glycol dicaprylate, polyoxyethylene dicaprylate, neopentyl glycol di2-ethylcaproate, diethylene glycol di2-ethylcaproate, di-2 Ethylcaproic acid polyoxypropylene, di2-ethylcaproic acid dipropylene glycol, di-2-ethylcaproic acid dipropylene glycol, dipelargonic acid diethylene glycol, dicapric acid diethylene glycol, dicapric acid propylene glycol, dicapric acid polyoxyethylene, dilauric acid neopentyl Glycol, diethylene glycol dilaurate, polyoxyethylene dilaurate, polyoxypropylene dilaurate, neopentyl glycol dimyristate, diethylene glycol dimyristate, dipropylene glycol dimyristate, polyoxypropylene dimyristate, polyoxyethylene dimyristate , Polyoxypropylene dimyristate, diethylene glycol dipentadecylate, dipal Neopentyl glycol titanate, diethylene glycol dipalmitate, polyoxyethylene dipalmitate, diethylene glycol dimargarate, neopentyl glycol distearate, ethylene glycol distearate, diethylene glycol distearate, polyoxyethylene distearate, polyoxypropylene distearate, distearate Acid ricinoleyl, diisostearate diethylene glycol, diisostearate polyoxyethylene, diisostearate propylene glycol, diisostearate polyoxypropylene, diarachidate diethylene glycol, dibehenate diethylene glycol, polyoxyethylene bisphenol A lauric acid ester, etc. Alcohol (also known as Geo) Saturated fatty acid diester with

  For example, ethylene glycol dicrotonate, propylene glycol dicrotonate, polyoxyethylene dicrotonate, ethylene glycol dipalmitoleate, ethylene glycol disabienate, ethylene glycol dioleate, polyoxyethylene dioleate, neopentyl glycol dioleate, hexyl glycol dioleate. , Propylene glycol dioleate, polyoxypropylene dioleate, ethylene glycol dielaidate, polyoxypropylene dielaidate, ethylene glycol divaccenate, ethylene glycol dilinoleate, propylene glycol dilinoleate, neopentyl glycol dilinoleate, ethylene glycol dilinolenate, dilinolene Acid polyoxyethylene, propylene dilinolenate Recall, polyoxyethylene dilinoleate, neopentyl glycol dilinolenate, ethylene glycol dipinolenate, ethylene glycol dieleostearate, ethylene glycol distearidate, ethylene glycol diboseopentaenoate, ethylene glycol digaderate, ethylene glycol diicosadienate, diicosatriene Acid ethylene glycol, dieicosenoic acid ethylene glycol, dieicosadienoic acid ethylene glycol, dieicosatrienoic acid ethylene glycol, dieicosatetraenoic acid ethylene glycol, dieicosapentaenoic acid ethylene glycol, dimead acid ethylene glycol, diarachidonic acid ethylene glycol, dierucic acid ethylene glycol, Didocosadienoic acid ethylene glycol, dia Unsaturated monobasic acids such as ethylene glycol rhenate, ethylene glycol diosbondate, ethylene glycol diiwase acid, ethylene glycol didocosahexaenoate, polyoxyethylene di-2-ethylcaproic acid ether / capric acid ester, and divalent alcohol (alias: Unsaturated fatty acid diester with diol);

  For example, caproic acid triglyceride, caprylic acid triglyceride, 2-ethylcaproic acid triglyceride, 2-ethylcaproic acid polyoxyethylene triglyceride, 2-ethylcaproic acid polyoxypropylene triglyceride, pelargonic acid triglyceride, capric acid triglyceride, lauric acid triglyceride, lauric acid Acid polyoxyethylene triglyceride, myristic acid triglyceride, myristic acid polyoxyethylene triglyceride, pentadecyl acid triglyceride, palmitic acid triglyceride, palmitic acid polyoxyethylene triglyceride, margaric acid, stearic acid diglyceride, stearic acid triglyceride, stearic acid polyoxyethylene triglyceride, Isostearic acid triglyceride, arachidic acid Liglyceride, behenic acid triglyceride, trimethylolpropane tricaproate, trimethylolpropane tricaprylate, trimethylolpropane tri-2-ethylcaproate, polypolyoxyethylene trimethylolpropane tri-2-ethylcaproate, trimethylolpropane tricaprylate, trilaurate trilaurate Methylolpropane, trimethylolpropane trilaurate, polyethylene glycol trimethylolpropane trilaurate, trimethylolpropane dimyristate, trimethylolpropane trimyristate, trimethylolpropane tripalmitate, trimethylolpropane tripalmitate, tristearic acid Trimethylolpropane, tristearic acid polyoxyethylene trimethyl Roll propane, trimethylol propane triisostearate, pentaerythritol tetracaproate, pentaerythritol tetracaprylate, pentaerythritol tetra-2-ethylcaproate, pentaerythritol tetracaprate, pentaerythritol tetralaurate, pentaerythritol tetramyristate, mono Pentaerythritol palmitate, Pentaerythritol dipalmitate, Pentaerythritol tripalmitate, Pentaerythritol tetrapalmitate, Pentaerythritol monostearate, Pentaerythritol distearate, Pentaerythritol tristearate, Pentaerythritol tetrastearate, Pentatetraisostearate Erythritol, tetra-2-ethyl Diglyceryl pronate, diglyceryl tetralaurate, diglyceryl tetramyristate, diglyceryl tetrapalmitate, diglyceryl tetrastearate, polyoxyethylene sorbitate hexa-2-ethylcaproate, polyoxyethylene sorbit hexalaurate, hexamyristin Acid polyoxyethylene sorbit, hexapalmitic acid polyoxyethylene sorbit, tristearate polyoxyethylene sorbit, hexastearate polyoxyethylene sorbit, hexaisostearate polyoxyethylene sorbit, tetralauric acid polyglyceryl, tetrastearate polyglyceryl, hexastearin Saturated fatty acid polyhydric ester of saturated monobasic acid such as polyglyceryl acid and polyhydric alcohol;

  For example, crotonic acid triglyceride, palmitoleic acid triglyceride, sabienoic acid triglyceride, oleic acid diglyceride, oleic acid triglyceride, elaidic acid triglyceride, vaccenic acid triglyceride, linoleic acid diglyceride, linoleic acid triglyceride, linolenic acid diglyceride, linolenic acid triglyceride, pinolenic acid triglyceride, Eleostearic acid triglyceride, stearidonic acid triglyceride, boseopentaenoic acid triglyceride, gadoleic acid triglyceride, icosadienoic acid triglyceride, icosatrienoic acid triglyceride, eicosenoic acid triglyceride, eicosadienic acid triglyceride, eicosatrienoic acid triglyceride, eicosatetraenoic acid triglyceride, eicosapentaenoic acid Trig Ceride, Meadic acid triglyceride, Arachidonic acid triglyceride, Erucic acid triglyceride, Docosadienoic acid triglyceride, Adrenic acid triglyceride, Ozubondic acid triglyceride, Iwasic acid triglyceride, Docosahexaenoic acid triglyceride, Tetracrotonic acid pentaerythritol, Tetrapalmitoleic acid pentaerythritol, Tetrasabienoic acid penta Erythritol, pentaerythritol monooleate, pentaerythritol dioleate, pentaerythritol trioleate, pentaerythritol tetraoleate, pentaerythritol tetraelaidate, pentaerythritol tetravacenoate, pentaerythritol tetralinoleate, pentaerythritol dilinolenate, trilinolene. Acid pentaery Litol, pentaerythritol tetralinolenate, pentaerythritol tetrapinolenate, pentaerythritol tetraeleostearate, pentaerythritol tetrastearate, pentaerythritol tetraboseopentaenoate, pentaerythritol tetragadrate, pentatricosadienoate penta Erythritol, pentaerythritol tetriicosatrienoate, pentaerythritol tetraeicosenoate, pentaerythritol tetraeicosadienoate, pentaerythritol tetraeicosatrienoate, pentaerythritol tetraeicosatetraenoate, pentaerythritol tetraeicosapentaenoate, tetramead Acid pentaerythritol, tetraarachidonic acid pentaerythritol, tetraerucic acid pen Taerythritol, pentaerythritol tetradocosadienoate, pentaerythritol tetraadrenoate, pentaerythritol tetraosdenoate, pentaerythritol tetraywashiate, pentaerythritol tetradocosahexaenoate, polyoxyethylene triglyceride crotonic acid, palmitoleic acid polyoxyethylene triglyceride, linoleic acid Polyoxyethylene triglyceride, linolenic acid polyoxyethylene triglyceride, oleic acid polyoxyethylene triglyceride, tetrapalmitoleic acid polyoxyethylene pentaerythritol, tetralinoleic acid polyoxyethylene pentaerythritol, tetralinolenic acid polyoxyethylene pentaerythritol, hexacrotonic acid poly Oxyethylene sorbit, Xapalmitoleic acid Polyoxyethylene sorbite Trioleic acid Polyoxyethylene sorbit, Tetraoleic acid polyoxyethylene sorbit, Hexaoleic acid polyoxyethylene sorbit, Hexalaidic acid polyoxyethylene sorbit, Tetralinoleic acid polyoxyethylene sorbit, Hexalinoleic acid Unsaturated monobasic acids and polyhydric alcohols such as polyoxyethylene sorbit, tetralinolenic acid polyoxyethylene sorbit, hexalinolenic acid polyoxyethylene sorbit, hexastearidonic acid polyoxyethylene sorbit, hexaeicosenoic acid polyoxyethylene sorbit Unsaturated fatty acid polyvalent ester of

  For example, glyceryl mono-2-ethylcaproate, glyceryl di2-ethylcaproate, glyceryl tri-2-ethylhexanoate, glyceryl monobehenate, glyceryl monocaprylate, glyceryl tricaprylate, glyceryl trilaurate, glyceryl tricaprate, triisostearate. Glyceryl, glyceryl dibehenate, glyceryl tribehenate, glyceryl tribehenate, polyoxyethylene glyceryl monolaurate, polyoxyethylene glyceryl monomyristate, polyoxyethylene glyceryl monostearate, polyoxyethylene glyceryl monooleate, mono-2-ethylcapron Acid trimethylolpropane, di2-ethylcaproic acid trimethylolpropane, tri-2-ethylcaproic acid trimethylolpropane Polyoxyethylene trimethylol propane monolaurate, polyoxyethylene trimethylol propane monomyristate, polyoxyethylene trimethylol propane monostearate, polyoxyethylene trimethylol propane monooleate, polyoxyethylene trimethylol propane monolinoleate, mono Linolenic acid polyoxyethylene trimethylolpropane, polyoxyethylene sorbitan monostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate Ester, Polyoxyethylene glyceryl monoisostearate, Pentaeryth Tall mono laurate, pentaerythritol monomyristate, pentaerythritol monostearate, pentaerythritol monooleate, fatty acid monoesters of monobasic acids with polyhydric alcohols such as pentaerythritol mono linoleic acid esters.

In the fatty acid ester (c1), as the epoxy modified ester obtained by further modifying the ester of (3), (1) or (2) with epoxy, the unsaturated fatty acid monoester, unsaturated fatty acid diester, or unsaturated fatty acid polyvalent An epoxy-modified ester obtained by reacting an ester with a peracid such as m-chloroperbenzoic acid or dimethyloxirane to epoxidize the olefinic double bond contained in the unsaturated fatty acid ester can be mentioned.
The fatty acid ester (c1) can be used alone or in combination of two or more kinds.

The phosphoric acid ester (c2) is an ester compound obtained by dehydration condensation of phosphoric acid and the above-mentioned tetravalent or less alcohol having 22 or less carbon atoms.
For example, monomethyl phosphate, monoethyl phosphate, monopropyl phosphate, monobutyl phosphate, monohexyl phosphate, mono-2-ethylhexyl phosphate, monoapril phosphate, monopelargon phosphate, monocaprin phosphate, monoundecyl phosphate, phosphate Mono-2-butyloctyl, monolauryl phosphate, monotridecyl phosphate, monomyristyl phosphate, monopentadecyl phosphate, monopalmityl phosphate, monoisocetyl phosphate, monoheptadene phosphate, monostearyl phosphate, monoisostearyl phosphate, Monononadecyl phosphate, monoarachidyl phosphate, monooctyldodecyl phosphate, monoheneicosan phosphate, monobehenyl phosphate, mono-2- (2-butoxyethoxy) ethyl phosphate, mono-2- (2-methoxyethoxy) ethyl phosphate Yama Phosphate saturated monocarboxylic esters such as alkylene oxide adducts thereof;

  For example, monopalmitrail phosphate, monoelaidyl phosphate, monooleyl phosphate, monolinoleyl phosphate, monoeline linoleyl phosphate, monolinolenyl phosphate, monoercyl phosphate, or unsaturated phosphates such as alkylene oxide adducts thereof. Monoester;

  For example, dimethyl phosphate, diethyl phosphate, dipropyl phosphate, dibutyl phosphate, dihexyl phosphate, di2-ethylhexyl phosphate, diapril phosphate, diperalgon phosphate, dicaprin phosphate, diundecyl phosphate, di2-diphosphate. Butyl octyl, dilauryl phosphate, ditridecyl phosphate, dimyristyl phosphate, dipentadecyl phosphate, dipalmityl phosphate, diisocetyl phosphate, diheptadene phosphate, distearyl phosphate, diisostearyl phosphate, dinonadecyl phosphate, diarachidyl phosphate , Dioctyldodecyl phosphate, diheneicosane phosphate, dibehenyl phosphate, di2- (2-butoxyethoxy) ethyl phosphate, di2- (2-methoxyethoxy) ethyl phosphate, or alkylene oxide adducts thereof. Phosphoric acid saturated di Ester;

  For example, dipalmitrail phosphate, dielaidyl phosphate, dioleyl phosphate, dilinoleyl phosphate, dielidelinoleyl phosphate, dilinolenyl phosphate, diersyl phosphate, or unsaturated phosphonate diesters of these alkylene oxide adducts, etc. ;

  For example, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, trihexyl phosphate, tri-2-ethylhexyl phosphate, triapril phosphate, triperalgon phosphate, tricaprin phosphate, triundecyl phosphate, triundecyl phosphate. 2-butyloctyl, trilauryl phosphate, tritridecyl phosphate, trimyristyl phosphate, tripentadecyl phosphate, tripalmityl phosphate, triisocetyl phosphate, triheptadene phosphate, tristearyl phosphate, triisostearyl phosphate, phosphorus Trinonadecyl acid salt, triarachidyl phosphate, trioctyldodecyl phosphate, triheneicosan phosphate, ditribehenyl phosphate, tri-2- (2-butoxyethoxy) ethyl phosphate, tri2- (2-methoxyethoxy) ethyl phosphate and , Other phosphate saturated triesters such as alkylene oxide adducts thereof;

  For example, tripalmitoleyl phosphate, trielaidyl phosphate, trioleyl phosphate, trilinoleyl phosphate, trielidolinoleyl phosphate, trilinolenyl phosphate, triercyl phosphate, or unsaturated phosphates such as alkylene oxide adducts thereof. Triesters;

  For example, for example, polyoxyethylene oleyl ether phosphate, polyoxyethylene lauryl ether phosphate, polyoxyethylene cetyl ether phosphate, polyoxyethylene octyl ether phosphate, polyoxyethylene decyl ether phosphate, etc. Addition number of ethylene oxide (EO) 2 to 20 polyoxyalkylene alkyl ether phosphate ester;

For example, polyoxyethylene oleyl phenyl ether phosphate, polyoxyethylene lauryl phenyl ether phosphate, polyoxyethylene cetyl phenyl ether phosphate, polyoxyethylene octyl phenyl ether phosphate, polyoxyethylene decyl phenyl ether phosphate Examples thereof include esters and polyoxyethylene alkylphenyl ether phosphates having an addition mole number of ethylene oxide (EO) of 2 to 20, such as polyoxyethylene ethylphenyl ether phosphate.
The phosphoric acid ester (c2) can be used alone or in combination of two or more kinds.

The boric acid ester (c3) is an ester compound obtained by dehydration condensation of boric acid and the above-mentioned tetravalent or less alcohol having 22 or less carbon atoms.
For example, methoxydiethylene glycol ether borate, methoxytriethylene glycol ether borate, methoxytetraethylene glycol ether borate, ethoxytriethylene glycol ether borate, ethoxydiethylene glycol ether borate, ethoxytetraethylene glycol ether borate Ester, propoxy triethylene glycol ether borate ester, triethylene glycol monobutyl ether borate ester, diethylene glycol monobutyl ether borate ester, butoxy tetraethylene glycol ether borate ester, butoxy triethylene glycol ether borate ester, butoxy tetraethylene glycol ether Borate ester Xypentoxydiethylene glycol ether borate, pentoxytriethylene glycol ether borate, 2-ethylhexyloxydiethylene glycol ether borate, diethylene glycol monopropyl ether ether borate, triethylene glycol monopropyl ether borate, polyethylene glycol mono Addition of ethylene oxide (EO) such as butyl ether borate ester, polyethylene glycol monopropyl ether borate ester, polyethylene glycol monobutyl ether borate ester, etc. Polyoxyalkylene alkyl ether borate ester having 2 to 20 moles;

  For example, dipropylene glycol monomethyl ether borate, dipropylene glycol monopropyl ether borate, tripropylene glycol monopropyl ether borate, dipropylene glycol monobutyl ether borate, dipropylene glycol monomethyl ether borate, tri Propylene oxide such as propylene glycol monoethyl ether borate ester, tripropylene glycol monopropyl ether borate ester, tripropylene glycol monobutyl ether borate ester, polypropylene glycol monopropyl ether borate ester, polypropylene glycol monobutyl ether borate ester, etc. ) Polyoxyalkylene alkyl having an addition mole number of 2 to 20 Ether borate ester;

For example, polybutylene glycol monopropyl ether borate ester, polybutylene glycol monobutyl ether borate ester, and other polyoxyalkylene alkyl ether borate ester having an addition mole number of 2 to 20 of butylene oxide (BO);

For example, di (glycerin) borate monostearate, di (glycerin) borate sesquistearate, di (glycerin) borate monooleate, polyoxyethylene di (glycerin) borate monopalminate (EO addition mole number: 6 to 20), Examples thereof include glycerin ether borate esters such as polyoxyethylene di (glycerin) borate monooleate (EO addition mole number: 6 to 20).
The boric acid ester (c3) can be used alone or in combination of two or more kinds.

  The ester compound (C) preferably has a molecular weight (formula weight) of 200 to 2,000. When the molecular weight is within the above range, the compatibility with the polyurethane resin (A) is improved, so that the transparency and cohesive force are improved, the re-peeling property is improved, and the damage such as peeling the keratin of the skin is suppressed. Is possible.

  The ester compound (C) is preferably contained in an amount of 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the polyurethane urea resin (A). When the amount of the ester compound (C) is within the above range, the adhesive layer can be sufficiently plasticized and the flexibility is improved, so that the conformability to the skin is improved and the removability is further improved.

  Among these, the ester compound (C) is, for example, 2-ethylcaproic acid cetyl, 2-ethylcaproate from the viewpoints of industrial followability, skin followability, removability, and skin damage suppression. Isocetyl caproate, stearyl 2-ethylcaproate, isopropyl myristate, isocetyl myristate, octyldodecyl myristate, methyl laurate, butyl laurate, hexyl laurate, hexyldecyl dimethyloctanoate, methyl oleate, myristyl myristate, Isopropyl palmitate, 2-ethylhexyl palmitate, methyl stearate, butyl stearate, 2-ethylhexyl stearate, stearyl stearate, isotridecyl stearate, isopropyl isostearate, cholesteryl isostearate. Lauryl methacrylate, isopropyl oleate, butyl oleate, octyl oleate, octyl decyl oleate, neopentyl glycol di2-ethylcaproate, polyoxyethylene di2-ethylcaproate, propylene glycol dicaprylate, propylene glycol dicaprate. , Propylene glycol diisostearate, bis {2- (2-butoxyethoxy) ethyl adipate}, bis (2-butoxyethyl) adipate, diisodecyl adipate, bis (2-ethylhexyl) adipate, di2-ethylcaproic acid Neopentyl glycol, oxyethylene di2-ethylcaproate (EO addition mole number: 4 to 16), glyceryl tri-2-ethylcaproate, glyceryl monocaprylate, glyceryl tricaprylate, molybdenum Glyceryl behenate, glyceryl monobehenate, glyceryl tri-2-ethylcaproate, glyceryl trilaurate, glyceryl tricaprate, glyceryl triisostearate, polyoxyethylene triglyceride 2-ethylcaproate (EO addition mole number: 2 to 16), poly Fatty acid esters such as oxyethylene bisphenol A lauric acid ester, glyceryl trioleate, trimethylolpropane tri-2-ethylcaproate, oleic acid triglyceride, pentaerythritol monooleate, pentaerythritol monostearate, pentaerythritol tetrapalmitate, and the like, Tri-2-ethylhexyl phosphate, trioctyl phosphate, polyoxyethylene oleyl ether phosphate (EO addition mole number: 2 to 16), Phosphoric acid ester such as polyoxyethylene lauryl ether phosphate (EO addition mole number: 2 to 16), polyoxyethylene octyl ether phosphate (EO addition mole number: 2 to 16), or triethylene glycol monopropyl Examples thereof include ether borate ester, polyethylene glycol monobutyl ether borate ester (EO addition mole number: 2 to 16), and polyoxyethylene glycerin ether borate ester (EO addition mole number: 2 to 16).

<Patch drug (D)>
Further, the patch drug (D) will be described.
In one embodiment of the pressure-sensitive adhesive of the present invention, the pressure-sensitive adhesive may contain an adhesive patch (D) in addition to the above essential components.

  The patch drug (D) includes both the transdermal drug (d1) and the transdermal absorption enhancer (d2) for transdermally administering the transdermal drug (d1), It is called a patch drug (D), which is often liquid at room temperature, and it is possible to enhance the penetration of the drug into the skin by including it in the adhesive layer. The patch drug (D) preferably contains at least one of the transdermal drug (d1) and the transdermal absorption enhancer (d2). Here, the normal temperature is 25 ° C.

The transdermal drug is not particularly limited and may include any drug for wound treatment, local administration, systemic administration and the like. For example, anti-inflammatory analgesics, steroidal anti-inflammatory agents, vasodilators, antihypertensive diuretics, anesthetics, antihistamines, antitumor agents, antihypertensive / arrhythmic agents, antidepressants / anxiolytics, local anesthetics, hormone agents, Examples include asthma / nasal allergy therapeutic agents, anticoagulants, antispasmodics, fat-soluble vitamins, and the like.
The content of the transdermal drug varies depending on the type of the drug and the purpose of use of the patch, but is contained in the range of 0.1% by weight to 30% by weight based on the total weight of the pressure-sensitive adhesive for medical use. It is preferable.

The transdermal absorption enhancer may be a compound that improves skin permeability, and is more preferably a compound that has a function of improving the solubility and diffusibility of the drug in the adhesive layer. For example, silicones such as dimethylpolysiloxane, animal and vegetable oils such as olive oil, hydrocarbons such as liquid paraffin and wax, higher fatty acids such as lauric acid, myristic acid and oleic acid, hexyldecanol, octyldodecanol, isostearyl alcohol and the like. Nonionic surface actives such as higher alcohols, alcohols such as 2-hexyldecanol, 2-octyldecanol and glycerin, polyoxyethylene nonylphenyl ether, fatty acid glycerin ester, fatty acid polyethylene glycol, polyglycerin fatty acid ester, sucrose fatty acid ester Agents, liquid resins such as polybutene, polyisoprene, polyacrylic acid, polymethacrylic acid, oil-based vitamins such as retinol, retinol palmitate, tocophenol, tocophenol acetate And the like. Further, the monohydric alcohol fatty acid ester described in the above ester compound (C) such as isopropyl myristate, hexyl laurate, octyldodecyl myristate, butyl stearate and decyl oleate can also be used as a percutaneous absorption enhancer. .
When these percutaneous absorption enhancers are contained, the viscosity of the medical adhesive layer can be adjusted. The content of the transdermal absorption enhancer varies depending on its type and polarity, the type of pressure-sensitive adhesive, the polarity and the molecular weight, etc. It is preferable to contain in the range.

<Tackifying resin (E)>
Further, the tackifying resin (E) will be described.
In one embodiment of the pressure-sensitive adhesive of the present invention, the pressure-sensitive adhesive may contain a tackifying resin (E) in addition to the above essential components.
The tackifying resin (E) can easily adjust the adhesion to the base material, the adhesion to the skin, and the cohesive force. Examples of the tackifying resin (E) include rosin, hydrogenated rosin, rosin ester, terpene resin, modified terpene resin, hydrogenated terpene resin, terpene phenol resin, petroleum resin, coumarone indene resin, phenol resin, xylene resin, Examples thereof include alicyclic saturated hydrocarbon resin. Among these, rosin-based resins and hydrogenated petroleum resins are preferable from the viewpoint of compatibility with the polyurethane urea resin (A) and suppression of skin irritation.
These may be used alone or in combination of two or more. The content of the tackifying resin varies depending on its type, polarity and the like, but is usually preferably in the range of 1% by weight to 50% by weight based on the total weight of the pressure-sensitive adhesive.

<Hydrolysis inhibitor (F)>
Further, the hydrolysis resistant agent (F) will be described.
In one embodiment of the pressure-sensitive adhesive of the present invention, the pressure-sensitive adhesive may contain a hydrolysis inhibitor (F) in addition to the above essential components.
Depending on the type of the polyurethane urea resin (A), when the hydrolysis inhibitor (F) is included, the polyurethane urea resin (A) is generated when the hydrolysis occurs in a high temperature and high humidity atmosphere or in an aqueous medium. Capable of blocking carboxyl groups. The hydrolysis inhibitor (F) is preferably, for example, a carbodiimide-based, isocyanate-based, oxazoline-based, or epoxy-based agent, and a carbodiimide-based agent is preferable because it can suppress hydrolysis more effectively.
The hydrolysis inhibitor (F) is preferably contained in an amount of 0.01 to 2.0 parts by weight, more preferably 0.02 to 1.5 parts by weight, and 0 to 100 parts by weight of the polyurethane urea resin (A). More preferably, 0.05 to 1.0 part by weight. The hydrolysis inhibitors can be used alone or in combination of two or more kinds.

  Further, the hydrolysis inhibitor (F) is preferably used in combination with an antioxidant described in the other component (P) described later, and by using the hydrolysis inhibitor, hydrolysis resistance is further improved, Decomposition of the suppressor itself and thermal yellowing can also be suppressed.

  The carbodiimide-based hydrolysis inhibitor is a compound having a carbodiimide group in the molecule. Examples of monocarbodiimide compounds include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, diphenylcarbodiimide, naphthylcarbodiimide and the like.

An example of the polycarbodiimide compound is a high molecular weight polycarbodiimide produced by decarboxylation condensation reaction of diisocyanate in the presence of a carbodiimidization catalyst, and such a compound includes those obtained by decarboxylation condensation reaction of the following diisocyanate. To be For example, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethoxy-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 3, 3'-dimethyl-4,4'-diphenyl ether diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane One of diisocyanate, tetramethylxylylene diisocyanate, or a mixture thereof can be used.
In addition, as a carbodiimidization catalyst, 1-phenyl-2-phospholen-1-oxide, 3-methyl-2-phospholen-1-oxide, 1-ethyl-3-methyl-2-phospholen-1-oxide, 1- Examples thereof include ethyl-2-phospholen-1-oxide, and phospholene oxides such as 3-phospholene isomers thereof.

<Other ingredients (P)>
In one embodiment of the pressure-sensitive adhesive of the present invention, other components (P) may be appropriately added to the pressure-sensitive adhesive in addition to the above essential components, as long as the effects of the present invention are not impaired. Is also possible.
The other component (P) is, for example, a reduction in shrinkage due to polymerization and curing, a reduction in thermal expansion coefficient, an improvement in dimensional stability, an improvement in elastic modulus, suppression of redox, a viscosity adjustment, an improvement in thermal conductivity, an improvement in strength, an improvement in toughness, and coloring. From the viewpoint of improvement and the like, organic or inorganic additives and fillers can be added. The filler is composed of polymers, ceramics, metals, metal oxides, metal salts, dyes and pigments, and the like. The shape of the filler is preferably, for example, particulate or fibrous. In addition, additives include antioxidants, flame retardants, storage stabilizers, thixotropy imparting agents, dispersion stabilizers, fluidity imparting agents, thickeners, humectants, pH adjusters, leveling agents and defoamers. As a method of addition, in addition to normal mixing, it is also possible to dissolve, semi-dissolve or microdisperse the polymer blend or polymer alloy in the pressure-sensitive adhesive.

<Pressure sensitive adhesive>
Next, the pressure sensitive adhesive will be described.
The pressure-sensitive adhesive is conventionally referred to as a pressure-sensitive adhesive, and is an adhesive that adheres only by applying pressure for a short time at room temperature because it has a viscous property regardless of solidification of the adhesive. . The pressure-sensitive adhesive of the present invention is a pressure-sensitive adhesive containing a polyurethane urea resin (A) and a reactive compound (B) having a functional group capable of reacting with a hydroxyl group. The constituent monomer units include a polyol (a1) unit, a polyisocyanate (a2) unit and an amine compound (a3) unit, and the polyurethane urea resin (A) does not have an aromatic ring and has an alkylene side chain. A reactive compound (B) having an oxide unit and a hydroxyl group, having a weight average molecular weight of 10,000 to 500,000, and having a functional group capable of reacting with the hydroxyl group with respect to 100 parts by weight of the polyurethane urea resin (A). ) 0.1 to 50 parts by weight is contained, and if necessary, ester compound (C), patch drug (D), tackifying resin (E), hydrolysis Control agent (F) and other components (P) is obtained by appropriately mixing.

  It is preferable that the pressure-sensitive adhesive of the present invention has its viscosity appropriately adjusted according to its usage form. The pressure-sensitive adhesive of the present invention can use the following organic solvents in order to adjust the viscosity. In particular, the organic solvent is an alcohol solvent such as methanol, ethanol or isopropyl alcohol, a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone, an ester solvent such as methyl acetate, ethyl acetate or butyl acetate, cyclohexane, toluene or xylene. It is preferable to use various organic solvents such as hydrocarbon solvents, water, and mixtures thereof. However, caution is required when using a solvent having active hydrogen that may react with the reactive compound (B), such as an alcohol solvent. It is also possible to reduce the viscosity by heating the pressure sensitive adhesive without using additional solvent.

  The viscosity of the pressure-sensitive adhesive of the present invention is 3,000 to 20, at a nonvolatile content concentration (NV) of 50% when measured with a B-type viscometer at 25 ° C. from the viewpoint of forming an adhesive layer. It is preferably 000 mPa · s, and more preferably 4,000 to 15,000 mPa · s. When the viscosity is less than 20,000 mPa · s, the adhesive layer having a thickness of 0.5 to 300 μm can be easily formed, and the transdermal absorbability of the transdermal drug can be improved. Further, when the viscosity is 3,000 mPa · s or more, it becomes easy to control the thickness of the adhesive layer. In this embodiment, the film thickness, viscosity, or non-volatile content concentration of the adhesive layer is appropriately set according to the application of the laminate.

<Method for manufacturing pressure-sensitive adhesive>
As the method for producing the polyurethane urea resin (A), first, the polyol (a1) is reacted with the polyisocyanate (a2) to produce a urethane prepolymer (X) having at least one isocyanate group. Next, the urethane prepolymer (X) thus obtained is reacted with the amine compound (a3) to prepare a polyurethane urea resin (A), and a reactive compound (B) having a functional group capable of reacting with the hydroxyl group is prepared. By reacting, a pressure sensitive adhesive can be obtained.
More specifically, the urethane prepolymer (X) obtained by reacting the polyol (a1) and the polyisocyanate (a2) does not have an aromatic ring and has a primary amine compound having one amino group (a3-). 1-1-1) 2 molar equivalents and an ethylenically unsaturated compound having two double bond groups (a3-1-1-2) 1 molar equivalent are formed from a diamine compound (a3-1). -1) or a primary diamine compound (a3) having no aromatic ring and two amino groups in the urethane prepolymer (X) obtained by reacting the polyol (a1) and the polyisocyanate (a2). -1-2-1) 1 molar equivalent and an ethylenically unsaturated compound (a3-1-2-2) having 1 double bond group 2 molar equivalent are formed from and the diamine compound (a3- 1-2) react, and powder The first step of producing a urethane urea resin (Y) having an isocyanate group in, the urethane urea resin (Y) is reacted with the reaction-terminating amine compound (a3-2-1) to produce a polyurethane urea resin (A). A second step for producing a pressure-sensitive adhesive by mixing the polyurethane urea resin (A) with a reactive compound (B) having a functional group capable of reacting with a hydroxyl group. It is a method for producing a pressure-sensitive adhesive characterized by including the above.

<< First step of producing urethane urea resin (Y) >>
First, the first step of producing the urethane urea resin (Y) having an isocyanate group at the terminal will be described.
The urethanization reaction for producing the urethane prepolymer (X) by reacting the polyol (a1) and the polyisocyanate (a2) can be performed by various methods, but is roughly classified into the following two methods.
[I] A method in which all of the polyol (a1), the polyisocyanate (a2), the organic solvent, and the catalyst are charged into a polymerization tank and reacted.
[Ii] A method in which a polyol (a1), a catalyst and an organic solvent are charged into a polymerization tank, polyisocyanate (a2) is added dropwise from a dropping tank to cause a reaction, and then a catalyst is additionally added if necessary.
[Ii] is preferable when the reaction is precisely controlled. The reaction temperature for obtaining the urethane prepolymer (X) is preferably 140 ° C. or lower. More preferably, it is 50 to 130 ° C. When the temperature is higher than 140 ° C, it becomes difficult to control the reaction rate, and the urethane prepolymer (X) having a predetermined weight average molecular weight and structure cannot be obtained. The urethanization reaction may be carried out in the presence of a catalyst at 50 to 130 ° C. for 1 to 20 hours, although no catalyst is required.

  The mixing ratio of the polyol (a1) and the polyisocyanate (a2) largely depends on the reactivity of the compound, the use of the obtained resin, and the like. In order for the urethane prepolymer (X) to have at least one isocyanate group, the isocyanate group in the polyisocyanate (a2) may be more than 1 mol per 1 mol of the hydroxyl group in the polyol (a1). It is necessary, preferably 1.01 to 4.00 mol, and more preferably 1.05 to 2.00 mol. Within this range, the reactivity with the reactive compound (B) becomes good, so that an adhesive layer having high transparency can be easily obtained, the adhesion to the curved surface portion is improved, and the contamination of the base material at the time of peeling is suppressed. it can.

  The end point of the reaction is judged by measuring the isocyanate content (% by weight) by titration, or by disappearing the characteristic absorption based on the isocyanate group (NCO) by measuring the infrared absorption spectrum (IR). Details of the method for measuring the isocyanate content by titration will be described in Examples.

The urethane urea resin (Y) is produced by the urea-forming reaction between the isocyanate group in the urethane prepolymer (X) obtained above and the amino group of the diamine compound (a3-1), and the following two methods Is mentioned.
[Iii] A method in which the urethane prepolymer (X) is charged into a polymerization tank and the diamine compound (a3-1) is added dropwise to cause a reaction.
[Iv] A method in which the diamine compound (a3-1) is charged in a polymerization tank and the urethane prepolymer (X) is added dropwise.
If there is no problem in the reaction, the method [iii], which is easy to operate, is preferable. The temperature of the urea reaction is preferably 100 ° C or lower. More preferably, it is 70 ° C. or lower. Even at 70 ° C, the reaction rate is high, and if it cannot be controlled, 50 ° C or lower is more preferable. When the temperature is higher than 100 ° C., it is difficult to control the reaction rate, and it is difficult to obtain the polyurethane urea resin (A) having a predetermined weight average molecular weight and structure.
Further, when an alcoholic solvent is used as the organic solvent, it is preferable to keep the temperature in the reaction system at 50 ° C. or lower, more preferably 40 ° C. or lower when the diamine compound (a3-1) is dropped.
In addition, when using the primary amine compound (a3-1-1-1-1) which has a hydroxyl group contained in the diamine compound (a3-1), or the primary diamine compound which has two amino groups ( a3-1-2-1) and an ethylenically unsaturated compound having a hydroxyl group (a3-1-2-2-1), both the amino group and the hydroxyl group are urethane prepolymers ( Although it is possible to react with the terminal isocyanate group of X), the reactivity of the amino group is higher and it preferentially reacts with the isocyanate group.

Here, 2 molar equivalents of a primary amine compound (a3-1-1-1) having one amino group and an ethylenically unsaturated compound (a3 having no aromatic ring and two double bond groups). The method for producing the diamine compound (a3-1-1), which is formed by 1-1-2) and 1 molar equivalent is described below.
2 molar equivalents of a primary amine compound (a3-1-1-1) having one amino group and 1 molar equivalent of an ethylenically unsaturated compound (a3-1-1-2) having two double bond groups The diamine compound (a3-1-1) formed from and is preferably formed by an addition reaction. More specifically, as the ethylenically unsaturated compound (a3-1-1-2) ratio, the first diamine compound (a3-1-1) having one amino group so that at least the amino group remains With respect to 2 mol of the primary amino group contained in the primary amine compound (a3-1-1-1), preferably 0.5 to 1.0 mol, more preferably 0.7 to 1.0 mol, It is preferable to carry out an addition reaction with the ethylenically unsaturated compound (a3-1-1-2). Within this range, the effect of introducing the ethylenically unsaturated compound (a3-1-1-2) is obtained, and the storage stability is further improved, which is preferable.

Next, 1 molar equivalent of a primary diamine compound (a3-1-2-1) having two amino groups and an ethylenically unsaturated compound (a3-1-2-2) 2 having one double bond group The method for producing the diamine compound (a3-1-2), which is formed by using and the molar equivalents of and, will be described.
1 molar equivalent of a primary diamine compound (a3-1-2-1) having two amino groups and 2 molar equivalents of an ethylenically unsaturated compound (a3-1-2-2) having one double bond group It is preferable that the diamine compound (a3-1-2) formed from is similarly formed by an addition reaction. More specifically, as the ratio of the diamine compound (a3-1-2-1), the ethylenically unsaturated compound (a3-1-2) so that at least an amino group remains in the diamine compound (a3-1-2). -2) has a ratio of 1.0 to 2.0 mol, more preferably 1.0 to 1.5 mol, based on 2 mol of the double bond group, and the diamine compound (a3-1-2-). It is preferable to carry out a Michael addition reaction with 1). Within this range, the effect of introducing the primary diamine compound (a3-1-2-1) having two amino groups is obtained, and the storage stability is further improved, which is preferable.
As a method for synthesizing the diamine compound (a3-1), a known method for reaction can be used as it is. For example, Michael, AJ Prakt. Chem. 1887, 35, 349, RE Steiger, Org. Synth., Coll. Vol. 3, 91 (1955)., R. Mozingo, JH McCracken, Org. Synth., Coll. Vol. 3 , 258 (1955). Can be used.

  The ethylenically unsaturated compound (a3-1-1-2) having two double bond groups or the ethylenically unsaturated compound (a3-1-2-2) having one double bond group is ( In the case of (meth) acrylic acid ester, especially acrylic acid ester, etc., the reaction proceeds at 10 to 150 ° C. in the presence of a catalyst such as alcohol, if necessary. A reaction temperature of 40 to 150 ° C is preferable, although it depends on the kind of the ethylenically unsaturated compound used. If the reaction temperature is too high, an ester amide exchange reaction occurs, which is not preferable.

  Further, although a catalyst may or may not be used, when it is used, examples of usable catalysts include tetraethylammonium fluoride, tetrabutylammonium hydroxide, potassium hydroxide, tetramethylguanidine and dia. Examples thereof include zabicycloundecene, sodium t-butyrate, tri-n-octylphosphine and triphenylphosphine. Further, when the ethylenically unsaturated compound does not have an electron-withdrawing group, the reaction becomes possible in the presence of a metal catalyst, and in this case, when the reaction is carried out at 60 to 100 ° C. while heating in the presence of the catalyst, an appropriate reaction occurs. Speed is preferable.

  Further, the organic solvent used in the production may or may not be used, but when used, it is not limited to the kind, and the organic solvent described below can be used, in particular, methyl ethyl ketone, toluene, acetone. Known solvents such as benzene and the like can be used. When an organic solvent is used, the solution concentration is preferably 20% by weight or more, more preferably 50% by weight or more. If the concentration is less than this, the reaction is difficult to proceed, which is not preferable. Furthermore, as the reaction time, the ethylenically unsaturated compound (a3-1-1-2) having two double bond groups to be used or the ethylenically unsaturated compound (a3-1 having one double bond group) is used. -2-2) Depending on the type, it will be completed in 30 minutes to 6 hours.

<< Second step of producing polyurethane urea resin (A) by reacting urethane urea resin (Y) with amine compound (a3-2) >>
Next, the second step of producing the polyurethane urea resin (A) by further reacting the urethane urea resin (Y) with the amine compound (a3-2) will be described.
Among the amino compounds (a3), the amine compound (a3-2) is used for inactivating by reacting with the isocyanate group remaining in the urethane urea resin (Y), and as described above, the reaction terminator. When used as, a reaction stopping amine compound (a3-2-1) is used. When the reaction-terminating amine compound (a3-2-1) is used as a reaction terminator, the molecular weight and solution viscosity of the polyurethane urea resin (A) can be controlled, or the resin reacts with unreacted isocyanate groups remaining at the terminals. It is possible to stabilize the reaction activity of.

  The amount of the reaction-terminating amine compound (a3-2-1) used in the amine compound (a3-2) differs depending on whether the amine compound (a3-2-1) is mixed with the diamine compound (a3-1) or added last alone. However, in the case of mixing and adding, the amino group in the reaction-terminating amine compound (a3-2-1) is added to 1 mol of the isocyanate group in the urethane prepolymer (X) per> mol of NH bond. It is preferably used in an amount of 0.5 mol or less, more preferably 0.3 mol or less, and when added alone at the end, it is 0 mol based on 1 mol of the isocyanate group finally present. The amount is 0.01 to 3.0 mol, and preferably 0.02 to 3.0 mol for the purpose of stabilizing the polyurethane urea resin (A). Outside this range, adverse effects such as reduced film formability and discoloration may be observed.

  The end point of the reaction is judged by measuring the isocyanate group content (wt%) by titration or by disappearance of the isocyanate group peak by IR measurement. The details of the method for measuring the isocyanate group content by titration will be described in Examples.

  Further, at the time of producing the urethane prepolymer (X), known catalysts such as the tertiary amine compounds and the organometallic compounds described above can be used. The organometallic compound catalyst used when synthesizing the urethane prepolymer (X) significantly accelerates the reaction when the urethane prepolymer (X) reacts with the amine compound (a3). The reaction between the isocyanate group and the amino group is originally very fast, but in the presence of the organometallic compound catalyst, the reaction is further promoted, which may make control difficult. At this time, if a chelate compound is present, a chelate is formed with this organometallic compound catalyst, the catalytic ability is adjusted, and the reaction with the amine compound (a3) is easily controlled.

  Examples of the chelate compound include acetylacetone, dimethylglyoxime, oxine, dithizone, polyaminooxy acids such as ethylenediaminetetraacetic acid (alias: EDTA), oxycarboxylic acids such as citric acid, condensed phosphoric acid, and the like. Among the chelate compounds, acetylacetone is preferable because it is soluble in an organic solvent, has volatility, and can be easily removed if necessary.

  Further, the chelate compound remains in the polyurethane urea resin (A) after the reaction. The pressure sensitive adhesive containing the polyurethane urea resin (A) is mixed with the reactive compound (B). At this time, the chelate compound is the reaction rate between the polyurethane urea resin (A) and the reactive compound (B). Can also be adjusted, and as a result, a pressure sensitive adhesive having excellent storage stability and pot life can be provided.

In producing the polyurethane urea resin (A), a known organic solvent is preferably used. The use of organic solvent serves to facilitate reaction control. Examples of the solvent used for such purpose include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol and n-butyl alcohol, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl. Ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n-amyl ketone, methyl isoamyl ketone, diethyl ketone, ethyl-n-propyl ketone, ethyl isopropyl ketone, ethyl-n-butyl ketone, ethyl isobutyl ketone, di-n- Ketones such as propyl ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone and isophorone, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, acetate Butyl, hexyl acetate, octyl acetate, methyl lactate, propyl lactate, butyl lactate and other esters, ethylene glycol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol Butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dipropyl ether, tripropylene glycol monomethyl ether, and other glycols and glycol ethers, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol Monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate And glycol acetates such as dipropylene glycol monomethyl ether acetate, saturated hydrocarbons such as n-hexane, isohexane, n-nonane, isononane, dodecane and isododecane, and 1-hexene, 1-heptene, 1-octene and the like. Cyclic saturated hydrocarbons, cyclohexane, cycloheptane, cyclooctane, cyclodecane, decalin, etc., cyclic saturated hydrocarbons, cyclohexene, cycloheptene, cyclooctene, 1,1,3,5,7-cyclooctatetraene, cyclododecene, etc. Examples thereof include unsaturated hydrocarbons, aromatic hydrocarbons such as benzene, toluene and xylene, and dioxane, acetonitrile, tetrahydrofuran, diglyme, dimethyl sulfoxide, N-methylpyrrolidone, dimethylformamide and the like.
Among these, ethyl acetate, toluene, and methyl ethyl ketone are preferable from the viewpoint of the solubility of the polyurethane resin (A) and the boiling point of the solvent.

The blending amount of the organic solvent may be appropriately determined in consideration of the composition of the polyurethane resin (A), the viscosity, the concentration of nonvolatile components, and the like. The concentration of non-volatile components other than the organic solvent at the time of synthesizing the polyurethane resin (A) is preferably 40 to 99% by weight, more preferably 50 to 95% by weight. When the concentration is within the predetermined range, the reactivity is improved. The organic solvent may be used alone or in combination of two or more kinds.
Water can also be used if the reaction can be controlled. For example, if a polyurethane urea resin having an ethylene oxide skeleton is formed, it can be dispersed or dissolved in water.

<< The third step of mixing the polyurethane urea resin (A) and the reactive compound (B) having a functional group capable of reacting with a hydroxyl group to form a pressure-sensitive adhesive >>
Further, the third step of mixing the polyurethane urea resin (A) with the reactive compound (B) having a functional group capable of reacting with a hydroxyl group will be described.
The pressure-sensitive adhesive of the present invention is characterized in that the polyurethane urea resin (A) contains the reactive compound (B), and is a mixer such as a Henschel mixer, a disper, an attritor, a high speed mixer, or a homomixer. It can be obtained by mixing with. At this time, if necessary, considering the solubility of the ester compound (C), the patch agent (D), the tackifying resin (E), the hydrolysis inhibitor (F) and the other component (P), Can be mixed.
At this time, it is preferable to remove air bubbles or bubbles contained in the pressure-sensitive adhesive by degassing under reduced pressure, or remove unexpected foreign matters by filtration or the like, if necessary.

  The reaction between the hydroxyl group contained in the polyurethane urea resin (A) and the reactive functional group in the reactive compound (B) may be at any timing after mixing. For example, the reaction does not proceed immediately after mixing (or only a part of the reaction proceeds), and after the pressure-sensitive adhesive is applied to the substrate, it reacts during heating and drying to bond while forming a cross-linked coating film. Performance may be exhibited. The timing of mixing is also not particularly limited, and after applying one of the polyurethane urea resin (A) and the reactive compound (B) to the surface of the base material, the other is separately applied, and when heated and dried, The reaction may proceed. Alternatively, the polyurethane urea resin (A) and the reactive compound (B) may be coated on different substrate surfaces, the coated surfaces may be bonded together, and then heat-dried to allow the reaction to proceed. . Preferably, a pressure-sensitive adhesive, which is a mixed solution of the polyurethane urea resin (A) and the reactive compound (B), is applied onto a substrate and crosslinked and cured by heating to form an adhesive layer. At this time, the surface of the adhesive layer has a removable adhesive property.

<Adhesive sheet>
Next, the adhesive sheet will be described.
The adhesive sheet using the pressure-sensitive adhesive of the present invention (also referred to as a pressure-sensitive adhesive film) is preferably used for percutaneously absorbable adhesive sheet applications that can be a percutaneous absorption preparation, and is used on the base material (G) described below. Is formed with an adhesive layer made of the above pressure-sensitive adhesive, and it is preferable that a sheet-shaped substrate (also referred to as a release liner) having a surface subjected to a release treatment is laminated.
In the case of producing an adhesive sheet, after applying a pressure-sensitive adhesive to a substrate described later by a suitable method according to a conventional method, when the pressure-sensitive adhesive contains a liquid medium such as an organic solvent or water, , The liquid medium is removed by a method such as heating, or when the pressure-sensitive adhesive does not contain the liquid medium to be volatilized, the adhesive layer in the molten state is cooled and solidified, and An adhesive layer can be formed. For example, a pressure-sensitive adhesive is applied to the release treated surface of the release liner, dried, and a method of creating a substrate by laminating it, or a pressure-sensitive adhesive is directly applied to a substrate other than the release liner and dried, Examples include a method in which the release-treated surface of the release liner is attached to the surface of the adhesive layer.

  The method of applying the pressure sensitive adhesive is not particularly limited. For example, various well-known methods such as Meyer bar, applicator, brush, spray, roller, gravure coater, die coater, kiss coater, lip coater, comma coater, blade coater, knife coater, reverse coater, spin coater, dip coater, etc. Can be applied. Further, the form such as thin film coating or thick film coating can be selected without particular limitation depending on the application.

  When the adhesive layer is formed using the pressure-sensitive adhesive of the present invention, the thickness of the adhesive layer is preferably 0.5 to 300 μm, more preferably 1 to 100 μm. When the film thickness is within the above range, the adhesive sheet can serve as a percutaneously absorbable adhesive sheet and can obtain a sufficient adhesive force.

  The basic laminated construction of the adhesive sheet is a single-sided adhesive sheet such as substrate / adhesive layer / release liner or a double-sided adhesive sheet such as release liner / adhesive layer / substrate / adhesive layer / release liner. The laminated body thus laminated on the release liner is called an adhesive sheet. In use, the release liner is peeled off and the adhesive layer is applied to the skin surface. The pressure-sensitive adhesive not only has adhesiveness at the moment the adhesive layer touches the skin surface at the time of application, but also as an adhesive other than the pressure-sensitive adhesive (hereinafter simply referred to as adhesive). Unlike the above, it is necessary that it does not completely solidify during sticking, has tack and moderate hardness, and has cohesive force for maintaining the stuck state. The cohesive force largely depends on the molecular weight and the crosslink density.

  The base material (G) constituting the adhesive sheet is used as a sheet-shaped support, and a flexible base material that is usually used for a medicated patch such as a transdermal preparation can be used and is not particularly limited. For example, various plastic films, woven / knitted / nonwoven fabrics, paper, and the like can be used. As various plastic films, for example, polyvinyl alcohol film (also called PVA film), polytriacetyl cellulose film (also called TAC film), polypropylene film (also called PP film), polyethylene film (also called PE film), polycyclo Films of polyolefin resins such as olefin films (also referred to as COP films) and ethylene-vinyl acetate copolymer films (also referred to as EVA films), polyethylene terephthalate films (also referred to as PET films) and polybutylene terephthalate films (also referred to as PBT films) ) And other polyester resin films, polycarbonate resin films (also called PC films), polynorbornene resin films, Arylate-based resin film, polyacrylic acid ester-based resin film, polyphenylene sulfide resin film (also referred to as PPS film), polystyrene-based resin film (also referred to as PST film), polyamide-based resin film (also referred to as PA film) , A polyimide resin film (also referred to as a PI film), an oxirane resin film, and the like. Among these substrates, a PVA film, a TAC film, a COP film, a polyester resin film, a PC film, and the like are particularly preferable.

In addition, various plastic films have physical surfaces such as corona discharge, plasma treatment, flame treatment, etc., chemical treatment for modifying the film surface with acid or alkali, etc. A film with a substantially increased surface area, or metal oxides such as silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, and yttrium, or non-metal inorganic oxides are deposited on the surface. It is possible to suitably use a pressure-sensitive adhesive such as a plastic film that has been subjected to an easy-adhesion treatment or that has been provided with functionality depending on the application.
When various plastic films are used as transdermal absorbable adhesive sheets, fatty acid amide, polyethyleneimine, long-chain alkyl-based additives, etc. may be added to the release surface on the opposite side to form a release layer. It is possible to provide a coating layer made of any appropriate release agent such as silicone, long chain alkyl, and fluorine.

  Examples of the woven / knitted / nonwoven fabrics include woven / knitted / nonwoven fabrics such as polyester, polyolefin, cellulose ester, polyurethane, and polyamide.

  Examples of the release liner include those obtained by using the above-mentioned substrate (G) as a sheet-like substrate and subjecting the surface to the release treatment as described above.

  As these sheet-like base materials, a single-layer base material or a multi-layer base material in which a plurality of base materials are laminated can be used. When the adhesive sheet is used as a percutaneously absorbable adhesive sheet, the substrate (G) may be laminated with other commonly used functional layers such as a surface protective layer.

  The thickness of the base material (G) and the release liner used for the adhesive sheet depends on the kind of the transdermally absorbable adhesive sheet, but in the case of the base material (G), it is usually 50 μm to 300 μm, preferably , 70 μm to 200 μm, and in the case of a release liner, 3 μm to 100 μm, preferably 5 μm to 50 μm.

  Moreover, among the above-mentioned base materials (G), those having a coarse and porous structure such as a non-woven fabric may be liable to fall out by the method of applying the one dissolved in the above-mentioned organic solvent to the base material (G). Even if it does not fall off, it will permeate into the interior, so it will consume extra dissolved material.Therefore, apply a pressure-sensitive adhesive to the release treated surface of the release liner, dry it, and bond the base material. The method of making is preferred.

  Hereinafter, specific examples of the present invention will be described together with comparative examples, but the present invention is not limited to the following examples. Further, in the following Examples and Comparative Examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified.

<Synthesis of diamine compound (a3-1-1)>
(Synthesis example 1)
The following compound {primary amine compound (a3-1-1), ethylenic non-condensation was added to the reaction tank and the dropping device of the reaction device equipped with a reaction tank, a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing pipe. Saturated compound (a3-1-2) and organic solvent} were charged in the following ratios, respectively.

[Reaction tank]
2-Aminoethanol (a3-1-1-1-1) 11.36 parts 2-Ethylhexylamine (a3-1-1-1-2-1) 1.60 parts M-1000 (a3-1-1-1) 1-2-2) 51.66 parts Toluene (organic solvent) 50 parts [Dripping device]
TPGDA (a3-1-1-2) 35.38 parts Toluene (organic solvent) 30 parts

After replacing the air in the reaction tank with nitrogen gas, the temperature was raised to 80 ° C. under stirring in a nitrogen atmosphere, and the mixture of the ethylenically unsaturated compound and the organic solvent was added dropwise over 1 hour from a dropping device. Then the reaction was started. The reaction was continued for 3 hours with further stirring. Then, after confirming that the characteristic absorption (811 cm ⁻¹ ) based on the double bond in the IR chart disappeared, 20 parts of toluene was added to adjust the concentration of nonvolatile components to 50%, and the mixture was cooled to 25 ° C. The reaction was completed. The obtained diamine compound is a diamine compound having a 2-ethylhexyl group as a substituent having 4 to 22 carbon atoms in the side chain and a hydroxyethyl group as a group having a hydroxyl group, and the solution appearance is colorless and transparent (25 ° C). )Met.

(Synthesis examples 2 to 19)
The amine compound (a3-1-1-1), the organic solvent, and, if necessary, the catalyst described in Table 1 were all charged into a polymerization tank, and the ethylenically unsaturated compound (a3-1-1-2) was used. , And the organic solvent were changed to be charged in a dropping device, and the diamine compound (a3-1-1) was synthesized in the same manner as in Synthesis Example 1. The end point of the reaction was determined by confirming that the characteristic absorption (811 cm ⁻¹ ) based on the double bond in the IR chart disappeared as in Synthesis Example 1. The compounds used as monomers in Table 1 represent the total value (parts) of the amount charged into the polymerization tank and the amount charged into the dropping device.
However, in Synthesis Example 10, benzylamine, which is a primary amine having an aromatic ring, was used instead of the diamine compound (a3-1-1).
In Synthesis Example 11, only the amine compound having no alkylene oxide unit was used for the reaction.
Moreover, the synthesis example 12 is the diacrylic acid ethylene oxide modification bisphenol A (EO addition mol number: 4) which is an ethylenically unsaturated compound which has an aromatic ring instead of the ethylenically unsaturated compound (a3-1-1-2). Changed to.
Further, in Synthesis Example 17, all the organic solvents used were changed to ethyl acetate.
In addition, in Synthesis Example 18, tetraethylammonium fluoride was added as a catalyst and charged in the reaction layer to react.

  The solution appearance of the resulting solution of the diamine compound was determined according to the method described below, and the results are shown in Table 1. In addition, the diamine compounds obtained in Synthesis Examples 1 to 9 and 13 to 18 are diamine compounds (a3-1), and the diamine compounds obtained in Synthesis Examples 10 to 12 are diamine compounds (a3-1). There is no diamine compound.

<Appearance of solution>
The solution appearance of the solutions of the diamine compounds obtained in Synthesis Examples 1 to 18 was visually observed under the condition of 25 ° C. It is good if it is colorless and transparent.

The abbreviations of the materials used in Synthesis Examples 1 to 18 are shown below. In Table 1, the blank column means no compounding.
-Compound (a3-1-1-1-1)
2AE: 2-aminoethanol, 4AB: 4-aminobutanol, 2APO: 2-aminopropane-1,3-diol (also known as serinol), EOA: 2- [2- {2- (2-aminoethoxy) ethoxy} Ethoxy] ethane-1-ol compound (a3-1-1-1-2-1)
2EHAm: 2-ethylhexylamine, LAm: laurylamine, SAm: stearylamine compound (a3-1-1-1-2-2)
M1000: polyether monoamine (EO addition mole number: 19 mol, PO addition mole number: 3 mol) ["Jeffermin M-1000" manufactured by Hunstman], M600: polyether monoamine (EO addition mole number: 1 mol, PO addition mole number) : 9 mol) ["Jeffermin M-600" manufactured by Hunstman)
-Compound (a3-1-1-1-2-3)
EAm: ethylamine / aromatic amine BzAm: benzylamine / ethylenically unsaturated compound (a3-1-1-2)
NDA: 1,9-nonanediol diacrylate, TPGDA: tripropylene glycol diacrylate, 14 EGA: polyethylene glycol diacrylate # 600, ADCD: tricyclodecanedihydroxymethyl diacrylate, TEGVE: tetraethylene glycol divinyl ether / aromatic ethylenic Unsaturated compound BADA: ethylene oxide diacrylate-modified bisphenol A (EO addition mole number: 4)
・ Organic solvent TOL: Toluene, EAC: Ethyl acetate ・ Catalyst TEAF: Tetraethylammonium fluoride

<Synthesis of diamine compound (a3-1-2)>
(Synthesis example 21)
The following compound {diamine compound (a3-1-2-1), ethylenically unsaturated is added to the reaction tank and the dropping device of the reaction device equipped with a reaction tank, a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing pipe. Compound (a3-1-2-2) and organic solvent} were charged in the following ratios, respectively.

[Reaction tank]
Isophorone diamine (a3-1-2-1) 27.19 parts Toluene (organic solvent) 50 parts [Dripping device]
4-hydroxybutyl acrylate (a3-1-2-2-1) 36.34 parts Lauryl acrylate (a3-1-2-2-2-1) 4.04 parts AM90G (a3-1-2-2) -2-2) 32.44 parts Toluene (organic solvent) 30 parts

After replacing the air in the reaction tank with nitrogen gas, the temperature was raised to 80 ° C. under stirring in a nitrogen atmosphere, and the mixture of the ethylenically unsaturated compound and the organic solvent was added dropwise over 1 hour from a dropping device. Then the reaction was started. The reaction was continued for 3 hours with further stirring. Then, after confirming that the characteristic absorption (811 cm ⁻¹ ) based on the double bond in the IR chart disappeared, 20 parts of toluene was added to adjust the concentration of nonvolatile components to 50%, and the mixture was cooled to 25 ° C. The reaction was completed. The obtained diamine compound is a diamine compound having a lauryl group as a substituent having 4 to 22 carbon atoms in the side chain and a hydroxybutyl group as a group having a hydroxyl group, and the solution appearance is colorless and transparent (25 ° C.). there were.

(Synthesis examples 22 to 39)
All of the materials listed in Table 2 were charged in a polymerization tank with a diamine compound (a3-1-2-1), an organic solvent, and, if necessary, a catalyst to obtain an ethylenically unsaturated compound (a3-1-2-2). , And the organic solvent were changed to be charged in a dropping device, and the diamine compound (a3-1-2) was synthesized in the same manner as in Synthesis Example 21. The end point of the reaction was determined by confirming the disappearance of the characteristic absorption (811 cm ⁻¹ ) based on the double bond in the IR chart as in Synthesis Example 21. The compounds used as monomers in Table 2 represent the total value (parts) of the amount charged into the polymerization tank and the amount charged into the dropping device.
However, in Synthesis Example 30, benzyl acrylate, which is an aromatic acrylate, was used instead of the ethylenically unsaturated compound (a3-1-2-2).
Further, in Synthesis Example 31, only the ethylenically unsaturated compound having no alkylene oxide unit was changed and reacted.
In addition, in Synthesis Example 32, m-xylylenediamine, which is an aromatic diamine, was used instead of the diamine compound (a3-1-2-1) and reacted.
In addition, in Synthesis Example 37, all the organic solvents used were changed to ethyl acetate.
In addition, in Synthesis Example 38, tetraethylammonium fluoride was added as a catalyst and charged in the reaction layer to react.

  The solution appearance of the obtained solution of the diamine compound was determined according to the method described below, and the results are shown in Table 2. The diamine compounds obtained in Synthesis Examples 21 to 29 and 33 to 38 are diamine compounds (a3-2), and the diamine compounds obtained in Synthesis Examples 30 to 32 are diamine compounds (a3-2). There is no diamine compound.

<Appearance of solution>
The solution appearance of the diamine compound solutions obtained in Synthesis Examples 21 to 39 was visually observed under the condition of 25 ° C. It is good if it is colorless and transparent.

The abbreviations of the materials used in Synthesis Examples 21 to 38 are shown below. In Table 2, the blank column means no compound.
-Compound (a3-1-2-2-1)
2HEA: 2-hydroxyethyl acrylate, 4HBA: 4-hydroxybutyl acrylate, FA2D: polycaprolactone acrylate (number of moles of CL added: 2) ["PLACCEL FA2D" manufactured by Daicel), AE400: polyethylene glycol acrylate (EO Addition mole number: 10) [NOF CORPORATION “Blenmer AE400”], AP400: polypropylene glycol acrylate (EO addition mole number: 6) [NOF Corporation “Blenmer AP400”]
-Compound (a3-1-2-2-2-1)
BA: butyl acrylate, LA: lauryl acrylate, IBVE: isobutyl vinyl ether compound (a3-1-2-2-2-2)
AM90: methoxypolyethylene glycol acrylate (number of moles of EO added: 9) [Shin Nakamura Chemical Co., Ltd. "NK ester AM90G"], DPMA: methoxydipropylene glycol acrylate (number of moles of PO added: 2)) "Light acrylate DPM-A" manufactured by Kogyo Co., Ltd.]
-Compound (a3-1-2-2-2-3)
EAm: ethylamine / aromatic acrylate BzA: benzyl acrylate / diamine compound (a3-1-2-1)
HDAm: ethylenediamine, HMDAm: hexamethylenediamine, IPDAm: isophoronediamine, EDR148: polyetherdiamine (EO addition mole number: 2) ["Jeffermin EDA-148" manufactured by Hunstman], D400: polyetherdiamine (PO addition mole) Number: 6) ["Jeffermin D-400" manufactured by Hunstman]
-Aromatic diamine XDAm: m-xylylenediamine-Organic solvent TOL: Toluene, EAC: Ethyl acetate-Catalyst TEAF: Tetraethylammonium fluoride

<Synthesis of polyurethane urea resin>
(Synthesis Example 51)
The following monomer {polyol (a1), polyisocyanate (a2), amine compound is added to the reaction tank and the dropping device of the polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing pipe. (A3), catalyst, and organic solvent} were charged in the following ratios, respectively. At this time, the organic solvent in the polymerization tank was charged so that the reaction concentration in the polymerization tank was 80%, and the organic solvent in the dropping device was charged so that the total reaction concentration was 65% after completion of the dropping.
In addition, since the diamine (a3-1-1) uses a non-volatile content concentration of about 50%, the organic solvent used for the dropping device is about 50% of the organic solvent contained in the diamine (a3-1-1) solution. The value was set with the minutes taken into consideration.

[Polymerization tank]
EHD (a1-1) 1.32 parts PEG1000 (a1-2) 17.02 parts PP1000 (a1-2) 42.54 parts P1010 (a1-3) 17.02 parts HDI (a2) 15.71 parts Toluene ( Organic solvent) 24.30 parts DBU (catalyst) 0.0014 parts [Dripping device]
Diamine compound (a3-1-1) (from Synthesis Example 1) 6.27 parts Toluene (organic solvent) 30.26 parts

After replacing the air in the polymerization tank with nitrogen gas, the mixture was heated to 90 ° C. under stirring in a nitrogen atmosphere to start polymerization, and the reaction was carried out for 4 hours. Then, it cooled to 40 degreeC, and the mixture containing the said diamine compound (a3-1-1) and the organic solvent was dripped over 1 hour from the dropping device. After the dropwise addition was completed, the reaction was continued for 2 hours with further stirring and then cooled to 25 ° C. to obtain a urethane urea resin (Y) solution. After confirming the remaining amount (%) of isocyanate groups by titration described below, 0.11 parts of dibutylamine (a3-2-1) and 46.34 parts of ethyl acetate were added to make the nonvolatile concentration of the resin solution about 50%. It was adjusted. Then, the mixture was stirred for 1 hour, and after confirming that the characteristic absorption (2,270 cm ⁻¹ ) based on the isocyanate group on the IR chart had disappeared, the reaction was terminated.
Thereby, a polyurethane urea in which an ethyl group and a methyl group are introduced from the polyol (a), and a hydroxyethyl group, a 2-ethylhexyl group, and an alkylene oxide unit are introduced as substituents from the diamine compound (a3-1-1). A solution containing the resin was obtained.
The polyurethane urea resin (A) solution has a colorless and transparent solution appearance (25 ° C.), a solution viscosity (Vis) of 6,500 mPa · s (25 ° C.), a weight average molecular weight (Mw) of 77,000 and a hydroxyl group. Value (OHV) was 6.5 mg KOH / g.

(Synthesis examples 52 to 92)
The materials listed in Table 3 were changed so that the polyol (a1), polyisocyanate (a2), organic solvent, and catalyst were all charged in a polymerization tank, and the diamine compound (a3-1) and organic solvent were charged in a dropping device. Except for the above, the urethane urea resin was synthesized in the same manner as in Synthesis Example 31. Then, after confirming the remaining amount of the isocyanate group by titration, the reaction-terminating amine compound (a3-2-1) and an organic solvent were added to eliminate the characteristic absorption (2,270 cm ^-1 ) based on the isocyanate group in the IR chart. Each polyurethane urea resin was synthesized by the same method as in Synthesis Example 51, such as confirming that The compounds used as the monomers shown in Table 3 represent the total value (parts) of the amount charged into the polymerization tank and the amount charged into the dropping device.
However, the organic solvents used in Synthesis Examples 67 and 90 were all changed to ethyl acetate.
In Synthesis Example 91, the catalyst was changed to dioctyltin dilaurate, the organic solvent used during the synthesis of the urethane prepolymer (X) was changed to toluene, and the organic solvent charged to the dropping apparatus was changed to acetylacetone.
In Synthesis Example 89, benzylamine (aromatic amine) was used instead of the diamine compound (a3-1-1).
The polyurethane urea resins obtained in Synthesis Examples 51 to 59, 63 to 78, 81 to 85 and 89 to 92 are polyurethane urea resins (A), and Synthesis Examples 60 to 62, 79, 80 and 86 to 89. The polyurethane urea resin obtained in step 1 is a polyurethane urea resin that is not the polyurethane urea resin (A).

(Synthesis example 151)
The following monomer {polyol (a1), polyisocyanate (a2), amine compound is added to the reaction tank and the dropping device of the polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing pipe. (A3), catalyst, and organic solvent} were charged in the following ratios, respectively. At this time, the organic solvent in the polymerization tank was charged so that the reaction concentration in the polymerization tank was 80%, and the organic solvent in the dropping device was charged so that the total reaction concentration was 65% after completion of the dropping.
In addition, since the diamine compound (a3-1-2) uses a nonvolatile concentration of about 50%, the organic solvent used for the dropping device is about the organic solvent contained in the diamine compound (a3-1-2) solution. The value was set with 50% taken into consideration.

[Polymerization tank]
EHD (a1-1) 1.34 parts PEG1000 (a1-2) 17.30 parts PP1000 (a1-2) 43.25 parts P1010 (a1-3) 17.30 parts HDI (a2) 15.97 parts Toluene ( Organic solvent) 23.79 parts DBU (catalyst) 0.0014 parts [Dripping device]
Diamine compound (a3-1-1) (from Synthesis Example 51) 4.70 parts Toluene (organic solvent) 29.86 parts

After replacing the air in the polymerization tank with nitrogen gas, the mixture was heated to 90 ° C. under stirring in a nitrogen atmosphere to start polymerization, and the reaction was carried out for 4 hours. Then, it cooled to 40 degreeC, and the mixture containing the said diamine compound (a3-1-2) and the organic solvent was dripped over 1 hour from the dropping device. After the dropwise addition was completed, the reaction was continued for 2 hours with further stirring and then cooled to 25 ° C. to obtain a urethane urea resin (Y) solution. After confirming the remaining amount (%) of isocyanate groups by titration described below, 0.11 parts of dibutylamine (a3-2-1) and 46.35 parts of ethyl acetate were added to make the nonvolatile concentration of the resin solution about 50%. It was adjusted. Then, the mixture was stirred for 1 hour, and after confirming that the characteristic absorption (2,270 cm ⁻¹ ) based on the isocyanate group on the IR chart had disappeared, the reaction was terminated.
Accordingly, from the polyol (a), an alkyl group having 6 to 8 carbon atoms [also referred to as an alkyl group (C6 to C8)]. ] And a methyl group, or from the diamine compound (a3-1-2), a solution containing a polyurethaneurea resin having a hydroxybutyl group, a lauryl group and an alkylene oxide unit introduced as a substituent was obtained.
This polyurethane urea resin (A) solution has a colorless and transparent solution appearance (25 ° C.), a solution viscosity (Vis) of 7,500 mPa · s (25 ° C.), a weight average molecular weight (Mw) of 79,000, and a hydroxyl group. The value (OHV) was 6.7 mgKOH / g.

(Synthesis examples 152 to 192)
The materials listed in Table 4 were changed so that the polyol (a1), polyisocyanate (a2), organic solvent, and catalyst were all charged in a polymerization tank, and the diamine compound (a3-1) and organic solvent were charged in a dropping device. Except for the above, urethane urea resins were synthesized in the same manner as in Synthesis Example 151. Then, after confirming the remaining amount of the isocyanate group by titration, the secondary amines (a3-2-1) used as the reaction terminator and an organic solvent were added, and the characteristic absorption based on the isocyanate group of the IR chart (2,270 cm Each polyurethane urea resin was synthesized in the same manner as in Synthesis Example 151, for example, by confirming that ⁻¹ ) disappeared. The compounds used as monomers shown in Table 4 represent the total value (parts) of the amount charged into the polymerization tank and the amount charged into the dropping device.
However, the organic solvents used in Synthesis Examples 167 and 190 were all changed to ethyl acetate.
Further, in Synthesis Example 191, the catalyst was changed to dioctyltin dilaurate, the organic solvent used during the synthesis of the urethane prepolymer (X) was changed to toluene, and the organic solvent charged to the dropping apparatus was changed to acetylacetone.
In Synthesis Example 189, benzylamine (aromatic amine) was used instead of the diamine compound (a3-1-2).
The polyurethane urea resins obtained in Synthesis Examples 151-159, 163-178, 181-185 and 189-192 are polyurethane urea resins (A), and Synthesis Examples 160-162, 179, 180 and 186-189. The polyurethane urea resin obtained in step 1 is a polyurethane urea resin that is not the polyurethane urea resin (A).
The polyurethane urea resin obtained in Synthesis Examples 151-158, 161-175, 180, 181, 184-187, 189-191, 194-198 is a polyurethane urea resin (A), and Synthesis Examples 159, 160. 176 to 79, 182, 183, 188, 192, and 193 are polyurethane urea resins other than the polyurethane urea resin (A).

  The solution appearance (25 ° C.), non-volatile content concentration (NV), solution viscosity (Vis), weight average molecular weight (Mw), and hydroxyl value (OHV) of the obtained polyurethane urea resin solution were determined according to the methods described below, The results are shown in Tables 3 and 4. In addition, the methods for measuring the acid value (AV), the residual amount (%) of the isocyanate group (NCO), and the glass transition temperature (Tg) are also described.

<Appearance of solution>
The solution appearance of the obtained polyurethane urea resin solution was visually observed under the condition of 25 ° C. It is good if it is colorless and transparent.

<< Nonvolatile matter concentration (NV) >>
About 1 g of the obtained polyurethane urea resin solution was weighed in a metal container, dried in an oven at 150 ° C. for 20 minutes, cooled to 25 ° C., and the residue was weighed to calculate the residual ratio, and the nonvolatile content was calculated. The concentration (solid content) was defined (unit:%).

<Solution viscosity (Vis)>
The obtained polyurethane urea resin solution was mixed with a rotor No. 5 at 25 ° C. using a B-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.). 3. Rotation speed was 0.5 to 100 rpm, and the viscosity was measured under the condition of rotation for 1 minute to obtain the solution viscosity (mPa · s).

<Average molecular weight>
The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured using Showa Denko GPC (gel permeation chromatography). The number average molecular weight (Mn) and the weight average molecular weight (Mw) were determined by using the converted value of polystyrene as a standard substance.
Device name: Showa Denko GPC (gel permeation chromatography) "Shodex GPC System-21"
Column: Tohso GMHXL: 4 lines, Tosoh HXL-H: 1 line Connected in series.
Mobile phase solvent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min Column temperature: 40 ° C

<< Hydroxy group value (OHV) >>
About 1 g of the sample was precisely weighed in a ground-in stopper Erlenmeyer flask, and 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution was added and dissolved. Next, 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make the volume 100 ml) was added, and the mixture was stirred for 1 hour. To this, phenolphthalein reagent solution was added as an indicator and held for 30 seconds. Thereafter, the solution was titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned red.
The hydroxyl value was determined by the following equation. The hydroxyl value was the numerical value of the dry state of the resin (unit: mgKOH / g).
Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.25} / S] / (non-volatile concentration / 100) + D
However, S: sampling amount (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: Empty experiment consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: titer of 0.1N alcoholic potassium hydroxide solution
D: Acid value (mgKOH / g)

<Acid value (AV)>
About 1 g of a sample was precisely weighed and placed in a stoppered Erlenmeyer flask, and dissolved by adding 100 ml of a mixed solution of toluene / ethanol (volume ratio: toluene / ethanol = 2/1). To this, phenolphthalein TS was added as an indicator, and after holding for 30 seconds, titration was performed with a 0.1N alcoholic potassium hydroxide solution until the solution turned red.
The acid value was calculated by the following formula. The acid value was the numerical value of the dry state of the resin (unit: mgKOH / g).
Acid value (mgKOH / g) = {(5.611 × a × F) / S} / (nonvolatile concentration / 100)
However, S: sampling amount (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: titer of 0.1N alcoholic potassium hydroxide solution

<< Residual amount (%) of isocyanate group (NCO) >>
About 1 g of a sample was precisely weighed in a ground-in stopper Erlenmeyer flask, and 25 ml of chlorobenzene and di-n-butylamine / o-dichlorobenzene (weight ratio: di-n-butylamine / o-dichlorobenzene = 1 / 24.8). Add 10 ml of the mixed solution and dissolve. To this, 80 g of methanol and bromphenol blue reagent were added as indicators and titrated with a 0.1N alcoholic hydrochloric acid solution. Titration was continued until the solution turned yellow green and was held for 30 seconds. The NCO residual amount (%) was calculated by the following formula.
NCO residual amount (%) = [0.42 × (B−C) × F] / S
However, S: sampling amount (g)
B: Consumption of 0.1N alcoholic hydrochloric acid solution required for sample titration (ml)
C: Consumption of 0.1N alcoholic hydrochloric acid solution required for titration in blank test (ml)
F: titer of 0.1N alcoholic hydrochloric acid solution

<Glass transition temperature (Tg)>
A robot DSC (differential scanning calorimeter, “RDC220” manufactured by Seiko Instruments Inc.) was connected to an “SSC5200 disk station” (manufactured by Seiko Instruments Inc.) and used for measurement.
Approximately 10 mg of the sample was placed in an aluminum pan, weighed and set in a differential scanning calorimeter, and the same type of aluminum pan without the sample was used as a reference and held at a temperature of 100 ° C. for 5 minutes, and then liquid nitrogen was used. Quenched to 120 ° C. Then, the temperature was raised at a temperature rising rate of 10 ° C./min, and the glass transition temperature (Tg, unit: ° C.) was determined from the obtained DSC chart.

The abbreviations of the materials used in Synthesis 51 to 92 (described in Table 3) and Synthesis 151 to 192 (described in Table 4) are shown below. In addition, in Tables 3 and 4, blank columns mean that there is no compounding.
-Low molecular weight polyols (a1-1) (Tables 3 and 4)
DD: PRIPOL-2033 [manufactured by CRODA Coating & Polymers], EHD: 2-ethyl-1,3-hexanediol, ODD: 1,12-octadecanediol / polyether polyols (a1-2)
PEG600: PEG600 (Mn = 600, hydroxyl value = 180, acid value <0.5, linear liquid type) [manufactured by Sanyo Chemical Industries], PEG1000: PEG1000 (Mn = 1,000, hydroxyl value = 112, acid value < 0.5, linear wax type) [manufactured by Sanyo Chemical Industries], PP-1000: Newpol PP-1000 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type, diol ) [Manufactured by Sanyo Chemical Industries], HB400: Newpol 50HB-400 (Mn = 1,340, hydroxyl value = 84, acid value <0.5, linear liquid type) [manufactured by Sanyo Chemical Industries], PTG1000: PTG 1000 (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear wax type) [Hodogaya Chemical Co., Ltd.], G3000: ADEKA POLYAE Le G-3000B (Mn = 3,000, hydroxyl value = 56, acid number <0.5, linear liquid type, triol) [manufactured by Adeka Corporation]
・ Polyester polyols (a1-3)
P1010: Kuraray polyol P1010 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type, diol) [manufactured by Kuraray], Y9-10: ADEKA NEWACE Y9-10 (Mn = 1) 2,000, hydroxyl value = 110, acid value <1, linear liquid type) [manufactured by Adeka], TA22: Phantol TA22-735A (Mn = 1,400, hydroxyl value = 80, acid value <1, linear liquid type) ) [Hitachi Chemical Co., Ltd.]
・ Polyamide polyols (a1-4)
TPAE: TPAE617 (Mn = 15,000, hydroxyl value = 16, acid value = 1, linear type, diol) [manufactured by T & K TOKA]
・ Polycarbonate polyols (a1-5)
C1015N: Kuraray polyol C-1015N (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type, diol) [Kuraray Co., Ltd.]
-Aromatic polyester polyol P2013: Kuraray polyol P2013 (Mn = 2,000, hydroxyl value = 56, acid value <1, aromatic ring-containing linear liquid type) [manufactured by Kuraray Co., Ltd.]
・ Polyisocyanate (a2)
HDI: hexamethylene diisocyanate, IPDI: 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, TDI: 2,4-tolylene diisocyanate compound (a3-1-1)
Diamine compound: Diamine compound obtained in each synthesis example described in Table 1 (Synthesis examples 1 to 18)
・ Compound (a3-1-2)
Diamine compound: Diamine compound obtained in each synthesis example described in Table 2 (Synthesis examples 21 to 38)
・ Compound (a3-2-1)
DBAm: dibutylamine, DEAm: amine compound having an aromatic ring BZAm: benzylamine, catalyst DBU: diazabicycloundecene, DOTDL: dioctyltin dilaurate, organic solvent ACAC: acetylacetone, TOL: toluene, EAC: ethyl acetate

  Using the polyurethane urea resin obtained in the above synthesis example, pressure sensitive adhesives were prepared by the following methods.

(Examples 1-68, 101-168, Comparative Examples 1-13, 21-33)
According to the weight ratio (part) of the polyurethane urea resin obtained in each synthesis example and the reactive compound (B) shown in Table 5 or 6, to 100 parts of the polyurethane urea resin, an ester compound (C ), An adhesive patch (D), a tackifying resin (E), a hydrolysis inhibitor (F) or another component (P) at a weight ratio (part) listed in Table 5 or 6, and an organic solvent. As a result, ethyl acetate was added to adjust the nonvolatile content to be 50% to obtain a pressure-sensitive adhesive. The obtained pressure-sensitive adhesive was applied to each substrate, dried, cured, and laminated to prepare an adhesive sheet, which was evaluated by the following method. The respective results are shown in Table 7 or 8.

<< Evaluation of pot life >>
For each pressure-sensitive adhesive, after blending, the viscosity at 25 ° C. was set every 1 hour until 8 hours later, using a B-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.) at 25 ° C., rotor No. The pot life was evaluated at 3 stages by measuring under conditions of 3, 12 rpm and 1 minute rotation. In case of "○" or "△" evaluation, there is no problem in actual use.
◯: Viscosity increase rate up to 8 hours is less than 50%. Good.
Δ: Viscosity increase rate up to 8 hours is 50% or more and less than 100%. Practically usable x: Separation or turbidity of the solution layer occurs, gelation occurs, or viscosity increase rate is 100% or more in less than 8 hours. Not practical.
Here, the viscosity increase rate was calculated by the following method.
Viscosity increase rate (%) = 100 × {(viscosity after storage for 8 hours) − (viscosity immediately after adjustment)} / (viscosity immediately after adjustment)

<< Evaluation of coatability >>
The resulting pressure-sensitive adhesive was used as a substrate on a release-treated polyethylene terephthalate film having a thickness of 38 μm (Cerapeal MF: manufactured by Toray Film Co., Ltd.) (hereinafter referred to as “release liner”), and the thickness after drying. Having a thickness of 25 μm, and dried with hot air at 100 ° C. for 2 minutes to form an adhesive layer. Then, a 100 μm thick polyethylene terephthalate film (PET film) was attached to the coated surface to prepare an adhesive sheet composed of a 100 μm thick PET film / adhesive layer / release liner. Then, the state of the adhesive layer surface (coated surface) after peeling off the release liner was visually observed and evaluated in three levels. In case of "○" or "△" evaluation, there is no problem in actual use.
◯: A smooth coated surface was obtained. Good.
Δ: Some repelling and foaming are observed at the end of the coated surface. Can be used for practical purposes.
Poor: Repelling, foaming and streaking were observed on the coated surface. Bad.

<Evaluation of workability>
Each adhesive sheet prepared by the same method as the above-mentioned “Evaluation of coatability” was cured for 7 days in an environment of 23 ° C. and 50% relative humidity. After that, it is cut into a width of 100 mm and a length of 100 mm, 20 pieces of this are piled up, and the state of protrusion of the adhesive layer from the edge of the adhesive sheet when pressed for 1 hour under the condition of 40 ° C.-60 Kg / cm ² is as follows. It was evaluated in three stages. In case of "○" or "△" evaluation, there is no problem in actual use.
◯: No protrusion of the adhesive layer is observed. Good.
Δ: Adhesion layer protrusion of less than 0.3 mm is observed, but it can be used practically.
X: The protrusion of the adhesive layer of 0.3 mm or more is observed. Bad.

<< Measurement of peel strength >>
Apply the obtained pressure-sensitive adhesive to a polyethylene terephthalate film (PET film) having a thickness of 50 μm as a base material so that the thickness after drying becomes 30 μm, and dry with hot air at 100 ° C. for 2 minutes. Then, the adhesive layer was formed. Then, a 38 μm release liner (Cerapeal MF: manufactured by Toray Film Co., Ltd.) is bonded to the coated surface to prepare an adhesive sheet having a constitution of 50 μm thick PET film / adhesive layer / release liner, and 23 ° C. and 50% relative humidity. It was cured in the environment for 7 days.
Each prepared adhesive sheet is cut into a width of 25 mm and a length of 100 mm, the release liner is peeled off, and the exposed adhesive layer is attached to a bakelite plate having a thickness of 2 mm under an environment of 23 ° C. and a relative humidity of 50%, and 5 kg. The rubber roller of No. 1 was reciprocated once and allowed to stand for 20 minutes. Then, after sticking to a bakelite plate and letting it stand for 20 minutes, under the same environment, using a tensile tester (“Tensilon” manufactured by Orientec Co., Ltd.), peeling was performed under conditions of a peeling speed of 300 mm / min and a peeling angle of 180 degrees. The strength was measured. The peel strength was evaluated as an adhesive strength in four levels. In the case of "◎", "○" or "△", there is no problem in actual use.
A: Peel strength is 15.0 (N / 25 mm) or more. Very good.
◯: Peel strength is 12.0 (N / 25 mm) or more and less than 15.0 (N / 25 mm). Good Δ: Peel strength is 8.0 (N / 25 mm) or more and less than 12.0 (N / 25 mm). . Practical is possible.
X: Peel strength is less than 8.0 (N / 25 mm). Poor and impractical.

<< Evaluation of removability >>
Above, each adhesive sheet prepared by the same method as in <Measurement of peeling strength> is cut into a size of 25 mm x 150 mm, the release liner is peeled off, the adhesive layer surface is lightly pressed with a finger, and the finger is released. The extent to which the adhesive in the pressed portion adheres to the finger was visually evaluated. This removability was evaluated on a 4-point scale. In the case of "◎", "○" or "△", there is no problem in actual use.
⊚: No glue adhered to fingers. Very good.
◯: The adhesive adheres to the finger at a maximum of about 1/4. Good.
Δ: The adhesive adheres to the finger at a maximum of about 1/3. Practical is possible.
X: The adhesion of the adhesive exceeds about ⅓, and it adheres almost entirely. Poor and impractical.

<< Evaluation of skin irritation >>
Each of the adhesive sheets prepared by the same method as in <Measurement of Peeling Strength> was cut into a size of 30 mm x 300 mm, the release liner was peeled off to leave the adhesive layer exposed, and then the test piece was removed. At 12 hours after the application to the upper arm of the subject, the condition of the skin surface was evaluated by visual observation, and a three-level evaluation was performed. In case of "○" or "△" evaluation, there is no problem in actual use.
○: No erythema. Good.
Δ: Very weak erythema. Practical is possible.
×: There is erythema. Poor and impractical.

<Evaluation of retention of transdermal absorption enhancer>
Each of the adhesive sheets prepared by the same method as in <Measurement of peel strength> was cut into a size of 100 mm x 100 mm to prepare a test piece. After the preparation, the test piece was allowed to stand in an environment of 23 ° C. and 65% RH for 1 month, and then the release liner was peeled off to leave the adhesive layer entirely exposed. Whether or not droplets of isopropyl acid had appeared was visually evaluated in four levels. In the case of "◎", "○" or "△", there is no problem in actual use.
⊚: There are no droplets at all. Very good.
◯: Droplet appears very slightly. Good.
Δ: Droplets appear on part of the surface of the adhesive layer. Practical is possible.
X: Droplets appear on the entire surface of the adhesive layer. Poor and impractical.

<Evaluation of drug skin permeability>
Each of the adhesive sheets prepared by the same method as in <Measurement of Peeling Strength> was cut into a circular shape (= 3.14 cm ² ) having a diameter of 2 cm to prepare a test piece. The peeled back skin of a nude mouse was set in a Franz diffusion cell, the release liner was peeled from the prepared test piece, the exposed adhesive layer was attached to this skin, and the skin permeability was examined. A phosphate buffer (pH 7.2) was used as the receptor solution, and the amount of methyl salicylate transferred from the test piece to the receptor solution through the skin was measured by HPLC after 24 hours. The skin permeability of methyl salicylate was calculated by dividing the amount of methyl salicylate in the receptor fluid after 24 hours by the amount of methyl salicylate in the test piece and multiplying by 100, and the following four-level evaluation was performed. . In the case of "◎", "○" or "△", there is no problem in actual use.

⊚: 80 [%] ≦ skin transmittance. Very good.
◯: 60 [%] ≦ skin transmittance <80 [%]. Good.
Δ: 40 [%] ≦ skin transmittance <60 [%]. Practical is possible.
X: Practical impractical due to poor skin transmittance <40 [%].

<< Evaluation of water vapor transmission rate >>
The pressure-sensitive adhesive thus obtained was coated on the release liner so that the thickness after drying was 30 μm, and dried by hot air at 100 ° C. for 2 minutes to form an adhesive layer. Then, a separately prepared release liner was attached to the adhesive layer to prepare a test piece in which the adhesive layer was sandwiched between the release liners, and cured for 7 days in an environment of 23 ° C. and 50% relative humidity.
The water vapor transmission rate was evaluated according to the moisture permeability test method for textiles (JIS L1099 A-2 "water method").
In a moisture permeable cup adjusted to a measurement environment temperature of 40 ° C. in advance, about 42 ml of water having a measurement environment temperature of 40 ° C. was prepared, and the release liners on both sides of the test piece were peeled off and attached to the moisture permeable cup, Place packing and ring one after another, fix with a nut, and seal the mounting side with vinyl adhesive tape.
The total mass of the test body including the moisture permeable cup (the total mass of the moisture permeable cup, the adhesive test piece, the packing, the ring, and the butterfly nut) is measured, and the initial test body total mass a ₀ is obtained.
The total mass a ₂ of the test body after exposing the moisture permeable cup to the environment of temperature 40 ° C. and relative humidity 50% for 2 hours was measured, and further, the total mass a ₂₄ of the test body 24 hours after the start of the test was measured. The water vapor transmission rate [g / m ² · h] was calculated by the following formula.
P = {(a ₂ −a ₂₄ ) / S} × 24/22
However, P: moisture permeability [g / m ² · h]
a ₂ : Mass of test body 2 hours after the start of measurement [g]
a ₂₄ : mass of test sample 24 hours after the start of measurement [g]
The moisture permeability P was measured from the above formula to obtain the water vapor transmission rate, and the evaluation was performed in the following four stages. In the case of "◎", "○" or "△", there is no problem in actual use.
⊚: 2,000 [g / m ² · h] ≦ water vapor permeability. Very good.
◯: 1,000 [g / m ² · h] ≦ water vapor permeability <2,000 [g / m ² · h]. Good.
Δ: 500 [g / m ² · h] ≦ water vapor permeability <1,000 [g / m ² · h]. Practical is possible.
X: Moisture permeability <500 [g / m ² · h] Poor and impractical.

Materials used in Examples and Comparative Examples are shown below. In addition, in Tables 5 and 6, the blank column means that there is no compounding.
-Polyurethane urea resin Compounds obtained in each synthesis example described in Table 1 or 2 (Table 3: Synthesis Examples 51 to 92, Table 4: 151 to 192)
-Reactive compound (B) having a functional group capable of reacting with a hydroxyl group
HDI / TMP: hexamethylene diisocyanate trimethylolpropane adduct, HDI / Nu: hexamethylene diisocyanate trimer having an isocyanurate ring, IPDI / TMP: 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate Trimethylolpropane adduct, XDI / TMP: xylylenediisocyanate trimethylolpropane adduct, MAS: 3-aminopropyltrimethoxysilane, EPS: 3-glycidoxypropyltrimethoxysilane, PMMM: pentamethoxymethylolmelamine・ Ester compound (C)
RS735: Polyethylene glycol diethylhexanoate [“ADEKA CIZER RS735” manufactured by ADEKA CORPORATION), POEOP: polyoxyethylene octyl ether phosphate ester, T80: polyoxyethylene di (glycerin) borate monooleate (EO addition mole number: 6 to 20) ) ["Emalbon T-80" manufactured by Toho Chemical Co., Ltd.]
・ Pharmaceutical drug (D)
MSC: methyl salicylate, MIP: isopropyl myristate / tackifying resin (E)
EH: Hydrogenated rosin ester [Arakawa Chemical Co., Ltd. "Ester gum H"], FTR: Petroleum resin [Mitsui Chemicals "FTR8100"]
・ Hydrolysis inhibitor (F)
CBI: Carbodiimide [Nisshinbo Co., Ltd., trade name Carbodilite V-09GB]
・ Other ingredients (P)
AO50: Phenol type antioxidant ["ADEKA STAB AO-50" manufactured by ADEKA CORPORATION]

As described above, the pressure-sensitive adhesive of the present invention is used in Examples 1 to 4, 8 to 24, 28 to 32, 36 to 53, 55 to 60, 63 to 68, 101 to 104, 108 to 119 and 123 to. 132, 136-153, 155-160, 163-168, pot life, coatability, processability, peeling strength, removability, skin irritation, drug retention, skin permeability, and water vapor permeability. In all cases, "△" evaluation (practical level) is 2 or less out of 10 items, and all others are "○" evaluation (good level) or "◎" evaluation (excellent level) and therefore excellent. I understand.
Further, in Examples 5 to 7, 25 to 27, 33 to 35, 54, 61, 62, 105 to 107, 120 to 122, 133 to 135, 154, 161, and 162, the evaluation of “Δ” of each evaluation ( Practical level is 3 to 9 out of 9 items, and there is no “x” evaluation (defective level), so that it can be used without any practical problems.
On the other hand, in Comparative Examples 1 to 13 and 21 to 33, pot life, coatability, processability, peel strength, removability, skin irritation, drug retention, skin permeability, and water vapor permeability It turns out that either is extremely inferior.

  Since the pressure-sensitive adhesive according to the present invention has excellent adhesiveness and removability, and also has excellent water vapor permeability, it has an optical field (for example, a protective film etc.), a construction field (for example, exterior and interior). , Equipment, etc.), electrical equipment field (for example, home appliances, kitchen equipment, air conditioning, etc.), transport equipment field (for example, ships, automobiles, etc.), furniture field, miscellaneous goods field, and other various fields other than optical fields such as industrial fields. In, it is also possible to use it for applications other than the transdermal absorbable adhesive sheet.

Claims (11)

A pressure-sensitive adhesive comprising a polyurethane urea resin (A) and a reactive compound (B) having a functional group capable of reacting with a hydroxyl group,
As a monomer unit constituting the polyurethane urea resin (A), a polyol (a1) unit, a polyisocyanate (a2) unit and an amine compound (a3) unit are contained,
The amine compound (a3) contains a diamine compound (a3-1) having two iminopropionic acid ester structures,
The polyurethane urea resin (A) has no aromatic ring, has an alkylene oxide unit and a hydroxyl group in its side chain, and has a weight average molecular weight of 10,000 to 500,000,
A pressure-sensitive adhesive containing 0.1 to 50 parts by weight of a reactive compound (B) having a functional group capable of reacting with a hydroxyl group, based on 100 parts by weight of a polyurethane urea resin (A). In 100% by weight of the total of the monomer units constituting the polyurethane urea resin (A),
45 to 94% by weight of the polyol (a1) unit,
5 to 30% by weight of polyisocyanate (a2) unit,
Amine compound (a3) unit is 1 to 25% by weight
The pressure-sensitive adhesive according to claim 1, wherein the pressure-sensitive adhesive is included.   The pressure-sensitive adhesive according to claim 1, wherein the polyol (a1) contains a polyether diol having no aromatic ring.   Content of the alkylene oxide unit in polyurethane urea resin (A) is 25 to 80 weight%, The pressure sensitive adhesive in any one of Claims 1-3 characterized by the above-mentioned. The pressure-sensitive adhesive according to any one of claims 1 to 4, wherein the diamine compound (a3-1) having two iminopropionic acid ester structures has a hydroxyl group. The pressure-sensitive adhesive according to any one of claims 1 to 5, wherein the amine compound (a3-1) having two iminopropionic acid ester structures has an alkylene oxide unit having a hydroxyl group or an alkoxy group at the terminal. Agent. Reactive compound (B) is a pressure sensitive adhesive according to any claims 1-6, characterized in that it comprises a polyisocyanate (b1). Furthermore, pressure sensitive adhesive according to any one of claims 1 to 7, characterized in that it comprises an ester compound (C). Furthermore, pressure sensitive adhesive according to any one of claims 1-8, characterized in that it comprises at least one of the percutaneous absorption drug (d1) or percutaneous absorption promoter (d2). At least on one surface, an adhesive sheet adhesive layer formed from pressure sensitive adhesive according to any claims 1-9 is laminated base material (G). The urethane prepolymer (X) obtained by reacting the polyol (a1) and the polyisocyanate (a2) is reacted with a diamine compound (a3-1) having two iminopropionic ester structures to form an isocyanate group at the end. A first step of producing a urethane urea resin (Y) having
The urethane urea resin (Y) is reacted with the reaction-terminating amine compound (a3-2-1) to have an alkylene oxide bond group and a hydroxyl group in the side chain and having a weight average molecular weight of 10,000 to 500,000. The second step of producing the polyurethane urea resin (A),
And a third step of mixing 0.1 to 50 parts by weight of the reactive compound (B) having a functional group capable of reacting with a hydroxyl group with 100 parts by weight of the polyurethane urea resin (A). A method for producing a pressure-sensitive adhesive.