JP2015004052A - Two-component type curable composition for forming adhesive coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a two-component type curable composition for forming an adhesive coating film having excellent safety, workability, flexibility, curability, water resistance, coating film strength, adhesiveness, and air permeability.SOLUTION: A two-component type curable composition for forming an adhesive coating film comprises an active hydrogen component (A) containing ethylene oxide adduct (a1) of a bisphenol compound having a hydroxyl value at 50 to 250 mgKOH/g and an organic polyisocyanate component (B). The active hydrogen component (A) can further contain polyoxyethylene glycol, polyoxyalkylene polyol (a21) which has a hydroxypropyl terminal with its content of primary hydroxy group at least 40%, and/or EO adduct (a22) of (a21).

Description

  The present invention relates to a composition for forming an adhesive film excellent in safety, workability, flexibility, curability, water resistance, adhesiveness, film strength and breathability, and particularly suitable for fixing a wound on a skin. The present invention relates to an adhesive film-forming composition.

  The material used to fix wounds by covering wounds or incisions on the skin surface, etc. has a low viscosity at the time of application and good workability. Disappearance and film formation are required. Further, it has a sufficient adhesive force to the skin immediately after curing until the wound is closed, but after that, the adhesive force decreases with time and it is required to be easily peelable from the skin. It has been proposed to use a cyanoacrylate adhesive as such a material (see, for example, Patent Document 1). However, the cyanoacrylate adhesive described in Patent Document 1 has a characteristic that it cures in a short time. However, formaldehyde is generated by hydrolysis, and there is a problem in safety. There are problems such as stuffiness due to moisture and a decrease in adhesive strength.

  Further, as an adhesive having high adhesive strength to the skin, a urethane-based surgical composition composed of an isocyanate functional polyalkylene oxide and a diamine has been proposed (see, for example, Patent Document 2). However, the surgical composition described in Patent Document 2 uses a large amount of diamine in the adhesive, and there is a concern about skin irritation caused by amine. In addition, due to the rapid curing reaction between isocyanate and diamine, there are problems in that workability at the time of coating is poor, and since a large number of urea bonds are present, the film is hard and the followability to stretch and contraction of the skin is poor.

International Publication No. 1997/31598 Special table 2009-518138 gazette

  The present invention has been made in view of the above problems, and an object of the present invention is a two-component curable type that is excellent in safety, workability, flexibility, curability, water resistance, film strength, adhesion, and breathability. It is providing the composition for adhesive film formation.

  As a result of intensive studies to solve the above problems, the present inventors have reached the present invention. That is, the present invention is a two-component curable adhesive comprising an active hydrogen component (A) containing an ethylene oxide adduct (a1) of a bisphenol compound having a hydroxyl value of 50 to 250 mgKOH / g and an organic polyisocyanate component (B). A composition for forming an adhesive film; an external composition for immobilizing a skin wound comprising the above composition; and an adhesive comprising the above composition.

When the composition for forming a two-component curable adhesive film of the present invention is applied so as to cover a wound or incision site on the skin surface to form a film and used for fixing a wound, the following effects are exhibited.
(1) High safety and low skin irritation.
(2) The viscosity of the mixed solution at the time of application is low and the workability is good.
(3) Since the flexibility of the film is high, the feeling of use is good.
(4) Curability is high, the curing reaction proceeds immediately after coating, and tack disappears in a short time.
(5) Since it has water resistance, it is strong against water and has high durability.
(6) It is excellent in the balance between the cohesive strength of the film and the adhesive strength with the skin, and is easy to peel off when peeled off from the skin.
(7) Since it has moisture permeability, it can prevent rash caused by sweat and stuffiness.
In addition, when used as an adhesive with leather, wood, paper, plastic, ceramic, metal, etc. as the adherend, it is excellent in safety, workability, curability, adhesion, water resistance and durability, When used, it does not have the property of being easily peeled off with time, and has excellent adhesive strength.

  The composition for forming a two-component curable adhesive film comprises an active hydrogen component (A) containing an ethylene oxide (hereinafter abbreviated as EO) adduct (a1) of a bisphenol compound having a hydroxyl value of 50 to 250 mgKOH / g. It consists of an organic polyisocyanate component (B).

Examples of the bisphenol compound used in (a1) include bisphenol A [2,2-bis (4-hydroxyphenyl) propane], bisphenol B [2,2-bis (4-hydroxyphenyl) butane], bisphenol C [2, 2-bis (4-hydroxy-3-methylphenyl) propane], bisphenol E [1,1-bis (4-hydroxyphenyl) ethane], bisphenol F (dihydroxydiphenylmethane), bisphenol S [bis (4-hydroxyphenyl) Sulfone], bisphenol AP [1,1-bis (4-hydroxyphenyl) -1-phenylethane], bisphenol AF [2,2-bis (4-hydroxyphenyl) hexafluoropropane] and the like.
Of these, bisphenol A, bisphenol B and bisphenol F are preferred from the viewpoints of workability, film strength, flexibility, adhesiveness and air permeability, and bisphenol A is more preferred.

  The hydroxyl value of the EO adduct (a1) of the bisphenol compound is usually 50 to 250 mgKOH / g, preferably 100 to 250 mgKOH / g, more preferably from the viewpoints of workability, film strength, flexibility, adhesiveness and air permeability. 150-250 mg KOH / g. The hydroxyl value is measured according to JIS K1557-1.

  Among (a1), from the viewpoint of film strength, an EO adduct of bisphenol A, bisphenol B or bisphenol F is more preferable, and an EO adduct of bisphenol A is more preferable.

  The content of (a1) in the active hydrogen component (A) is preferably 1% by weight or more, more preferably 5% based on the weight of (A) from the viewpoints of workability, film strength, flexibility and adhesiveness. % Or more. (A1) may be used alone or in combination of two or more.

  The active hydrogen component (A) is a polyether polyol (a2) having a hydroxyl value other than (a1) of 5 to 1058 mgKOH / g, a polyester polyol (a3) having a hydroxyl value of 20 to 375 mgKOH / g and / or a hydroxyl value. The polyhydric alcohol (a4) of 350-1900 mgKOH / g and the amine compound (a5) whose total amine value is 20-500 mgKOH / g can be contained. (A2), (a3), (a4) and (a5) may be used singly or in combination of two or more.

  As the polyether polyol (a2) having a hydroxyl value of 5 to 1058 mgKOH / g other than (a1), a polyhydric alcohol (a4) having a hydroxyl value of 350 to 1900 mgKOH / g described later to an alkylene oxide having 2 to 15 carbon atoms ( Hereinafter, it is obtained by adding AO). As AO to be used, EO, 1,2-propylene oxide (hereinafter abbreviated as PO), 1,3-propylene oxide, 1,2-, 1,3-, 2,3- or 1,4-butylene oxide (Hereinafter, butylene oxide is abbreviated as BO), α-olefin oxide having 5 to 12 carbon atoms, epihalohydrin (epichlorohydrin, epibromohydrin, etc.), styrene oxide, cyclohexene oxide, and a combination of two or more thereof. The binding mode when used in combination may be either block or random. Of these, EO and PO are preferred.

  Of (a2), from the viewpoint of flexibility, polyoxyethylene glycol, polyoxyalkylene polyols having a hydroxypropyl terminal and a primary hydroxyl group content of at least 40%, EO of (a21) and (a21) are preferred. This is an adduct (a22).

  As a polyoxyalkylene polyol (a21), the compound shown, for example by General formula (1) is mentioned.

  X in the general formula (1) is an m-valent residue obtained by removing m active hydrogen atoms from a compound having m active hydrogen atoms, and m is an integer of 2 to 20. When m exceeds 20, the viscosity of the polyoxyalkylene polyol (a21) becomes high, the viscosity at the time of application of the mixed liquid of the active hydrogen component (A) and the organic polyisocyanate component (B) becomes high, and workability is poor. Become. The compound having m active hydrogen atoms constituting the residue X includes a hydroxyl group-containing compound, an amino group-containing compound, a carboxyl group-containing compound, and a thiol, a hydroxyl group, a primary or secondary amino group, a carboxyl group, and a mercapto. And compounds having at least one group selected from the group.

  Examples of the hydroxyl group-containing compound include a polyhydric alcohol (a4) having a hydroxyl value of 350 to 1900 mg KOH / g described later; a castor oil-based polyol described later; a polymer or oligomer having m hydroxyl groups and a number average molecular weight of 2,000 or less [ Polyalkadiene (4 to 10 carbon atoms) polyol, such as polybutadiene polyol and hydrogenated product thereof; (co) polymer of hydroxyalkyl (2 to 4 carbon atoms) (meth) acrylate; polyvinyl alcohol (saponification degree of 60% or more) Etc.]; polyhydric phenols [monocyclic polyhydric phenols (such as pyrogallol, catechol and hydroquinone), bisphenol compounds, etc.]; phosphoric acid compounds (such as phosphoric acid, phosphorous acid and phosphonic acid); and two or more of these A mixture is mentioned.

  The number average molecular weight in the present invention is measured by gel permeation chromatography using tetrahydrofuran as a solvent and polyoxypropylene glycol as a standard substance. The sample concentration may be 0.25% by weight, the column stationary phase may be TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (both manufactured by Tosoh Corporation), and the column temperature may be 40 ° C.

  Examples of amino group-containing compounds include primary monoamines [mono (cyclo) alkylamines having 1 to 20 carbon atoms (methylamine, ethylamine, butylamine, octylamine, dodecylamine, cyclohexylamine, etc.), aromatics having 6 to 12 carbon atoms. Aliphatic and araliphatic monoamines (aniline, toluidine, benzylamine, etc.)]; polyamines having two or more active hydrogens [aliphatic diamines having 2 to 12 or more carbon atoms {alkylenediamines such as ethylenediamine, propylenediamine, Hexamethylene diamine, mono- or di-alkyl (C1-C4) alkylene diamine (dimethylpropylenediamine, etc.)}, C6-C15 alicyclic diamine (1,4-diaminocyclohexane, isophorone diamine) And 4,4′-diaminocyclo Xylmethane, etc.), C6-C15 aromatic diamine {m- or p-phenylenediamine, tolylenediamine, diethyltoluenediamine, 4,4'-diaminophenylmethane and 2,2-bis (4,4'- Diaminophenyl) propane and the like}, araliphatic diamines having 8 to 15 carbon atoms (m- or p-xylylenediamine, etc.), heterocyclic polyamines having 4 to 10 carbon atoms {piperalidine, aminoalkyl (2 to 4 carbon atoms) ) Piperazine (for example, aminoethylpiperazine), aminoalkyl (carbon number 2 to 4) imidazole, etc.}, alkylene group polyalkylene polyamine having 2 to 4 carbon atoms {diethylenetriamine, dipropylenetriamine, triethylenetetramine, number average molecular weight 2, Up to 000 polyethyleneimine and mono-, di- or tri-a Kill (carbon number 1 to 4) polyalkylene polyamine (for example, dimethyldipropylene triamine)} and the like]; mono- or di-alkanolamine having 2 to 4 carbon atoms in the hydroxyalkyl group (monoethanolamine, monoisopropanolamine, diethanolamine) And diisopropanolamine etc.); polymers or oligomers having one or more amino groups and a number average molecular weight of 2,000 or less [aminoalkyl (carbon number 2 to 4) (meth) acrylate (co) polymer and poly Ether (poly) amine (such as polyoxypropylene diamine and polyoxypropylene triamine)]; and a mixture of two or more thereof.

  Examples of the carboxyl group-containing compound include aliphatic polycarboxylic acids having 2 to 36 carbon atoms (such as succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, and dimerized linoleic acid), and those having 8 to 15 carbon atoms. Aromatic polycarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.), unsaturated carboxylic acid polymer [(meth) acrylic acid (co) polymerization with a number average molecular weight of 2,000 or less And the like, and mixtures of two or more thereof.

  Examples of the thiol include 2 to 8 or more polyvalent polythiols having 2 to 6 carbon atoms (ethanedithiol, propanedithiol, 1,3- or 1,4-butanedithiol, 1,6-hexanedithiol, 3-methyl- 1,5-pentanedithiol, etc.).

  Of these, preferred are a hydroxyl group-containing compound and an amino group-containing compound, and more preferred are a polyhydric alcohol (a4) having a hydroxyl value of 350 to 1900 mg KOH / g described below and a castor oil-based polyol described below, Propylene glycol, glycerin, pentaerythritol, dipentaerythritol, sorbitol, polyglycerin (polymerization degree 2 to 10) and castor oil.

  A in General formula (1) is a C2-C12 alkylene group optionally substituted with a phenyl group or a halogen atom, a C2-C12 linear or branched alkylene group, C6-C6 10 cycloalkylene groups, and those substituted with these phenyl groups, halophenyl groups, or halogen atoms (Cl, Br, etc.).

  Specific examples of A include an ethylene group, 1,2- or 1,3-propylene group, 1,2-, 2,3-, 1,3- or 1,4-butylene group, having 5 to 12 carbon atoms. Examples include 1,2-alkylene groups (such as 1,2-dodecylene group), 1,2-cyclohexylene group, chloropropylene group, bromopropylene group, phenylethylene group, and chlorophenylethylene group.

  (AO) in the general formula (1) is obtained by adding the AO to a compound having m active hydrogen atoms constituting the residue X as described later. Two or more types of AO can be used in combination, and the bonding mode when p (A-O) is composed of two or more oxyalkylene groups may be either block or random. Preferable AO to be used is PO and 1,2-BO.

  Z in the general formula (1) is a propylene group, p is 0 or an integer of 1 to 199, q is an integer of 1 to 200, and satisfies p + q ≦ 200.

The polyoxyalkylene polyol (a21) has a hydroxypropyl group at the terminal. Confirmation of having a hydroxypropyl group terminal can be performed by, for example, ¹ H-NMR method. The hydroxypropyl group includes a primary hydroxyl group (hydroxyl group bonded to primary carbon) represented by the following chemical formula (2) and a secondary hydroxyl group (bonded to secondary carbon) represented by the chemical formula (2 ′). Hydroxyl group) -containing groups, but the primary hydroxyl group content (hereinafter, primary), which is the ratio of the number of primary hydroxyl group-containing groups to the total number of primary hydroxyl group-containing groups and secondary hydroxyl group-containing groups in (b). The conversion rate is preferably 40% or more, and more preferably 70% or more from the viewpoint of fast curability.

The primary rate can be determined by pretreatment (esterification) of the sample in advance and then measuring by ¹ H-NMR method.

Details of the ¹ H-NMR method will be described below.
<Sample preparation method>
About 30 mg of a measurement sample is weighed into an NMR sample tube having a diameter of 5 mm, and about 0.5 ml of deuterated solvent is added and dissolved. Thereafter, about 0.1 ml of trifluoroacetic anhydride is added to obtain a sample for analysis. As the deuterated solvent, for example, a solvent capable of dissolving the sample is appropriately selected from deuterated chloroform, deuterated toluene, deuterated dimethyl sulfoxide, deuterated dimethylformamide, and the like.
<NMR measurement>
¹ H-NMR measurement is performed under normal conditions.
<Calculation method of primary rate>
By the pretreatment method described above, the terminal hydroxyl group of the polyoxypropylene polyol reacts with the added trifluoroacetic anhydride to become a trifluoroacetic acid ester. As a result, a signal derived from a methylene group to which a primary hydroxyl group is bonded is observed at around 4.3 ppm, and a signal derived from a methine group to which a secondary hydroxyl group is bonded is observed at around 5.2 ppm. The primary rate is calculated by the following formula.
Primary rate (%) = [x / (x + 2 × y)] × 100 [where x is an integral value of a signal derived from a methylene group bonded with a primary hydroxyl group in the vicinity of 4.3 ppm, and y is 5. It is an integral value of a signal derived from a methine group to which a secondary hydroxyl group in the vicinity of 2 ppm is bonded. ]

  (A21) can be produced, for example, by the method described in JP-A No. 2000-344881. As a preferable example of (a21), PO is added to the active hydrogen-containing compound (h) represented by the following general formula (3) in the presence of a tris (pentafluorophenyl) borane catalyst (hereinafter abbreviated as TPB). Examples thereof include those obtained by ring-opening addition polymerization.

  X, A and m in the general formula (3) are the same as those in the general formula (1), and p is 0 or an integer of 1 to 199.

  Specific examples of (h) include the same compounds as those exemplified as the compound having m active hydrogen atoms constituting the residue of the general formula (1) when p is 0.

  (h) when p is 1 or more is a polyol obtained by (co) adding AO to a compound constituting the residue X using a conventionally known catalyst (such as an alkali metal hydroxide); Preferred examples include propylene glycol PO adduct, glycerin PO adduct, polyglycerin PO adduct, propylene glycol 1,2-BO adduct, glycerin 1,2-BO adduct, polyglycerin 1, Examples include 2-BO adducts, PO / 1,2-BO coadducts of glycerin (block or random), and the like.

  The amount of TPB used in producing (a21) by subjecting PO to ring-opening addition polymerization in (h) is not particularly limited, but is usually 0.00005 to 10% by weight, preferably 0, based on the weight of (a21). 0.0001 to 1% by weight.

  The number of moles of PO added is usually 1 to 200 moles, preferably 2 to 100 moles, and more preferably 3 to 30 moles per active hydrogen atom in (h). The number of added moles of all AOs per active hydrogen atom of the compound constituting the residue X (the sum of the first stage AO and the second stage PO) is usually 1 to 200 moles, preferably 3 to 100 moles. is there. When the number of added moles exceeds 200 moles, the viscosity of the polyoxyalkylene polyol (a21) increases, and the viscosity of the mixture of the active hydrogen component (A) and the organic polyisocyanate component (B) during coating increases. Workability is reduced.

  Therefore, q in General formula (1) is 1-200 normally, Preferably it is 2-100, More preferably, it is 3-30. Moreover, p + q in General formula (1) is 1-200 normally, Preferably it is 3-100.

  The reaction temperature for ring-opening addition polymerization of PO is usually 0 to 250 ° C, preferably 20 to 180 ° C. From the viewpoint of controlling the reaction temperature, a method in which PO is dropped into the mixture of (h) and TPB or a mixture of PO and TPB is dropped into (h) is preferable.

  Since the produced addition polymer contains TPB, it is adsorbed and removed using an adsorbent such as synthetic silicate (magnesium silicate, aluminum silicate, etc.) and activated clay.

  Preferable specific examples of (a21) include propylene glycol PO adduct, polyoxypropylene glycol (terminal secondary hydroxyl group) PO adduct, glycerin PO adduct, polyglycerin PO adduct, propylene glycol 1, PO adduct of 2-BO adduct (terminal secondary hydroxyl group), PO adduct of 1,2-BO adduct (terminal secondary hydroxyl group) of glycerol, 1,2-BO adduct of polyglycerin (secondary terminal) Hydroxyl group) PO adduct and castor oil PO adduct.

  The EO adduct (a22) of the polyoxyalkylene polyol (a21) in the present invention can be obtained by adding EO to (a21) by an ordinary method. The amount of the added oxyethylene group is 40% by weight or less, preferably 30% by weight or less, particularly preferably 10% by weight or less, based on the total weight of the oxyalkylene contained in (a22).

  The hydroxyl value of (a21) and (a22) varies depending on whether or not other polyols are used together and the type of polyol used together, but is preferably 5 to 800 mgKOH / g, more preferably 10 to 700 mgKOH / g, and particularly preferably 30 to 600 mg KOH / g.

  (A21) and (a22) may be used in combination of two or more. As an aspect of the combined use, for example, an initiator [a compound having m active hydrogen atoms constituting the residue X in the general formula (1)] having a different type [for example, based on a polyhydric alcohol (glycerin, etc.) And those based on polyamines (ethylenediamine, etc.), those having different numbers of functional groups [m in general formula (1)] [for example, those based on 2-3 functional compounds (ethylene glycol, glycerin, etc.) 4 to 8 functional compounds (based on pentaerythritol, sorbitol, sucrose, etc.), hydroxyl value or AO addition mole number [p + q in general formula (1)] [hydroxyl value 400 mgKOH / g or more ( For example, 450-700 mgKOH / g) and less than 400 mgKOH / g (for example, 30-300 mgKOH / g)]. That.

  When the polyether polyol (a2) is used, the content of (a2) in the active hydrogen component (A) is preferably 1% by weight or more, more preferably 3 to 95% by weight, based on the weight of (A). It is.

  Examples of the polyester polyol (a3) having a hydroxyl value of 20 to 375 mgKOH / g include polycarboxylic acids [aliphatic saturated or unsaturated polycarboxylic acids having 4 to 40 carbon atoms (adipic acid, azelaic acid, dodecanedioic acid, maleic acid, Fumaric acid, itaconic acid, dimerized linoleic acid, etc.) and / or aromatic polycarboxylic acid having 8 to 12 carbon atoms (terephthalic acid, isophthalic acid, etc.)] and polyol [polyhydric alcohol (a4) and / or A linear or branched polyester polyol from the AO adduct]; a polylactone polyol [for example, a polyhydric alcohol (a4) described later, etc. as an initiator, and a lactone having 4 to 12 carbon atoms (γ-butyrolactone, ε- Caprolactone, α-methyl-ε-caprolactone, ε-methyl-ε-caprolactone, γ-valerolactone, etc.) Polyol (for example, polycaprolactone polyol) subjected to ring-opening addition polymerization in the presence of a catalyst (an organometallic compound, a metal chelate compound, a fatty acid metal acylated product, etc.); AO (EO) on a polyester having a carboxyl group and / or a hydroxyl group at the terminal Polyether polyol obtained by addition polymerization of polyhydric alcohol (a4) and carbonate ester (dimethyl carbonate, etc.) described later; castor oil type Polyols [for example, castor oil, partially dehydrated castor oil, partially acylated castor oil, polyhydric alcohol (a4) described later or polyoxypropylene polyol containing the above (a21) and castor oil, or castor oil fatty acid Obtained by esterification reaction Castor oil fatty acid ester and the like] and the like. The valence of the polyester polyol (a3) is preferably 2 to 3, more preferably 2.

  When the polyester polyol (a3) is used, the content of (a3) in the active hydrogen component (A) is preferably 1% by weight or more, more preferably 2 to 20% by weight based on the weight of (A). is there.

  Examples of the polyhydric alcohol (a4) having a hydroxyl value of 350 to 1900 mg KOH / g include aliphatic polyhydric alcohol [aliphatic dihydric alcohol having 2 to 20 carbon atoms (alkylene glycol such as ethylene glycol, propylene glycol, 1,3- Butylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methylpentanediol, neopentylglycol, 1,9-nonanediol, etc.); Polyhydric alcohols (glycerin, trimethylolpropane, pentaerythritol, sorbitol, xylitol, mannitol, etc.); intermolecular or intramolecular dehydrates such as dipentaerythritol, polyglycerin (degree of polymerization 2-20) and sorbitan; Its derivatives (glycoxide etc. For example, glucose, fructose, sucrose and α-methyl glucoside, etc .; (bi) cycloalkylenediols having 6 to 15 carbon atoms {for example 1,4-dihydroxycyclohexane, 1,4-bis (hydroxymethyl) cyclohexane and 2,2 -Bis (4,4′-hydroxycyclohexyl) propane and the like}]; an aromatic ring-containing polyhydric alcohol having 8 to 15 carbon atoms [m- or p-xylylene glycol, 1,4-bis (hydroxyethyl) benzene and the like] Etc.

  When the polyhydric alcohol (a4) is used, the content of (a4) in the active hydrogen component (A) is preferably 50% by weight or less, more preferably 1 to 40% by weight, based on the weight of (A). It is.

  The amine compound (a5) having a total amine value of 20 to 500 mgKOH / g can be used for the purpose of improving workability and film strength. As the amine compound (a5) having a total amine value of 20 to 500 mgKOH / g, polyamines [aliphatic diamine {alkylene diamine, mono- or di-alkyl alkylene diamine, etc.}] having 2 to 4 active hydrogens; Mono- or di-alkanolamines; polymers or oligomers having one or two to four amino groups and a number average molecular weight of 3000 or less [aminoalkyl (meth) acrylate (co) polymers and polyether (poly) amines { Polyoxypropylenediamine, polyoxypropylenetriamine and poly (n = 2-6) alkylene (2-6 carbon atoms) poly (n = 3-7) amine (diethylenetriamine, dipropylenetriamine, dihexylenetriamine, triethylenetetramine, Tetraethylene pentamine, pentaethylene Kisamin and hexaethylene compounds} like] propylene oxide to an imino group are added; heptamine, etc.); and mixtures of two or more thereof.

  The content of (a4) in the active hydrogen component (A) when using the amine compound (a5) is preferably based on the weight of (A) from the viewpoints of safety, skin irritation, workability and film strength. Is 50% by weight or less, more preferably 1 to 40% by weight.

  As the organic polyisocyanate component (B), those conventionally used in the production of polyurethane can be used, and a chain aliphatic polyisocyanate having 4 to 22 carbon atoms having 2 to 3 or more isocyanate groups (b1). ), C8-C18 alicyclic polyisocyanate (b2), C8-C26 aromatic polyisocyanate (B3), C10-C18 araliphatic polyisocyanate (b4), and these polyisocyanates And the modified product (b5). An organic polyisocyanate component (B) may be used individually by 1 type, and may use 2 or more types together.

  Examples of the chain aliphatic polyisocyanate (b1) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, and 2,2,4- Trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2,6-di Isocyanato hexanoate.

  Examples of the alicyclic polyisocyanate (b2) having 8 to 18 carbon atoms include isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4′-dicyclohexylmethane diisocyanate (hereinafter abbreviated as hydrogenated MDI), cyclohexylene diisocyanate, Mention may be made of methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

  Examples of the aromatic polyisocyanate having 8 to 26 carbon atoms (b3) include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter abbreviated as TDI), and crude TDI. 4,4′- or 2,4′-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), crude MDI, polyarylpolyisocyanate, 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4 '-Diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4', 4 "-triphenylmethane triisocyanate and m- or p -Isocyanatophenylsulfonyl isocyanate.

  Examples of the araliphatic polyisocyanate (b4) having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate.

  As the modified polyisocyanate (b5) of (b1) to (b4), the modified polyisocyanate (urethane group, carbodiimide group, allohanate group, urea group, biuret group, uretdione group, uretoimine group, isocyanurate group) Or oxazolidone group-containing modified products), for example, modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, and isocyanurate-modified IPDI. Of the modified product.

  Examples of the urethane prepolymer having an isocyanate group include an isocyanate group-terminated urethane prepolymer obtained by reacting at least one selected from the polyisocyanates exemplified above and modified products thereof with an active hydrogen compound. Examples of the active hydrogen compound include (a1) of the present invention, polyoxyalkylene polyol containing the above (a21) and (a22), polyester polyol (a3), and polyhydric alcohol (a4).

  In the urethane prepolymer having an isocyanate group, the equivalent ratio of the NCO group in the polyisocyanate or the modified product thereof to the active hydrogen-containing group in the active hydrogen compound (NCO group / active hydrogen-containing group) is usually 1.1 / 1. -100/1, preferably 2 / 1-80 / 1, more preferably 3 / 1-60 / 1. The NCO group content in the urethane prepolymer is usually 3 to 35% by weight, preferably 5 to 30% by weight.

  The organic polyisocyanate component (B) is preferably a chain aliphatic polyisocyanate (b1) having 4 to 22 carbon atoms or an alicyclic polyisocyanate having 8 to 18 carbon atoms (b2) from the viewpoints of curability and flexibility. And modified products thereof (urethane group, carbodiimide group, allohanate group, urea group, biuret group, uretdione group, uretoimine group, isocyanurate group or oxazolidone group-containing modified product), more preferably a chain having 4 to 22 carbon atoms. Modified products of urethane-like aliphatic polyisocyanate (b1) (urethane group, carbodiimide group, allohanate group, urea group, biuret group, uretdione group, uretoimine group, isocyanurate group or oxazolidone group-containing modified product), particularly preferred are those of HDI Isocyanurate group-containing modified product.

  In the two-component curable adhesive film-forming composition comprising the active hydrogen component (A) and the organic polyisocyanate component (B) containing (a1) of the present invention, depending on the application and the degree of curability, A urethanization catalyst (C) can be used.

  Examples of (C) include metal catalysts and amine catalysts. Metal catalysts include tin catalysts (trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate, dibutyltin maleate, etc.), lead catalysts (lead oleate) , Lead 2-ethylhexanoate, lead naphthenate, lead octenoate, etc.], bismuth catalyst [bismuth carboxylate, bismuth alkoxide, chelate compound of dicarbonyl group and bismuth, etc.], titanium catalyst [isopropoxy Tri-N-ethylaminoethylaminato titanium, tetrabutyl titanate, tetraisopropoxybisdioctyl phosphite titanium, etc.], iron catalyst [iron carboxylate compounds (iron lactate, iron ricinoleate, etc.), ferrocene compounds (ferro Emissions, acetyl ferrocene, etc.), naphthenic acid metal salt of the phthalocyanine iron, etc.], and other metal catalysts [such as cobalt naphthenate, phenyl mercuric propionate, etc.].

  Examples of the amine catalyst include triethylenediamine, tetramethylethylenediamine, diazabicycloalkene [1,8-diazabicyclo [5,4,0] undecene-7 [DBU (manufactured by San Apro Co., Ltd., registered trademark)], etc.], dialkyl ( C1-C3) aminoalkyl (C2-C4) amine [dimethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, etc.], heterocyclic aminoalkyl (C2-C6) Examples include amines [2- (1-aziridinyl) ethylamine, 4- (1-piperidinyl) -2-hexylamine and the like], and N-methyl and N-ethylmorpholine.

  Of these, diazabicycloalkene, bismuth-based catalyst and tin-based catalyst are preferable, and DBU, bismuth carboxylate and dibutyltin dilaurate are particularly preferable.

  The use amount of the urethanization catalyst (C) varies depending on the application, but when high fast curability is required, it is preferably 1,000 ppm or less, particularly based on the weight of the two-component curable adhesive film-forming composition. Preferably it is 10-4500 ppm. (C) may be used alone or in combination of two or more.

  The NCO of (B) when the active hydrogen component (A) and the organic polyisocyanate component (B) constituting the two-part curable adhesive film forming composition of the present invention are mixed to form an adhesive film. The ratio of equivalents to equivalents of active hydrogen-containing groups (A) (equivalent of NCO / equivalent of active hydrogen-containing groups) is usually 1/5 to 5/1, preferably 1/4 to 4/1, more preferably 1/3 to 3/1.

  The two-component curable adhesive film-forming composition usually comprises a combination of two components, an active hydrogen component (A) and an organic polyisocyanate component (B). When the urethanization catalyst (C) is used, a combination of the three components (A), (B), and (C) may be used. Usually, a predetermined amount of (C) is previously added to (A) or (B ) Is used as a combination of two components mixed together.

  In the composition for forming a two-component curable adhesive film of the present invention, additives such as a plasticizer, an antioxidant, and an ultraviolet absorber may be used as necessary as long as the effects of the present invention are not impaired. An additive may be used individually by 1 type, or may use 2 or more types together. When these additives are used, a predetermined amount of the additive is usually mixed with (A) or (B) in advance.

  The plasticizer used in the present invention is for the purpose of reducing the viscosity of the two-part curable adhesive film-forming composition before curing to improve the coatability and adjusting the elasticity of the film after curing. For example, ester plasticizers [dibutyl phthalate, dioctyl phthalate, dioctyl adipate and polyoxyethylene glycol (molecular weight: 200) diadipate, etc.]; petroleum resin plasticizers;

  The content of the plasticizer is preferably 0 to 50% by weight, more preferably 1 to 30% by weight, based on the weight of the two-component curable adhesive film-forming composition.

  The antioxidant used in the present invention is added for the purpose of improving the storage stability. For example, a hindered phenol compound [triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxy] is used. Phenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and 2,2-thio-diethylenebis [3- (3,5-di-) t-butyl-4-hydroxyphenyl) propionate] and the like] and phosphite compounds [tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t- Butylphenyl) octyl phosphite, bis (2,6-di-t-butylphenyl) pentaerythritol di-phosphite and Rakisu (2,4-di -t- butyl-phenyl) 4,4'-biphenylene - di - phosphonite, etc.] and the like. The content of the antioxidant is 0.001 to 2% by weight, preferably 0.01 to 1% by weight, based on the weight of the two-component curable adhesive film forming composition.

  The two-part curable adhesive film-forming composition of the present invention is particularly suitable as an external composition for immobilizing wounds such as skin wounds or incision sites, but leather, wood, papers, plastics, ceramics. It can also be used for bonding a wide range of adherends such as metals.

  After a predetermined amount of components (A) and (B) of the two-component curable adhesive film forming composition is mixed, mixed with a static mixer or mechanical mixer, and then coated and reacted to form an adhesive film Can be made. The gelation time is usually 3 to 20 minutes, and complete curing requires 12 to 24 hours at room temperature.

  Further, the NCO group content in the mixed solution immediately after mixing (A) and (B) is usually 2 to 15% by weight, preferably 3 to 13% by weight.

The coating method of the composition for forming a two-component curable adhesive film is not particularly limited and can be applied by a known method. In the case of using it for fixing a wound on the skin, a method of applying using a brush, sponge or the like can be mentioned. In the case of using it for adhesion of other base materials, a method using a coating machine can be mentioned. Examples of the coating machine that can be used include a gravure coater, a reverse roll coater, a comma coater, a spin coater, a curtain coater, a slot coater, and a bar coater. The coating amount of the two-component curable adhesive film-forming composition is usually 1-1000 g / m ² , preferably 2-500 g / m ² , more preferably 3-100 g / m ² .

  The application temperature of the two-component curable adhesive film-forming composition is usually 15 to 40 ° C. when used for skin adhesion. When used for adhesion of other substrates, the temperature is usually 10 to 100 ° C., and preferably 20 to 80 ° C. from the viewpoint of coating properties and suppression of thermal deterioration. The viscosity of the two-component curable adhesive film-forming composition at the coating temperature is usually 0.01 to 100 Pa · s, preferably 0.02 to 50 Pa · s, more preferably 0.03 to 0.03 from the viewpoint of coating properties. 10 Pa · s. The viscosity in the present invention is measured with a B-type rotational viscometer.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. Below, a part shows a weight part.

The trade names and compositions used as raw materials are as follows.
・ "Sanniks GP-250"; polyoxypropylene triol [manufactured by Sanyo Chemical Industries, Ltd., hydroxyl value = 673 mgKOH / g]
・ "Sanniks GP-3000"; polyoxypropylene triol [manufactured by Sanyo Chemical Industries, Ltd., hydroxyl value = 56 mgKOH / g]
-"Sanix PP-1000"; polyoxypropylene diol [manufactured by Sanyo Chemical Industries, Ltd., hydroxyl value = 112 mgKOH / g]
・ "New Pole BPE-100"; EO 10 mol adduct of bisphenol A [manufactured by Sanyo Chemical Industries, Ltd., hydroxyl value = 167 mgKOH / g]
-"New Pole BPE-60"; EO 6 mol adduct of bisphenol A [manufactured by Sanyo Chemical Industries, Ltd., hydroxyl value = 228 mgKOH / g]
"PEG-200": polyoxyethylene diol [manufactured by Sanyo Chemical Industries, hydroxyl value = 561 mgKOH / g]
・ "New Pole GE-600"; polyoxyethylene triol [manufactured by Sanyo Chemical Industries, Ltd., hydroxyl value = 281 mgKOH / g]
"New Pole SE-240"; EO24 mol adduct of sorbitol [manufactured by Sanyo Chemical Industries, Ltd., hydroxyl value = 263 mgKOH / g]
-"Sun Amir TAP-10"; polyether amine [manufactured by Sanyo Chemical Industries, Ltd., total amine value = 250 mgKOH / g, 1,2 amine value = 152 mgKOH / g]
"D400": polyoxyalkylene diamine [Mitsui Chemical Fine Co., Ltd., total amine value = 250 mgKOH / g]
"Duranate TLA-100": Isocyanurate group-containing modified product of hexamethylene diisocyanate [Asahi Kasei Chemicals Co., Ltd., NCO group content = 23.5%, viscosity = 500 mPa.s]
"Millionate MT": 4,4'-MDI [Nippon Polyurethane Industry Co., Ltd., NCO% = 33.6]
"Neostan U-600"; mixture of bismuth tris (2-ethylhexanoate) and 2-ethylhexanoic acid [curing catalyst manufactured by Nitto Kasei Co., Ltd.]

<Production Example 1>
A stainless steel autoclave equipped with a stirrer, a temperature controller, a heat exchanger as a condensing facility, a raw material supply line and an exhaust line. After adding 250 parts and 0.09 part of TPB, stirring was started, and the pressure in the autoclave and the condensation facility was reduced to 0.005 MPa. 400 parts of PO was continuously put into the liquid phase over 12 hours while controlling the reaction temperature to be maintained at 70 to 80 ° C. through the raw material supply line. A refrigerant at −30 ° C. was circulated in order to condense and recover PO in the condensing facility. Subsequently, after aging at 70 ° C. for 4 hours, 30 parts of synthetic silicate [manufactured by Kyowa Chemical Industry Co., Ltd .; “KYOWARD 600”] and 40 parts of water were added and treated at 60 ° C. for 3 hours. After taking out, it filtered with a 1 micron filter, and it dehydrated, and the polyoxyalkylene polyol (a21-1) was obtained. The hydroxyl value of (a21-1) was 280 mgKOH / g, the viscosity was 280 mPa · s / 25 ° C., and the primary rate was 72%.

<Production Example 2>
Synthetic silicate and water are added to the polyoxypropylene polyol of Production Example 1 before the treatment, and 4.0 parts of potassium hydroxide and 200 parts of EO through the raw material supply line are controlled so that the reaction temperature is maintained at 130 to 140 ° C. However, it was put in over 6 hours. Subsequently, aging was performed at 130 to 140 ° C. for 3 hours. Next, 30 parts of synthetic silicate [manufactured by Kyowa Chemical Industry Co., Ltd .; “KYOWARD 600”] and 40 parts of water were added and treated at 60 ° C. for 3 hours. After taking out from the autoclave, it was filtered with a 1 micron filter and dehydrated for 2 hours to obtain an EO adduct (a22-1) of polyoxypropylene polyol. The hydroxyl value of (a22-1) was 224 mgKOH / g, the viscosity was 250 mPa · s / 25 ° C., and the primary rate was 90%.

<Production Examples 3 to 11>
A four-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube was charged with the polyol, amine compound and curing catalyst shown in Table 1 in the number of blended parts shown in Table 1, and stirred and mixed at 40-50 ° C. for 1 hour under a nitrogen stream Active hydrogen components (A-1) to (A-9) were obtained. The hydroxyl value of (A-1) was 311 mgKOH / g, and the viscosity was 750 mPa · s / 25 ° C. The hydroxyl value of (A-2) was 324 mgKOH / g, and the viscosity was 710 mPa · s / 25 ° C. The hydroxyl value of (A-3) was 300 mgKOH / g, and the viscosity was 700 mPa · s / 25 ° C. The hydroxyl value of (A-4) was 277 mgKOH / g, and the viscosity was 670 mPa · s / 25 ° C. The hydroxyl value of (A-5) was 246 mgKOH / g, and the viscosity was 820 mPa · s / 25 ° C. (A-6) had a hydroxyl value of 380 mgKOH / g and a viscosity of 200 mPa · s / 25 ° C. The hydroxyl value of (A-7) was 500 mgKOH / g, and the viscosity was 90 mPa · s / 25 ° C. The hydroxyl value of (A-8) was 384 mgKOH / g, the total amine value was 46 mgKOH / g, and the viscosity was 120 mPa · s / 25 ° C. The hydroxyl value of (A-9) was 404 mgKOH / g, the total amine value was 63 mgKOH / g, and the viscosity was 110 mPa · s / 25 ° C.

<Comparative Production Examples 1-2>
A four-necked flask equipped with a stirrer, a thermometer and a nitrogen introduction tube was charged with the polyols shown in Table 1, the comparative active hydrogen compound and the curing catalyst in the number of parts shown in Table 1, under a nitrogen stream at 40 to 50 ° C. Were mixed with stirring for 1 hour to obtain active hydrogen components (A′-1) to (A′-2) for comparison. The hydroxyl value of (A′-1) was 281 mgKOH / g, the total amine value was 519 mgKOH / g, and the viscosity was 150 mPa · s / 25 ° C. The hydroxyl value of (A′-2) was 477 mgKOH / g, and the viscosity was 120 mPa · s / 25 ° C.

<Production Example 12>
A four-necked flask equipped with a stirrer, thermometer and nitrogen inlet tube was charged with 55 parts of “Millionate MT”, 43 parts of “Sanix GP-3000” and 2 parts of “Sanix PP-1000” under a nitrogen stream. It was made to react at 70-80 degreeC for 4 hours, and the organic polyisocyanate component (B'-1) which consists of a NCO group terminal urethane prepolymer was obtained. (B′-1) had an NCO group content of 16.5% by weight and a viscosity of 1500 mPa · s / 25 ° C.

<Examples 1-9 and Comparative Examples 1-2>
Using the active hydrogen component (A) and the organic polyisocyanate component (B) listed in Table 2, the two-part curable adhesive film-forming composition of the present invention in the weight ratio shown in Table 2 and the two-part curable for comparison A composition for forming a mold adhesive film was obtained.
Table 2 shows the results of measuring or evaluating the viscosity of the mixed solution, the curing rate (tack-free time), the strength of the cured film, the initial adhesive strength, the skin adhesion and the skin irritation of each composition obtained. Show.

<Measurement method of viscosity of liquid mixture>
After mixing the active hydrogen component (A) and the organic polyisocyanate component (B) by adjusting the temperature to 25 ° C, the viscosity (mPa · s) after 30 seconds from the start of mixing while adjusting the temperature to 25 ° C is the rotational viscosity. Measured with a meter (B-type viscometer).

<Measurement method of curing speed (tack free time)>
A mixture of an active hydrogen component (A) and an organic polyisocyanate component (B) is coated on a PET film having a film thickness of 50 μm so as to have a film thickness of 20 μm using a bar coater, and the conditions are 23 ° C. and 50% RH. Under curing, the time (tack free time) until the surface tack (stickiness) disappears was measured.

<Measurement method of strength and elongation of cured film>
A mixture of the active hydrogen component (A) and the organic polyisocyanate component (B) was applied on the PET film subjected to the release treatment so as to have a film thickness of 50 μm using a bar coater, and the coating film was 23 ° C. and 60% RH. The film was cured under conditions for 24 hours to prepare a cured film of a two-component curable adhesive film forming composition. The obtained cured film was punched into a size of No. 3 dumbbell according to the method described in JIS K 6251, and was prepared at 100 mm / 23 ° C. using Autograph AG-IS (manufactured by Shimadzu Corporation). Pulling at a rate of minutes, the breaking strength and breaking elongation were measured.

<Measurement method-1 of initial adhesive force>
A mixture of the active hydrogen component (A) and the organic polyisocyanate component (B) is coated on a PET film having a thickness of 50 μm so as to have a thickness of 20 μm by using a bar coater. ) And then cured at 23 ° C. and 50% RH for 3 days to obtain a bonded sample. This sample was cut into a size of 200 mm long × 15 mm wide, and T-type peel strength at 23 ° C. was measured according to JIS K 6854-3 using Autograph AG-IS (manufactured by Shimadzu Corporation). . The pulling speed is 300 mm / min, and the unit is g / 15 mm.

<Measurement method-2 of initial adhesive force>
Three collagen sheets having a thickness of 50 μm were bonded together using a double-sided tape, and then cut into a size of 200 mm long × 15 mm wide to prepare a test sheet having a three-layer structure. After immersing the two test sheets in physiological saline for 24 hours and then pulling up and wiping off the surface physiological saline, one of the test sheets is spread on a glass plate, and the film thickness of the collagen sheet is 20 μm. Apply a mixture of the active hydrogen component (A) and the organic polyisocyanate component (B) using a bar coater, paste the other test sheet, and cure at 23 ° C. and 50% RH for 3 days. A bonded sample was obtained. The T-type peel strength at 23 ° C. was measured according to JIS K 6854-3 using Autograph AG-IS (manufactured by Shimadzu Corporation) for this bonded sample. The pulling speed is 300 mm / min, and the unit is g / 15 mm.

<Skin Adhesion-1>
Apply a mixture of active hydrogen component (A) and organic polyisocyanate component (B) on human skin (inside of left arm) so that the film thickness is about 50 μm, and the state of the film after 1 week (floating / peeling) ) And the ease of peeling when the film was peeled off was determined according to the following criteria. Moreover, the following property evaluated the followability of the film to the skin.
[Floating / peeling evaluation criteria]
◎: No floating / peeling ○: Area of floating / peeling part is less than 20% ×: Area of floating / peeling part is 20% or more
(Double-circle): It can peel off easily.
X: It is hard to peel off and a film | membrane remains in a part or whole surface of an application part.
[Evaluation criteria for skin follow-up]
A: There is almost no resistance to the skin surface due to the film when the arm is expanded or contracted.
○: There is a slight resistance to the skin surface due to the film when the arm is extended or contracted.
X: The resistance of the skin surface due to the film is large when the arm is expanded and contracted.

<Skin Adhesion-2>
Apply a mixture of active hydrogen component (A) and organic polyisocyanate component (B) on human skin (inside the left arm) so that the film thickness is about 50 μm, and soak in warm water at 40 ° C. for 1 hour after 24 hours. The state of the adhesive (floating / peeling) after the evaluation was evaluated.
[Floating / peeling after water resistance test]
◎: No floating / peeling ○: Area of floating / peeling part is less than 5% Δ: Area of floating / peeling part is 5% or more to less than 20% ×: Area of floating / peeling part is 20% or more

<Skin irritation>
Applying a mixture of active hydrogen component (A) and organic polyisocyanate component (B) on human skin (inside the left arm) so that the film thickness is about 50 μm, and skin pain until one week after application The occurrence of redness was observed.
[Skin irritation criteria]
A: No pain or redness.
X: Painful and redness occurred on the coated surface.

  The composition for forming a two-component curable adhesive film of the present invention has low irritation to the skin, is flexible, has high film strength, and is excellent in moisture permeability and adhesiveness. It is suitable as an external composition for fixing flaws, and can be used for bonding a wide range of adherends such as leather, wood, paper, plastic, ceramic and metal.

Claims (5)

  Composition for forming a two-component curable adhesive film comprising an active hydrogen component (A) containing an ethylene oxide adduct (a1) of a bisphenol compound having a hydroxyl value of 50 to 250 mgKOH / g and an organic polyisocyanate component (B) object.   The active hydrogen component (A) is further polyoxyethylene glycol, a polyoxyalkylene polyol (a21) in which the molecular terminal is a hydroxypropyl group and the primary hydroxyl group content is at least 40% and / or the above (a21) The composition for forming a two-component curable adhesive film according to claim 1, comprising an ethylene oxide adduct (a22). The polyoxyalkylene polyol (a21) is represented by the general formula (1), and 40% or more of -Z-OH which is a hydroxyl group-containing group located at the terminal is a group represented by the chemical formula (2). Item 2. A two-component curable adhesive film-forming composition according to Item 2.

[Wherein, X is an m-valent residue obtained by removing m active hydrogens from a compound having m active hydrogen atoms; A is a C 2-12 optionally substituted with a phenyl group or a halogen atom; Z is a propylene group; m is an integer of 2 to 20; p is an integer of 0 or 1 to 199, q is an integer of 1 to 200 and satisfies p + q ≦ 200. ]

  A composition for external use for immobilizing skin, comprising the composition according to claim 1.   An adhesive comprising the composition according to claim 1.