JP2020076074A - Curable composition - Google Patents

Abstract

To provide a curable composition excellent in contamination preventing property, durability and curing sheet adhesion preventive property.SOLUTION: There is provided a curable composition which comprises an isocyanate group-containing urethane prepolymer obtained by reacting an organic isocyanate compound and an active hydrogen-containing compound and a silane compound represented by the following general formula (1) and/or a partially hydrolyzed condensate of a silane compound, wherein the active hydrogen-containing compound contains a polyoxyalkylene-based triol, a polyoxyalkylene-based diol and a polyoxyalkylene-based monool. RSi-(OR)(1) (In the formula (1), R represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, multiple Rs may be the same or different, Ris a monovalent hydrocarbon group having one or more carbon atoms, at least one of (OR)s is an alkoxy group having 2 to 6 carbon atoms, multiple (OR)s may be the same or different and m is an integer of 1 to 4.SELECTED DRAWING: None

Description

  TECHNICAL FIELD The present invention relates to a curable composition which is excellent in anti-staining property, durability and anti-curing sheet adhesion property.

  A curable composition containing a polyurethane resin is widely used as a sealing material for construction and civil engineering, a waterproof material, an adhesive, and a coating material because it has excellent workability and adhesiveness. Polyurethane resin allows the physical properties of rubber after curing to be adjusted relatively freely from low modulus to high modulus (high elongation to low elongation). However, when a curable composition containing a polyurethane resin is designed to have a low modulus to a medium modulus, tackiness may remain on the surface after curing. In this case, dust or dirt is likely to adhere to the surface of the curable composition, and the surface is contaminated to cause a design defect. Especially when the curable composition is used outdoors or when the curable composition is in the process of being cured, the surface of the curable composition has a large stickiness (tack). The surface of the object is contaminated. Further, when a curable composition containing a polyurethane resin is used for construction and civil engineering, it is required to have excellent durability in order to meet the needs for a longer life of the material.

  On the other hand, when the curable composition is used, a curing tape or a curing sheet is often attached to the peripheral member so that the curable composition does not adhere to a place other than the use place. Further, after using the curable composition, when applying a topcoat paint to the surface or its peripheral members, in order to shorten the construction period, even if the curable composition is in the middle of curing It may also be attached to the surface of the object. In this case, the curing sheet adheres to the surface of the curable composition mainly due to the tackiness of the surface of the curable composition, and when the curing sheet is peeled off after applying the overcoat paint, the surface layer part of the curable composition is removed. May be peeled off by being pulled by the curing sheet. When the surface layer portion of the curable composition is peeled off, that portion must be repaired. Therefore, it is required to improve the property of preventing the curable composition from adhering to the curing sheet.

  A curable composition containing an isocyanate group-containing urethane prepolymer and a silane compound is known as a method for preventing contamination of the surface of the curable composition due to stickiness (for example, Patent Documents 1 and 2). The curable compositions described in these patent documents are excellent in preventing the surface of the curable composition from being contaminated by dust or dust by improving the stickiness of the surface of the curable composition. Curing sheet adhesion preventive property was not examined.

JP, 2008-201980, A JP, 2009-073382, A

  An object of the present invention is to provide a curable composition which is excellent in stain resistance, durability, and curing sheet adhesion prevention.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor found that a curable composition containing a specific urethane prepolymer had excellent anti-staining property, durability, and anti-curing sheet adhesion property. It came to completion.

That is, the present invention relates to a curable composition having the aspects shown in the following (1) to (10).
(1) An isocyanate group-containing urethane prepolymer obtained by reacting an organic isocyanate compound and an active hydrogen-containing compound is contained, and the active hydrogen-containing compound is a polyoxyalkylene-based triol, a polyoxyalkylene-based diol, and a polyoxyalkylene-based diol. A curable composition comprising an oxyalkylene monool.
(2) The polyoxyalkylene-based triol has a number average molecular weight of 1,000 to 30,000, and the polyoxyalkylene-based diol has a number average molecular weight of 1,000 to 30,000. The curable composition according to (1), wherein the monool has a number average molecular weight of 1,000 to 30,000.
(3) The curable composition according to (1) or (2), wherein the isocyanate group-containing urethane prepolymer has a branch density of 0.03 mmol / g or more.
(4) The content of the polyoxyalkylene-based monol is 5 to 30% by mass of the isocyanate group-containing urethane prepolymer, according to any one of (1) to (3). Curable composition.
(5) The curable composition according to any one of (1) to (4), wherein the isocyanate group-containing urethane prepolymer has a photoreactive unsaturated bond in the molecule.
(6) The curable composition according to any one of (1) to (5), which further contains a silane compound represented by the following general formula and / or a partial hydrolysis-condensation product of the silane compound.
R _4-m Si- (OR ¹ ) _m
(In the formula, R represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and when R is plural, they may be the same or different. R ¹ is a monovalent carbon atom having 1 or more carbon atoms. is a hydrogen group, at least one (OR ¹⁾ is an alkoxy group having 2 to 6 carbon atoms. (OR ¹⁾ is a plurality of time may be different even in the same .m is 1 It is an integer of 4.)
(7) The curable composition according to any one of (1) to (6), which further contains an oxazolidine compound.
(8) Further, at least one selected from a curing accelerating catalyst, a plasticizer, a weather resistance stabilizer, a filler, a thixotropic agent, an adhesion improver, a storage stability improver (dehydrating agent), a colorant and an organic solvent. Curable composition in any one of (1)-(7) characterized by containing 1 or more types of additives.
(9) The curable composition according to any one of (1) to (8), wherein the curable composition is a curable composition for construction or civil engineering.
(10) The curable composition is a sealing material composition, a waterproof material composition, an adhesive composition or a coating material composition, according to any one of (1) to (9). Curable composition.

  The curable composition of the present invention has excellent durability after curing, and also has excellent anti-staining property on the surface of the curable composition and anti-curing sheet adhesion property. Furthermore, since the curable composition of the present invention can be used as either a one-component curable composition or a two-component curable composition, it has a wide range of applications.

  The curable composition of the present invention contains an isocyanate group-containing urethane prepolymer obtained by reacting an organic isocyanate compound with an active hydrogen-containing compound (hereinafter, may be simply referred to as “urethane prepolymer”), and has the above-mentioned activity. The hydrogen-containing compound is characterized by containing a polyoxyalkylene-based triol, a polyoxyalkylene-based diol, and a polyoxyalkylene-based monol. Hereinafter, each component will be described in detail.

  The isocyanate group-containing urethane prepolymer functions as a curing component in the curable composition of the present invention and imparts good adhesion to the adhered surface to the composition after curing. In particular, a curable composition containing an isocyanate group-containing urethane prepolymer obtained by reacting an organic isocyanate compound with an active hydrogen-containing compound containing a polyoxyalkylene-based triol, a polyoxyalkylene-based diol and a polyoxyalkylene-based monol The cured product has excellent durability, the tackiness of the surface of the curable composition is reduced, and the surface of the curable composition is prevented from being contaminated by dust or dust and the curing sheet is prevented from adhering to the curing sheet. Will be excellent.

  The isocyanate group-containing urethane prepolymer is a resin having one or more isocyanate groups, and the isocyanate group reacts with the active hydrogen (group) -containing compound to form a urethane bond, a urea bond, etc., and thereby crosslink and cure.

  The isocyanate group-containing urethane prepolymer comprises an organic isocyanate compound and an active hydrogen-containing compound containing a polyoxyalkylene-based triol, a polyoxyalkylene-based diol, and a polyoxyalkylene-based monol, and a mole of isocyanate group / active hydrogen (group). The reaction is carried out in a batch or sequentially in a ratio of preferably 1.2 to 10/1, more preferably 1.2 to 5/1 so that isocyanate groups remain in the urethane prepolymer. You can When the molar ratio is less than 1.2 / 1, the viscosity of the urethane prepolymer becomes high and the workability of the curable composition deteriorates. If the molar ratio exceeds 10/1, the amount of carbon dioxide gas generated when the isocyanate group reacts with water increases, which causes foaming during curing.

  The isocyanate group content of the isocyanate group-containing urethane prepolymer is preferably 0.3 to 15% by mass, and particularly preferably 0.5 to 5% by mass. When the isocyanate group content is less than 0.3% by mass, the viscosity of the urethane prepolymer becomes high and the workability of the curable composition deteriorates. If the isocyanate group content exceeds 15% by mass, the amount of carbon dioxide gas generated when the isocyanate group reacts with water increases, which causes foaming during curing.

  The number average molecular weight of the isocyanate group-containing urethane prepolymer is preferably 1,500 or more, more preferably 1,500 to 20,000, still more preferably 1,500 to 15,000, and particularly 1,500 to 10,000. Is preferred. The number average molecular weight in the present invention is a polystyrene equivalent value measured by gel permeation chromatography (GPC).

  The branch density of the isocyanate group-containing urethane prepolymer is preferably 0.03 mmol / g or more, more preferably 0.03 to 0.1 mmol / g, and particularly preferably 0.03 to 0.08 mmol / g. When the branch density of the urethane prepolymer is less than 0.03 mmol / g, when the curing sheet is attached to the surface of the curable composition, the curing sheet adheres to the surface of the curable composition and is difficult to peel off. The branch density of the urethane prepolymer can be theoretically obtained by calculation from the raw material for producing the urethane prepolymer (content of the raw material having a branched structure).

  The content of the polyoxyalkylene monool in the isocyanate group-containing urethane prepolymer is preferably 5 to 30% by mass, and more preferably 5 to 20% by mass based on the total amount of the urethane prepolymer. When the content of the polyoxyalkylene monool in the urethane prepolymer is within the above range, the curable composition will have excellent durability (for example, the durability of JIS A 5758). In particular, if the branch density of the urethane prepolymer is increased, the physical properties after curing of the curable composition will be high modulus and low elongation, and the durability will tend to decrease, but the polyoxyalkylene in the urethane prepolymer will tend to decrease. By setting the content of the system monool in the above range, the physical properties after curing of the curable composition will be excellent even if the branch density of the urethane prepolymer is increased.

  As the method for producing the isocyanate group-containing urethane prepolymer, specifically, an organic isocyanate compound, a polyoxyalkylene-based triol, a polyoxyalkylene-based diol and a polyoxyalkylene-based mono are used in a reaction container made of glass or stainless steel. Examples include a method in which an active hydrogen-containing compound containing oar is charged and reacted with stirring at 50 to 120 ° C. in the presence or absence of a reaction catalyst or an organic solvent. At this time, since the urethane prepolymer thickens when the isocyanate group reacts with water such as moisture, it is preferable to replace the inside of the container with nitrogen gas in advance or to carry out the reaction under a nitrogen gas stream.

  An organic polyisocyanate can be mentioned as an organic isocyanate compound. The organic polyisocyanate is a compound having two or more isocyanate groups in the compound, and specifically, toluene polyisocyanate such as 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, 4,4′- Diphenylmethane polyisocyanate such as diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and 2,2'-diphenylmethane diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4,6 -Phenylene polyisocyanate such as trimethylphenyl-1,3-diisocyanate and 2,4,6-triisopropylphenyl-1,3-diisocyanate, naphthalene polyisocyanate such as 1,4-naphthalene diisocyanate and 1,5-naphthalene diisocyanate, Aromatic aromatic compounds such as chlorophenylene-2,4-diisocyanate, 4,4'-diphenylether diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate Examples include polyisocyanates. Further, 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, Aliphatic polyisocyanates such as decamethylene diisocyanate and lysine diisocyanate, aromatic aliphatic polyisocyanates such as o-xylylene diisocyanate, m-xylylene diisocyanate and p-xylylene diisocyanate, 1,4-cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenation Alicyclic polyisocyanates such as toluene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate and the like can be mentioned. Further, there may be mentioned polymeric isocyanates such as polymethylene polyphenyl polyisocyanate and crude toluene diisocyanate. Further, a modified isocyanate having one or more uretdione bond, isocyanurate bond, allophanate bond, buret bond, uretonimine bond, carbodiimide bond, urethane bond or urea bond, which is obtained by modifying these organic polyisocyanates, may be mentioned. These can be used alone or in combination of two or more.

  Among these, aliphatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, and modified isocyanates obtained by modifying these organic polyisocyanates are preferable because the curable composition has excellent weather resistance.

  Further, an organic monoisocyanate can be used together with the organic polyisocyanate. That is, a mixture of organic polyisocyanate and organic monoisocyanate can be used as the above-mentioned organic isocyanate compound. The organic monoisocyanate is a compound having one isocyanate group in the compound, and specifically, n-butyl monoisocyanate, n-hexyl monoisocyanate, n-hexadecyl monoisocyanate, n-octadecyl monoisocyanate, Examples thereof include p-isopropylphenyl monoisocyanate and p-benzyloxyphenyl monoisocyanate.

  The active hydrogen-containing compound is a compound having one or more active hydrogens (groups) in the compound. In the present invention, a polyoxyalkylene-based triol, a polyoxyalkylene-based diol, and a polyoxyalkylene-based monol are included. In the present invention, the “system” of polyoxyalkylene-based triol, polyoxyalkylene-based diol, and polyoxyalkylene-based monool is 50% by mass or more, and further 80% by mass or more of the portion excluding the hydroxyl group in the molecule, If 90% by mass or more is composed of polyoxyalkylene, it means that the remaining part may be modified with ester, urethane, polycarbonate, polyamide, poly (meth) acrylate, polyolefin or the like. It is most preferable that 95% by mass or more of the molecule excluding the hydroxyl group is composed of polyoxyalkylene.

  Polyoxyalkylene-based triols, polyoxyalkylene-based diols, and polyoxyalkylene-based monools can be obtained by ring-opening addition polymerization of alkylene oxide as an initiator in the presence of a polymerization catalyst. The total degree of unsaturation of the polyoxyalkylene-based triol, polyoxyalkylene-based diol, and polyoxyalkylene-based monool is preferably 0.1 meq / g or less, more preferably 0.07 meq / g or less, and especially 0.04 meq / g. The following are preferred.

  Examples of the polymerization catalyst include alkali metal compound catalysts such as sodium catalysts and potassium catalysts, cationic polymerization catalysts, complex metal cyanide complex catalysts such as zinc hexacyanocobaltate glyme complex and diglyme complex, and phosphazene compound catalysts. Of these, alkali metal compound catalysts and complex metal cyanide complex catalysts are preferable.

  As the initiator, a compound in which the number of active hydrogen (group) (hydroxyl group or amino group capable of reacting with alkylene oxide) in the molecule is 1 to 3 is used. A small amount of a compound having 4 active hydrogens (groups) in the molecule may be used in combination therewith.

  As the initiator for producing the polyoxyalkylene monool, a compound having one active hydrogen (group) is mainly used. Specific examples of the compound having 1 active hydrogen (group) include monohydric alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, and tert-butyl alcohol; phenol, Examples thereof include monohydric phenols such as nonylphenol; secondary amines such as dimethylamine and diethylamine.

  As an initiator for producing a polyoxyalkylene-based diol, a compound having 2 active hydrogens (groups) is mainly used. Specific examples of the compound having 2 active hydrogen atoms include dihydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol, bisphenol A and bisphenol F.

  As an initiator for producing a polyoxyalkylene-based triol, a compound having 3 active hydrogens (groups) is mainly used. Specific examples of the compound having 3 active hydrogens include trihydric alcohols such as glycerin and trimethylolpropane.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-epoxybutane, and 2,3-epoxybutane. Of these, propylene oxide, ethylene oxide, and a combination of propylene oxide and ethylene oxide are preferable, and further, a combination of propylene oxide and propylene oxide and ethylene oxide is preferable.

  As the polyoxyalkylene-based triol, polyoxypropylene triol, polyoxyethylene triol and polyoxyethylene propylene triol are preferable, and further polyoxypropylene triol and polyoxyethylene propylene triol are preferable. The number average molecular weight of the polyoxyalkylene-based triol is preferably 1,000 to 30,000, more preferably 1,000 to 20,000.

  The polyoxyalkylene-based diol is preferably polyoxypropylene diol, polyoxyethylene diol or polyoxyethylene propylene diol, more preferably polyoxypropylene diol or polyoxyethylene propylene diol. The number average molecular weight of the polyoxyalkylene-based diol is preferably 1,000 to 30,000, more preferably 1,000 to 20,000.

The polyoxyalkylene-based monool is preferably polyoxypropylene monool, polyoxyethylene monool or polyoxyethylene propylene monool, more preferably polyoxypropylene monool or polyoxyethylene propylene monool.
The number average molecular weight of the polyoxyalkylene monool is preferably 1,000 to 30,000, more preferably 1,000 to 20,000.

In the present invention, the “oxyethylene propylene” includes an oxyethylene group (—CH ₂ CH ₂ O—) and an oxypropylene group (—CH (CH ₃ ) CH ₂ O—) in the molecule.

  The active hydrogen-containing compound is a polyoxyalkylene-based triol, a polyoxyalkylene-based diol, or a polyoxyalkylene-based monool, as well as other polymer polyols, polymer polyamines, low-molecular polyols, low-molecular amino alcohols, low-molecular polyamines. Can be used together. Further, in order to impart weather resistance to the urethane prepolymer, an active hydrogen-containing compound having active hydrogen and a photoreactive unsaturated bond in the molecule can be used together. These can be used alone or in combination of two or more.

  Other polymer polyols are polymer polyols other than polyoxyalkylene-based triols and polyoxyalkylene-based diols. Specific examples include polyester polyols, polycarbonate polyols, polyoxyalkylene-based polyols, hydrocarbon-based polyols, poly (meth) acrylate-based polyols, and copolyols thereof. The number average molecular weight of the other polymer polyol is preferably 1,000 to 20,000. In addition, in this invention, "(meth) acrylate" means "acrylate and / or methacrylate."

  Polyester polyols include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, etc. A polycarboxylic acid of 1 or more of an anhydride of these acids or an alkyl ester such as methyl ester or ethyl ester, and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, One or more low molecular weight polyols such as 1,9-nonanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, ethylene oxide or propylene oxide adduct of bisphenol A, trimethylolpropane, glycerin and pentaerythritol. The polyester polyol obtained by reaction with is mentioned. In addition to these polycarboxylic acids and acid anhydrides, low molecular weight polyols, low molecular weight polyamines such as butylenediamine, hexamethylenediamine, xylylenediamine, isophoronediamine, low molecular weight compounds such as monoethanolamine and diethanolamine. Also included are polyester amide polyols obtained by reaction with one or more amino alcohols.

  As the polycarbonate polyol, dehydrochlorination reaction of low molecular weight polyols and phosgene used in the synthesis of the above polyester polyol, or transesterification reaction of the above low molecular weight polyols with diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate The ones obtained in.

  As the poly (meth) acrylate-based polyol, a (meth) acrylate monomer containing a hydroxyl group such as hydroxyethyl (meth) acrylate and another (meth) acrylic acid alkyl ester monomer are used as radical polymerization initiators. Examples thereof include those copolymerized in the presence or absence.

  Examples of the hydrocarbon-based polyol include polyolefin polyols such as polybutadiene polyol and polyisoprene polyol; polyalkylene polyols such as hydrogenated polybutadiene polyol and hydrogenated polyisoprene polyol; halogenated polyalkylene polyols such as chlorinated polypropylene polyol and chlorinated polyethylene polyol. Is mentioned.

  The above-mentioned other polymer polyols can be used alone or in combination of two or more kinds.

  In the isocyanate group-containing urethane prepolymer, a photoreactive unsaturated bond can be introduced into the urethane prepolymer for the purpose of imparting weather resistance. The urethane prepolymer introduced with a photoreactive unsaturated bond acts as a curing component in the curable composition of the present invention and imparts good adhesion to the adhered surface and excellent weather resistance to the composition after curing. It is a thing. The above-mentioned photoreactive unsaturated bond is an unsaturated bond that causes a chemical change such as polymerization in a relatively short time when exposed to light. Specific examples thereof include an unsaturated bond derived from a vinyl group, a vinylene group, and a (meth) acryloyl group. In the present invention, the “(meth) acryloyl group” means “acryloyl group and / or methacryloyl group”.

  The isocyanate group of the isocyanate group-containing urethane prepolymer having the photoreactive unsaturated bond introduced reacts with the active hydrogen-containing compound to crosslink and cure. In addition, the photoreactive unsaturated bond of the isocyanate group-containing urethane prepolymer introduced with a photoreactive unsaturated bond undergoes a polymerization reaction when exposed to light, and a cured film having excellent weather resistance on the surface of the curable composition. To form. It is considered that this cured film imparts excellent weather resistance to the curable composition. The photoreactive unsaturated bond is preferably an unsaturated bond derived from a (meth) acryloyl group because of its high weather resistance imparting effect.

As a method for introducing a photoreactive unsaturated bond into an isocyanate group-containing urethane prepolymer,
(A) An organic isocyanate compound, a high molecular weight active hydrogen-containing compound (number average molecular weight of 1,000 or more), and a low molecular weight active hydrogen-containing compound having active hydrogen and a photoreactive unsaturated bond in the molecule (number And an average molecular weight of less than 1,000) under the condition of excess isocyanate groups with respect to the total amount of active hydrogen.
(B) An organic isocyanate compound and a polymer (number average molecular weight of 1,000 or more) of active hydrogen-containing compound having active hydrogen and a photoreactive unsaturated bond in the molecule (for example, polyoxyalkylene triol mono (meta ) Acrylate, alkylene oxide adduct of (meth) acrylic acid, polybutadiene polyol) under the condition of excess isocyanate groups with respect to the total amount of active hydrogen; and (c) Organic isocyanate compound and intramolecular A low molecular weight (number average molecular weight less than 1,000) active hydrogen-containing compound (for example, (meth) acryloyl isocyanate) having a photoreactive unsaturated bond and an isocyanate group, and a polymer (number average molecular weight of 1,000 or more) A method of reacting the active hydrogen-containing compound of 1) under conditions of excess isocyanate groups with respect to the total amount of active hydrogen;
Is mentioned. The method (a) is preferable in terms of availability of raw materials and easiness of reaction. In addition, "(meth) acrylic acid" means "acrylic acid and / or methacrylic acid".

  In the present invention, an organic isocyanate compound, a polyoxyalkylene-based triol, a polyoxyalkylene-based diol, and a polyoxyalkylene-based monool, a low-molecular active hydrogen having active hydrogen and a photoreactive unsaturated bond in the molecule. It is preferable to use a method in which an active hydrogen-containing compound containing a containing compound is reacted under the condition of an isocyanate group excess with respect to the total amount of active hydrogen.

  Examples of the method of introducing the photoreactive unsaturated bond into the isocyanate group-containing urethane prepolymer include a method of charging the above-mentioned raw materials all at once or sequentially and reacting them. The equivalent ratio (isocyanate group / active hydrogen) of the isocyanate group of the organic isocyanate compound and the active hydrogen of the active hydrogen-containing compound (including the active hydrogen-containing compound having active hydrogen and a photoreactive unsaturated bond) is 1. 2 to 10/1 is preferable, and 1.2 to 5/1 is more preferable. The isocyanate group content in the isocyanate group-containing urethane prepolymer having a photoreactive unsaturated bond introduced is preferably 0.3 to 15% by mass, more preferably 0.5 to 5% by mass. If the isocyanate group content is less than 0.3% by mass, the molecular weight becomes too large, the viscosity increases, and the workability decreases. Further, since the number of crosslinking points in the urethane prepolymer is small, sufficient adhesiveness cannot be obtained. When the isocyanate group content exceeds 15% by mass, the amount of carbon dioxide gas generated when the isocyanate group reacts with water increases, which causes foaming during curing.

  The content of the photoreactive unsaturated bond in the isocyanate group-containing urethane prepolymer having the photoreactive unsaturated bond introduced is preferably 0.01 mmol / g or more, more preferably 0.03 to 1 mmol / g, Particularly, 0.05 to 0.5 mmol / g is preferable.

  The active hydrogen-containing compound (of low molecular weight and high molecular weight) having the above-mentioned active hydrogen and a photoreactive unsaturated bond is a compound having active hydrogen (group) such as hydroxyl group, amino group and carboxyl group in the compound and vinyl group. , A vinylene group, a (meth) acryloyl group, and other photoreactive unsaturated bonds. A compound having a hydroxyl group and a (meth) acryloyl group in the compound is preferable from the viewpoint of easy reaction and high weather resistance imparting effect. Further, the active hydrogen-containing compound having active hydrogen and a photoreactive unsaturated bond in the molecule preferably has a number average molecular weight of less than 1,000 in terms of easy reaction.

  As the active hydrogen-containing compound having a hydroxyl group and a (meth) acryloyl group, 2-hydroxyethyl (meth) acrylate, which is a monoester of an alkylene glycol such as ethylene glycol, propylene glycol, butylene glycol, and (meth) acrylic acid. , 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxypentyl (meth) acrylate, hydroxyneopentyl (meth) acrylate, 6-hydroxyhexyl ( (Meth) acrylate, hydroxyheptyl (meth) acrylate, hydroxyoctyl (meth) acrylate, and other monohydroxymono (meth) acrylates, glycerin, trimethylolpropane, pentaerythritol, and other alkylene polyols and (meth) acrylic acid Polyesters such as monoesters or diesters and triesters of glycerol, monohydroxypoly (meth) acrylates such as glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerin mono (Meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate and other polyhydroxymono (meth) acrylates, pentaerythritol di (meth) acrylate and other polyhydroxypoly (meth) acrylates Can be mentioned. In addition to these, dihydroxy glycols such as diethylene glycol, dipropylene glycol, polyoxyethylene polyols, polyoxypropylene polyols, and polyols obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to bisphenol A and bisphenol F (meth ) Acrylates, polyhydroxymono (meth) acrylates, polyhydroxypoly (meth) acrylates and active hydrogen of hydroxyalkyl (meth) acrylates such as (meth) acrylic acid and hydroxyethyl (meth) acrylate, ethylene oxide, propylene oxide Examples thereof include compounds having an alkylene oxide such as butylene oxide having a hydroxyl group, and compounds having a hydroxyl group such as a caprolactone modified product of hydroxyethyl acrylate. These can be used alone or in combination of two or more. Among these, monohydroxy poly (meth) acrylates and dihydroxy poly (meth) acrylates are preferable because the viscosity of the urethane prepolymer can be suppressed low and the effect of imparting weather resistance can be enhanced.

  The curable composition of the present invention may contain a silane compound and / or a partially hydrolyzed condensate of the silane compound. The silane compound and / or the partially hydrolyzed condensate of the silane compound, when combined with a urethane prepolymer, imparts the curable composition with the effects of anti-staining property and anti-curing sheet adhesion property. This is because when the curable composition is cured by water such as moisture, the silane compound and / or the partial hydrolysis-condensation product of the silane compound migrates to the surface of the curable composition from the middle of curing (bleed), It is considered that the stickiness on the surface of the curable composition is reduced by forming a hydrophilic film on the surface of the curable composition by being hydrolyzed by water such as the above and condensing while dealcoholating. By reducing the stickiness of the surface of the curable composition, it becomes difficult for dust and dirt to adhere to the surface of the curable composition, and the contamination prevention property is improved. Further, even if dust or dust adheres to the surface of the curable composition, it is possible to relatively easily remove the dust or dust by spraying rain, running water such as a shower, or compressed air.

The silane compound is a compound represented by the following general formula (1), and is a silane compound having at least one alkoxy group other than a methoxy group in the molecule.
R _4-m Si (OR ¹ ) _m (1)
(In the formula (1), R represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and when R is plural, they may be the same or different. R ¹ is 1 having 1 or more carbon atoms. is a valence of the hydrocarbon group, at least one (OR ¹⁾ good be different even for the same when it. (OR ¹⁾ is plural alkoxy group having 2 to 6 carbon atoms .m Is an integer of 1 to 4.)

  The R is a monovalent group having 1 to 6 carbon atoms and having no reactive functional group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, heptyl group, hexyl group and phenyl group. Hydrocarbon groups are mentioned.

The above (OR ¹ ) is an alkoxy group, and when m is 1, (OR ¹ ) is an alkoxy group other than a methoxy group. When m is 2, 3 or 4, at least one of (OR ¹ ) is an alkoxy group other than a methoxy group.

  Examples of the alkoxy group other than the methoxy group include alkoxy groups having 2 or more carbon atoms such as ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, pentoxy group, hexoxy group and phenoxy group.

  Examples of the silane compound include tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, and dimethoxydiethoxysilane. Be done. These can be used alone or in combination of two or more.

  The partially hydrolyzed condensate of the silane compound is a polymer obtained by partially hydrolyzing the alkoxy group of the silane compound in the presence or absence of a solvent and condensing the silane compound in a linear or three-dimensional manner. .. The partially hydrolyzed condensate of the silane compound is preferably from 2 to 20 mer from the viewpoint of transferability (bleeding) to the surface of the curable composition and film-forming property after transfer to the surface of the curable composition.

  Specific examples of the partial hydrolysis-condensation product of the silane compound include ethyl silicate 40 (average pentamer), ethyl silicate 48 (average decamer), and Colcoat Co., which include a partial hydrolysis-condensation product of tetraethoxysilane. EMS-485 (average 10-mer) containing partially hydrolyzed condensate of diethoxydimethoxysilane, manufactured by Colcoat Co .; MKC containing condensate partially butoxylized partially hydrolyzed condensate of tetramethoxysilane. Silicate MS58B15, MS58B30, MS51, MS56, MS57, MS56S, manufactured by Mitsubishi Chemical Co .; These can be used alone or in combination of two or more.

  The amount of the silane compound and / or the partially hydrolyzed condensate of the silane compound used is preferably 0.01 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the isocyanate group-containing urethane prepolymer. .. When the amount used is less than 0.01 parts by mass, the effect of preventing the surface of the curable composition from being contaminated and the effect of preventing the attachment of a curing sheet are small. When the amount used exceeds 20 parts by mass, the amount of alcohol generated by hydrolysis of the silane compound and / or the partial hydrolysis-condensation product of the silane compound increases, and the generated alcohol reacts with the isocyanate group of the urethane prepolymer. May cause curing failure.

  The curable composition of the present invention may contain an oxazolidine compound. The oxazolidine compound is a compound having one or more, preferably 1 to 6 in a molecule, an oxazolidine ring which is a saturated 5-membered heterocyclic ring containing an oxygen atom and a nitrogen atom. The oxazolidine compound functions as a latent curing agent for the isocyanate group-containing urethane prepolymer by reacting with water such as humidity to hydrolyze and the oxazolidine ring generates (regenerates) a secondary amino group and an alcoholic hydroxyl group. It is a thing. When the isocyanate group of the urethane prepolymer reacts with water such as moisture, it forms a urea bond and cures, but at this time, carbon dioxide gas is also generated, and carbon dioxide gas bubbles occur in the cured product, which deteriorates the appearance and cures. Problems such as breakage of products and deterioration of adhesiveness may occur. On the other hand, when a curable composition in which a urethane prepolymer and an oxazolidine compound are used in combination is reacted with water, water and the oxazolidine compound react preferentially, and the oxazolidine ring of the oxazolidine compound has a secondary amino group and an alcoholic hydroxyl group. (Active hydrogen group) is generated. Next, the active hydrogen groups (especially secondary amino groups) that are generated react preferentially with the isocyanate groups, so the generation of carbon dioxide gas due to the reaction of water and the isocyanate groups is suppressed, and foaming during curing of the curable composition occurs. Can be prevented.

  Moreover, when an aliphatic polyisocyanate or an alicyclic polyisocyanate is used as the organic polyisocyanate compound used for the isocyanate group-containing urethane prepolymer, the curing of the curable composition may be delayed. When an isocyanate group-containing urethane prepolymer and an oxazolidine compound are used in combination in the curable composition, the curable composition can be cured more quickly, and the amount of the curing accelerating catalyst described below can be reduced.

  Furthermore, by mixing the oxazolidine compound with a curable composition containing an isocyanate group-containing urethane prepolymer and a silane compound and / or a partial hydrolysis-condensation product of the silane compound, generation of cracks on the surface of the curable composition can be prevented. It has the effect of preventing. More specifically, the curable composition obtained by blending the isocyanate group-containing urethane prepolymer with the silane compound and / or the partially hydrolyzed condensate curable composition of the silane compound is a silane compound and / or a partially hydrolyzed silane compound. The decomposition condensate migrates (bleeds) to the surface of the curable composition and hydrolyzes to form a cured film on the surface of the curable composition. Since this cured film is hard, it is presumed that if the cured film is displaced during the curing of the curable composition, the displacement cannot be followed and a crack is generated on the surface of the curable composition. When an oxazolidine compound is further added, the cured film of the silane compound and / or the partially hydrolyzed condensate of the silane compound has flexibility due to the action of the secondary amino group and alcoholic hydroxyl group formed by hydrolysis of the oxazolidine compound. It is presumed that it will prevent the occurrence of cracks. Further, by combining an isocyanate group-containing urethane prepolymer, a silane compound and / or a partially hydrolyzed condensate of a silane compound, and an oxazolidine compound, even when the curable composition is in the middle of curing, the curing sheet adhesion prevention property is further improved. Becomes

  Examples of the oxazolidine compound include a urethane bond-containing oxazolidine compound, an ester group-containing oxazolidine compound, an oxazolidine silyl ether compound, and a carbonate group-containing oxazolidine compound. These oxazolidine compounds are obtained by reacting a hydroxyl group and a hydroxyl group of a compound having an oxazolidine ring with an isocyanate group of an organic polyisocyanate compound or a carboxyl group of an organic carboxylic acid compound. Among these oxazolidine compounds, urethane bond-containing oxazolidine compounds are preferable because they are easy to produce and have a low viscosity.

  Specific examples of the compound having a hydroxyl group and an oxazolidine ring include N-hydroxyalkyloxazolidine obtained by a dehydration condensation reaction between a secondary amino group of an alkanolamine and a carbonyl group of a ketone compound or an aldehyde compound. As a method for producing the compound having a hydroxyl group and an oxazolidine ring, 1 mol or more, preferably 1 to 1.5 mol, and more preferably 1 mol of a carbonyl group of an aldehyde compound or a ketone compound is used with respect to 1 mol of a secondary amino group of an alkanolamine. Is used in a solvent such as toluene and xylene, and the mixture is heated and refluxed to remove the water produced as a by-product, and a dehydration condensation reaction is carried out. Excessive aldehyde compounds and ketone compounds may be removed by distillation.

  Examples of the alkanolamine include diethanolamine, dipropanolamine and N- (2-hydroxyethyl) -N- (2-hydroxypropyl) amine. Examples of the ketone compound include acetone, diethyl ketone, isopropyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl-tert-butyl ketone, diisobutyl ketone, cyclopentanone and cyclohexanone. Examples of the aldehyde compound include acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, 2-methylbutyraldehyde, n-hexylaldehyde, 2-methylpentylaldehyde, n-octylaldehyde, 3,5. And aliphatic aldehyde compounds such as 5-trimethylhexylaldehyde; aromatic aldehyde compounds such as benzaldehyde, methylbenzaldehyde, trimethylbenzaldehyde, ethylbenzaldehyde, isopropylbenzaldehyde, isobutylbenzaldehyde, methoxybenzaldehyde, dimethoxybenzaldehyde and trimethoxybenzaldehyde. Any of these may be used alone or in combination of two or more.

  Among these, diethanolamine is preferable as the alkanolamine, in terms of ease of production of a compound having a hydroxyl group and an oxazolidine ring, and excellent foaming-preventing property when the curable composition cures. Of these, aldehyde compounds are preferable, and isobutyraldehyde, 2-methylpentylaldehyde, and benzaldehyde are more preferable.

  Examples of the compound having a hydroxyl group and an oxazolidine ring include 2-isopropyl-3- (2-hydroxyethyl) oxazolidine, 2- (1-methylbutyl) -3- (2-hydroxyethyl) oxazolidine, 2-phenyl-3- (2 -Hydroxyethyl) oxazolidine.

  The urethane bond-containing oxazolidine compound has an isocyanate group of an organic polyisocyanate compound and a hydroxyl group and a hydroxyl group of a compound having an oxazolidine ring, and an isocyanate group / hydroxyl group molar ratio is 0.9 / 1 to 1.2 / 1, preferably Preferable ones are those used at 0.95 / 1 to 1.05 / 1 and obtained by reacting at a temperature of 50 to 120 ° C. in the presence or absence of an organic solvent.

  As the organic polyisocyanate compound used for producing the urethane bond-containing oxazolidine compound, the same ones as those used for producing the above-mentioned urethane prepolymer can be mentioned. Among the organic polyisocyanate compounds, araliphatic polyisocyanates and aliphatic polyisocyanates are preferable, and xylylene diisocyanate and hexamethylene diisocyanate are particularly preferable.

  The ester group-containing oxazolidine compound can be obtained by reacting the above-mentioned compound having a hydroxyl group and an oxazolidine ring with a lower alkyl ester of dicarboxylic acid or polycarboxylic acid.

  The oxazolidine silyl ether compound is a compound having a hydroxyl group and an oxazolidine ring as described above, trimethoxysilane, tetramethoxysilane, triethoxysilane, dimethoxydimethylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, and 3-glycidoxypropyltrioxide. Obtained by dealcoholation reaction with an alkoxysilane such as methoxysilane or 3-glycidoxypropyltriethoxysilane.

  The carbonate group-containing oxazolidine compound can be obtained by reacting the above-mentioned compound having a hydroxyl group and an oxazolidine ring with a carbonate such as diallyl carbonate using a polyhydric alcohol such as diethylene glycol or glycerin.

  Any of these oxazolidine compounds may be used alone or in combination of two or more.

  The oxazolidine compound preferably does not have an active hydrogen-containing functional group such as an amino group or a hydroxyl group that reacts with an isocyanate group of the urethane prepolymer, or an isocyanate group. This is to prevent an increase in the viscosity of the urethane prepolymer and a decrease in the foaming prevention performance of the oxazolidine compound. However, in the production of the urethane bond-containing oxazolidine compound described above, a small amount of active hydrogen-containing functional group or isocyanate group may remain in the molecule depending on the selection of the molar ratio, but in this case, in order to achieve the object of the present invention. Can be regarded as not having. The "small amount" means that the amount of the active hydrogen-containing functional group or isocyanate group remaining in the molecule is preferably 0.05 mmol or less, more preferably 0.02 mmol or less per 1 g of the oxazolidine compound.

  When the oxazolidine compound is used, the amount of active hydrogen of the secondary amino group produced by hydrolysis (regeneration) of the oxazolidine compound is 0.1 to 1 mol per 1 mol of the isocyanate group of the urethane prepolymer. It is preferable that the amount is 0.3 to 1 mol, more preferably 0.5 to 1 mol. When the active hydrogen of the secondary amino group produced by hydrolysis of the oxazolidine compound (regeneration) is less than 0.1 mol, foaming prevention is insufficient, which is not preferable.

  The curable composition of the present invention may contain various additives, if necessary, in addition to the above-mentioned components within a range not impairing the object of the present invention. Additives are added to the curable composition and used to improve various properties of the curable composition such as viscosity adjustment, curing acceleration, and adhesiveness. Specific examples thereof include a curing acceleration catalyst, a plasticizer, a weather resistance stabilizer, a filler, a thixotropic agent, an adhesion improver, a storage stability improver (dehydrating agent), a colorant and an organic solvent. These can be used alone or in combination of two or more.

  The curing accelerating catalyst is used to accelerate the crosslinking and curing of the urethane prepolymer by reacting with water such as moisture. Further, when an oxazolidine compound is added to the curable composition, it is used to accelerate the reaction between the secondary amino group or alcoholic hydroxyl group generated from the oxazolidine compound and the isocyanate group of the urethane prepolymer. Further, the curing accelerating catalyst can also be used as a reaction catalyst in the production of the urethane prepolymer described above. When used as a reaction catalyst during the production of the urethane prepolymer, the reaction catalyst remaining in the urethane prepolymer may act as a curing acceleration catalyst for the curable composition.

  Specific examples of the curing accelerating catalyst include metal-based catalysts and amine-based catalysts.

  Examples of the metal-based catalyst include salts of metals and organic acids, salts of organic metals and organic acids, and metal chelate compounds. Examples of salts of metals and organic acids include salts of various metals such as tin, bismuth, zirconium, zinc and manganese with organic acids such as octylic acid, neodecanoic acid, stearic acid and naphthenic acid. Specific examples thereof include tin octylate, tin naphthenate, bismuth octylate, and zirconium octylate. As a salt of an organic metal and an organic acid, a reaction between dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimaleate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin diversate, dibutyltin oxide and a phthalate ester. Things can be mentioned. Examples of the metal chelate compound include dibutyltin bis (acetylacetonate), a tin-based chelate compound EXCESTAR C-501 manufactured by Asahi Glass Co., Ltd., zirconium tetrakis (acetylacetonate), titanium tetrakis (acetylacetonate), aluminum tris (acetylacetonate). Nato), aluminum tris (ethylacetoacetate), acetylacetone cobalt, acetylacetone iron, acetylacetone copper, acetylacetone magnesium, acetylacetone bismuth, acetylacetone nickel, acetylacetone zinc, acetylacetone manganese.

  Examples of amine-based catalysts include tertiary amines. Examples of the tertiary amines include triethylamine, tributylamine, triethylenediamine, hexamethylenetetramine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 1,4-diazabicyclo [2,2,2]. Examples include octane (DABCO) and salts of these tertiary amines and organic carboxylic acids.

  These curing acceleration catalysts can be used alone or in combination of two or more.

  Among these, a salt of a metal and an organic acid, a salt of an organic metal and an organic acid, and a metal chelate compound are preferable because of the excellent curability of the curable composition, and a salt of a tin and an organic acid, and bismuth. A salt with an organic acid, a salt with an organic tin and an organic acid, a salt with an organic bismuth and an organic acid, a tin chelate compound, and a bismuth chelate compound are preferable.

  The amount of the curing accelerating catalyst used is preferably 0.005 to 5 parts by mass, and more preferably 0.005 to 2 parts by mass with respect to 100 parts by mass of the urethane prepolymer.

  In addition to the above metal-based catalysts and amine-based catalysts, organic carboxylic acid-based catalysts, phosphoric acid ester-based catalysts, p-toluenesulfonyl monoisocyanate, and reaction products of p-toluenesulfonyl monoisocyanate and water can be used. Organic carboxylic acid type catalysts, phosphoric acid ester type catalysts, p-toluenesulfonyl monoisocyanate, and reaction products of p-toluenesulfonyl monoisocyanate and water are oxazolidine rings of oxazolidine compounds when an oxazolidine compound is added to a curable composition. It promotes the hydrolysis of. Of these, organic carboxylic acid catalysts are preferred. By promoting the hydrolysis of the oxazolidine ring, the generated secondary amino group and the alcoholic hydroxyl group (active hydrogen group) react with the isocyanate group of the urethane prepolymer to accelerate the curing of the curable composition. Furthermore, stickiness is improved from the initial stage of curing of the curable composition, and the curability of the curable composition is improved in stain resistance and curing sheet adhesion prevention.

  Examples of organic carboxylic acid catalysts include formic acid, acetic acid, propionic acid, caproic acid, oxalic acid, succinic acid, adipic acid, 2-ethylhexanoic acid (octylic acid), octenoic acid, lauric acid, oleic acid, stearic acid, etc. Examples thereof include α, β-unsaturated carboxylic acids such as aliphatic carboxylic acids, maleic acid and acrylic acid, and aromatic carboxylic acids such as phthalic acid, benzoic acid and salicylic acid.

  Examples of phosphoric acid ester-based catalysts include orthophosphoric acid ester compounds and phosphorous acid ester compounds. Examples of the orthophosphoric acid ester compound include ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, oleyl acid phosphate, and other acidic phosphoric acid ester compounds.As the phosphorous acid ester compound, triethyl phosphite, Triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, etc. oxalic acid triester compounds, dilauryl hydrogen phosphite, dioleyl Examples thereof include phosphite diester compounds such as hydrogen phosphite and diphenyl hydrogen phosphite.

  The reaction product of p-toluenesulfonyl monoisocyanate and water may be obtained by reacting p-toluenesulfonyl monoisocyanate and water in advance before blending with the curable composition of the present invention. , P-toluenesulfonyl monoisocyanate may be added to and reacted with while the curable composition is being blended, or may be reacted with water present in the curable composition.

  The plasticizer is used for the purpose of lowering the viscosity of the curable composition to improve workability and adjusting the physical properties of the rubber after curing of the curable composition. Specifically, phthalic acid esters such as dioctyl phthalate, diisononyl phthalate, dibutyl phthalate, and butylbenzyl phthalate; aliphatic carboxylic acid esters such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate, and butyl oleate. Low molecular weight plasticizers such as polyamines; polyoxyalkylene-based triols, polyoxyalkylene-based diols and polyoxyalkylene-based monools similar to those that can be used for the synthesis of the isocyanate group-containing urethane prepolymer described above are urethaned or etherified Or a high molecular weight plasticizer having an esterified number average molecular weight of 1,000 or more; a high molecular weight plasticizer having a number average molecular weight of 1,000 or more that does not react with an isocyanate group of polystyrenes such as poly-α-methylstyrene and polystyrene Agents. These can be used alone or in combination of two or more.

  The plasticizer is preferably used in an amount of 1 to 200 parts by mass, and more preferably 2 to 50 parts by mass, based on 100 parts by mass of the urethane prepolymer.

  The weather resistance stabilizer is used for the purpose of preventing oxidation, light deterioration and heat deterioration of the curable composition to further improve weather resistance and heat resistance. Examples of the weather resistance stabilizer include a hindered amine light stabilizer, a hindered phenol antioxidant, and an ultraviolet absorber. These can be used alone or in combination of two or more.

  Examples of the hindered amine light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (2,2,6,6-tetramethyl-1 (octyloxy) -4) decanedioate. -Piperidyl) ester, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate, Methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- [3- (3,3 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6 Low molecular weight compounds having a molecular weight of less than 1,000 such as 6-tetramethylpiperidine and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine; dimethyl succinate 1- (2-hydroxyethyl) -4- Hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl } {(2,2,6,6-Tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], N, N'-bis ( 3-Aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine In addition to the condensate, high molecular weight compounds having a molecular weight of 1,000 or more such as ADEKA STAB LA-63P and LA-68LD manufactured by ADEKA can be used.

  As hindered phenolic antioxidants, pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl) are used. -4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propioamide], benzenepropanoic acid 3,5-bis Examples include (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester and 2,4-dimethyl-6- (1-methylpentadecyl) phenol.

  As the ultraviolet absorber, a benzotriazole-based ultraviolet absorber such as 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole; 2- (4,6-diphenyl-1, Triazine-based UV absorbers such as 3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol; Benzophenone-based UV absorbers such as octabenzone; 2,4-di-tert-butylphenyl-3 Examples thereof include benzoate-based UV absorbers such as 5,5-di-tert-butyl-4-hydroxybenzoate.

  Among these, hindered amine-based light stabilizers, hindered phenol-based antioxidants, and mixtures thereof are preferable because of their high effect of improving weather resistance. The weather resistance stabilizer is preferably used in an amount of 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the urethane prepolymer.

  The filler is used as an extender for the curable composition and for the purpose of reinforcing the physical properties of the cured product. Examples include inorganic fillers and organic fillers. As the inorganic filler, heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, mica, kaolin, zeolite, graphite, diatomaceous earth, clay, talc, silicic anhydride, quartz, aluminum powder, zinc powder, hydroxide Inorganic powder fillers such as calcium, magnesium carbonate and alumina; inorganic fiber fillers such as glass fibers and carbon fibers; inorganic balloon fillers such as glass balloons, shirasu balloons, silica balloons and ceramic balloons. .. Examples of the organic filler include wood powder, walnut flour, chaff powder, pulp powder, rubber powder, thermoplastic or thermosetting resin powder, and other organic powder fillers; polyethylene balloons, saran microballoons, and other organic fillers. A balloon-shaped filler may be used. Further, a flame-retardant imparting filler such as magnesium hydroxide or aluminum hydroxide can be used. These can be used alone or in combination of two or more.

  The amount of the filler used is preferably 1 to 500 parts by mass, more preferably 10 to 300 parts by mass, and particularly preferably 10 to 200 parts by mass with respect to 100 parts by mass of the urethane prepolymer.

  The thixotropic agent is used for imparting thixotropy to a curable composition and preventing sagging or slump when the curable composition is used on a vertical surface or an inclined surface, or by bead coating the curable composition. , It is used for the purpose of maintaining the applied shape when applied with a comb-like iron. As the thixotropic agent, finely divided silica such as hydrophilic or hydrophobic colloidal silica; an inorganic thixotropic agent such as fatty acid surface-treated calcium carbonate; an organic thixotropic agent such as organic bentonite or fatty acid amide; Can be mentioned. These can be used alone or in combination of two or more.

  Of these, inorganic thixotropic agents are preferable, and fine powder silica and fatty acid surface-treated calcium carbonate are preferable, because they can impart stable thixotropy to the curable composition. The fatty acid surface-treated calcium carbonate is obtained by treating the surfaces of heavy calcium carbonate, light calcium carbonate and colloidal calcium carbonate with fatty acids such as fatty acids, fatty acid alkyl esters, fatty acid metal salts and fatty acid organic salts.

  Examples of the fatty acid include fatty acids having a carbon number of 10 to 25 such as 2-ethylhexanoic acid, lauric acid, mistyric acid, palmitic acid, stearic acid and hepic acid. Examples of the metal salt include sodium salt, potassium salt, calcium salt, aluminum salt, and examples of the organic salt include ammonium salt.

  As commercial products of fatty acid surface-treated calcium carbonate, there are Sealett 200, Calfine 200, Calfine 200M, Calfine 500, Calfine N-40, Calfine N-350 manufactured by Maruo Calcium Co .; Hakutanka CCR, Hakutanka CCR-S, Hakutanka CCR-B, VIGOT-10, VIGOT-15, Viscolite-SV, Viscolite-OS, Viscolite EL-20; NCC # 3010, NCC # 1010 of Nitto Koka Kogyo Co., Ltd. .. These can be used alone or in combination of two or more. Of these, calcium carbonate surface-treated with a fatty acid or a fatty acid metal salt is preferable because of its high thixotropic effect.

The average particle size of the fatty acid surface-treated calcium carbonate is preferably 0.01 to 1.0 μm, more preferably 0.01 to 0.3 μm. BET specific surface area of the fatty acid surface-treated calcium carbonate is preferably 5 to 200 m ² / g, further 10 to 60 m ² / g are preferred. If the average particle size is less than 0.01 μm or the BET specific surface area exceeds 200 m ² / g, the viscosity of the resulting curable composition will increase and the workability will deteriorate, which is not preferable. Further, if the average particle diameter exceeds 1.0 μm or the BET specific surface area falls below 5 m ² / g, the thixotropic effect is reduced, which is not preferable.

  The heat loss of the fatty acid surface-treated calcium carbonate is preferably 30 to 150 mg / g, and more preferably 50 to 120 mg / g, since the curable composition has good anti-curing sheet adhesion. The thermal loss of the fatty acid surface-treated calcium carbonate can be determined by thermogravimetric measurement (TG). Specifically, for example, it can be determined by the following measuring method.

[Measurement method of heat loss]
10 mg of fatty acid surface-treated calcium carbonate is weighed into a platinum sample pan having a diameter of 5 mm, and the temperature is raised from room temperature to 510 ° C. at a rate of 15 ° C./min using a thermogravimetric analyzer (TG8120, manufactured by Rigaku Corporation). At this time, the weight decreased in the range of 200 to 500 ° C. is measured to determine the heat loss (mg / g) per 1 g of the fatty acid surface-treated calcium carbonate.

  The amount of the thixotropic agent used is preferably 1 to 200 parts by mass, more preferably 5 to 150 parts by mass, based on 100 parts by mass of the urethane prepolymer.

  The adhesiveness improver is used for the purpose of improving the adhesiveness of the curable composition. Specific examples thereof include various coupling agents such as silane-based, aluminum-based, zirco-aluminate-based coupling agents and their partial hydrolysis-condensation products. Of these, a silane coupling agent or a partial hydrolysis-condensation product thereof is preferable because it has excellent adhesiveness.

  As the silane coupling agent, vinyltrimethoxysilane, vinylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) Examples include compounds having an alkoxysilyl group and having a molecular weight of 500 or less, such as -3-aminopropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane. Alternatively, a compound having a molecular weight of 200 to 3,000 is a partial hydrolysis-condensation product of these silane coupling agents. These can be used alone or in combination of two or more.

  The storage stability improver (dehydrating agent) is used for the purpose of improving the storage stability of the curable composition. Specific examples include vinyltrimethoxysilane, calcium oxide, and p-toluenesulfonyl isocyanate (PTSI) that act as a dehydrating agent by reacting with water present in the curable composition. These can be used alone or in combination of two or more.

  The colorant is used for the purpose of coloring the curable composition and imparting design properties to the cured product. Specific examples include inorganic pigments such as titanium oxide and iron oxide, organic pigments such as copper phthalocyanine, and carbon black. These can be used alone or in combination of two or more.

  The organic solvent is used for the purpose of lowering the viscosity of the curable composition and improving the extrudability and workability during casting and coating. As the organic solvent, any organic solvent that has good compatibility with other components in the curable composition and does not react with other components can be used without particular limitation. Specifically, carbonate solvents such as dimethyl carbonate, ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate and butyl acetate, aliphatic solvents such as n-hexane, and alicyclic solvents such as cyclohexane. Examples thereof include solvents, aromatic solvents such as toluene and xylene, and organic solvents such as petroleum fraction solvents such as mineral spirit and industrial gasoline. These can be used alone or in combination of two or more.

  The curable composition of the present invention reacts with water such as humidity to be cured, and thus can be used as a one-pack type moisture curable composition. Further, the curable composition of the present invention can be used as a two-component type reaction curable composition having a main component and an active hydrogen-containing compound such as polyamine or polyol as a curing agent. It is preferable to use it as a one-pack type moisture-curable composition because it does not require the trouble of mixing the main agent and the curing agent, and does not cause curing failure due to mixing mistakes or insufficient mixing and has excellent workability.

  When the curable composition of the present invention is used for construction, the material (member) to be constructed is mortar, concrete, ALC (Autoclaved Lightweight Concrete), glass, marble, granite, siding, tile, roof tile, brick. Inorganic materials such as: metal materials such as iron, copper, stainless steel, galvanium steel plate, galvanized steel, aluminum, titanium, acrylic resin, polyester resin, vinyl chloride, ABS (Acrylonitrile-Butadiene-Styrene copolymer), FRP (Fiber Reinforced Plastic), etc. Materials made of synthetic resin; wood materials such as wood and plywood.

  The method for producing the curable composition of the present invention is not particularly limited, but specifically, an isocyanate group-containing urethane prepolymer, and optionally a silane compound and / or a partial hydrolysis-condensation product of a silane compound, oxazolidine. Compounds and additives are charged in glass, stainless steel, iron, etc. in a mixing vessel equipped with a stirrer, water such as moisture is shut off, and the mixture is manufactured by stirring and mixing in a batch or continuous manner under a dry nitrogen stream. Can be mentioned.

  Since the curable composition of the present invention thickens and cures with water such as moisture, it is preferably stored in a container that can block water such as moisture and sealed. The container is not particularly limited as long as it can block water such as moisture. For example, a metal or resin pail can, an aluminum bag, a paper or resin cartridge can be used.

  Examples of the present invention will be shown below, but the present invention is not construed as being limited to the examples.

[Synthesis Example 1] (Synthesis of isocyanate group-containing urethane prepolymer PU-1)
620.4 g of polyoxypropylene diol (number average molecular weight 3,300, exenol 3021, manufactured by Asahi Glass Co., Ltd.), polyoxy, while flowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube, heating / cooling device Propylene triol (number average molecular weight 4,000, Triol-MN-4000, manufactured by Mitsui Chemicals, Inc.) 160.0 g, polyoxypropylene monool (number average molecular weight 3,080, preminol 1003, manufactured by Asahi Glass Co., Ltd.) 100.0 g 119.6 g of isophorone diisocyanate (molecular weight 222.3, manufactured by Evonik Japan) and 0.2 g of dibutyltin dilaurate (Neostan U-100, manufactured by Nitto Kasei Co., Ltd.) were charged with stirring and heated to 75 to 85 ° C. And reacted for 4 hours. The reaction was terminated when the isocyanate group content became the theoretical value (2.3% by mass) or less, and the isocyanate group-containing urethane prepolymer PU-1 was synthesized. The isocyanate group-containing urethane prepolymer PU-1 was a viscous liquid which was transparent at room temperature and had an isocyanate group content of 2.1% by mass measured by titration. The isocyanate group-containing urethane prepolymer PU-1 has a branch density (theoretical value) of 0.04 mmol / g.

[Synthesis Example 2] (Synthesis of isocyanate group-containing urethane prepolymer PU-2)
581.8 g of polyoxypropylene diol (number average molecular weight 3,300, exenol 3021, manufactured by Asahi Glass Co., Ltd.), polyoxy, while flowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube, heating / cooling device Propylene triol (number average molecular weight 4,000, Triol-MN-4000, manufactured by Mitsui Chemicals, Inc.) 160.0 g, polyoxypropylene monool (number average molecular weight 3,080, preminol 1003, manufactured by Asahi Glass Co., Ltd.) 100.0 g , 30.0 g of pentaerythritol triacrylate (molecular weight 298) were charged, and while stirring, isophorone diisocyanate (molecular weight 222.3, manufactured by Evonik Japan) 128.2 g and dibutyltin dilaurate (Neostan U-100, manufactured by Nitto Kasei). 0.2 g was charged, heated and reacted at 75 to 85 ° C. for 4 hours. The reaction was terminated when the isocyanate group content fell below the theoretical value (2.3% by mass), and the isocyanate group-containing urethane prepolymer PU-2 was synthesized. The isocyanate group-containing urethane prepolymer PU-2 was a viscous liquid that was transparent at room temperature and had an isocyanate group content of 2.1% by mass measured by titration. The isocyanate group-containing urethane prepolymer PU-2 has a branch density (theoretical value) of 0.04 mmol / g and an acryloyl group content (theoretical value) of 0.3 mmol / g.

[Synthesis Example 3] (Synthesis of isocyanate group-containing urethane prepolymer PU-3)
In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen seal tube, and a heating / cooling device, 798.6 g of polyoxypropylene diol (number average molecular weight 3,300, exenol 3021, manufactured by Asahi Glass Co., Ltd.) was added while flowing nitrogen gas. 80.0 g of propylene triol (number average molecular weight 4,000, Triol-MN-4000, manufactured by Mitsui Chemicals, Inc.) was charged, and 121.4 g of isophorone diisocyanate (molecular weight 222.3, manufactured by Evonik Japan) while stirring, dibutyltin dilaurate. (Neostan U-100, manufactured by Nitto Kasei Co., Ltd.) was charged in an amount of 0.2 g, heated, and reacted at 75 to 85 ° C. for 4 hours. The reaction was terminated when the isocyanate group content became the theoretical value (2.3% by mass) or less, and the isocyanate group-containing urethane prepolymer PU-3 was synthesized. The isocyanate group-containing urethane prepolymer PU-3 was a viscous liquid that was transparent at room temperature and had an isocyanate group content of 2.1 mass% measured by titration. The isocyanate group-containing urethane prepolymer PU-3 has a branch density (theoretical value) of 0.02 mmol / g.

[Synthesis Example 4] (Synthesis of urethane bond-containing oxazolidine compound O-1)
435.0 g of diethanolamine (molecular weight 105) and 183.0 g of toluene were charged into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen seal tube, an ester tube, and a heating / cooling device, and isobutyraldehyde (molecular weight 72.1) was added while stirring. 328.0 g was charged, the mixture was heated while flowing nitrogen gas and the reflux dehydration reaction was continued at 110 to 150 ° C., and water (74.5 g) as a byproduct was taken out of the system. After completion of the reaction, the mixture was further heated under reduced pressure (50 to 70 hPa) to remove toluene and unreacted isobutyraldehyde to obtain an intermediate reaction product N-hydroxyethyl-2-isopropyloxazolidine.

  Next, 348.0 g of hexamethylene diisocyanate (molecular weight 168) was added to 659.0 g of the obtained N-hydroxyethyl-2-isopropyloxazolidine, and the mixture was heated at 80 ° C. for 8 hours, and the measured NCO content by titration was 0.0. The reaction was terminated at the time point when the content reached to mass%, and a urethane bond-containing oxazolidine compound O-1 having two oxazolidine rings in the molecule was obtained. The urethane bond-containing oxazolidine compound O-1 was liquid at room temperature.

[Example 1]
100 g of the isocyanate group-containing urethane prepolymer PU-1 obtained in Synthesis Example 1 was charged into a kneading container equipped with a stirrer, a heating / cooling device and a nitrogen seal tube while flowing nitrogen gas, and the mixture was stirred at 100 to 110 ° C. in advance. 20 g of heavy calcium carbonate (Whiten B, manufactured by Shiraishi Calcium Co.) dried in a dryer to a water content of 0.05% by mass or less, fatty acid surface-treated calcium carbonate A (white luster CCR-S, heat loss) 34.4 mg / g, manufactured by Shiraishi Industry Co., Ltd.), 100 g of titanium oxide, 10 g of titanium oxide and 10 g of diisononyl phthalate (DINP) were charged and mixed until the contents became uniform. Next, 2 g of partially hydrolyzed condensate A of a silane compound (a mixture of tetraethoxysilane and an oligomer of tetraethoxysilane (an average pentamer), ethyl silicate 40, manufactured by Colcoat), 5 g of dimethyl carbonate, and a hindered amine light stabilizer were added to 5 g of dimethyl carbonate. (ADEKA STAB LA-63P, manufactured by ADEKA), 1 g, hindered phenolic antioxidant {pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]} (irganox 1010, manufactured by BASF Corporation), 12 g of the urethane bond-containing oxazolidine compound O-1 obtained in Synthesis Example 4 and 0.03 g of dibutyltin dilaurate (Neostan U-100, manufactured by Nitto Kasei Co., Ltd.) were charged. Further mix until the material is uniform. Then, the mixture was degassed under reduced pressure at 50 to 100 hPa, filled in a container, and sealed to prepare a curable composition.

[Example 2]
The same as Example 1 except that 2 g of a partial hydrolysis condensate B of a silane compound (polybutoxymethoxysiloxane, MKC silicate MS58B30, manufactured by Mitsubishi Chemical Corporation) was used instead of using the partial hydrolysis condensate A of a silane compound. Was performed to prepare a curable composition.

[Example 3]
The same as in Example 1 except that 100 g of fatty acid surface-treated calcium carbonate B (Calfine N-40, loss on heat 95.0 mg / g, manufactured by Maruo Calcium Co., Ltd.) was used instead of using the fatty acid surface-treated calcium carbonate A. An operation was performed to prepare a curable composition.

[Example 4]
A curable composition was prepared in the same manner as in Example 1, except that 100 g of the isocyanate group-containing urethane prepolymer PU-2 obtained in Synthesis Example 2 was used instead of the isocyanate group-containing urethane prepolymer PU-1. Was prepared.

[Example 5]
A curable composition was prepared in the same manner as in Example 2 except that 100 g of the isocyanate group-containing urethane prepolymer PU-2 obtained in Synthesis Example 2 was used instead of the isocyanate group-containing urethane prepolymer PU-1. Was prepared.

[Example 6]
A curable composition was prepared in the same manner as in Example 3, except that 100 g of the isocyanate group-containing urethane prepolymer PU-2 obtained in Synthesis Example 2 was used instead of the isocyanate group-containing urethane prepolymer PU-1. Was prepared.

[Example 7]
A curable composition was prepared in the same manner as in Example 1, except that 0.5 g of acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was further added.

[Example 8]
A curable composition was prepared in the same manner as in Example 3 except that 0.5 g of acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was further added.

[Example 9]
A curable composition was prepared in the same manner as in Example 4, except that 0.5 g of acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was further added.

[Example 10]
A curable composition was prepared in the same manner as in Example 6, except that 0.5 g of acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was further added.

[Comparative Example 1]
Instead of using the isocyanate group-containing urethane prepolymer PU-1 in Example 1, 100 g of the isocyanate group-containing urethane prepolymer PU-3 obtained in Synthesis Example 3 was used, and the partially hydrolyzed condensate A of the silane compound was used. A curable composition was prepared by performing the same operation except that it was not performed.

[Comparative example 2]
A curable composition was prepared in the same manner as in Example 1 except that 100 g of the isocyanate group-containing urethane prepolymer PU-3 obtained in Synthesis Example 3 was used instead of the isocyanate group-containing urethane prepolymer PU-1. Was prepared.

[Comparative Example 3]
A curable composition was prepared in the same manner as in Example 2, except that 100 g of the isocyanate group-containing urethane prepolymer PU-3 obtained in Synthesis Example 3 was used instead of the isocyanate group-containing urethane prepolymer PU-1. Was prepared.

<Evaluation A of Curable Composition>
The following evaluations were performed using the curable compositions of Examples 1 to 6 and Comparative Examples 1 to 3. The evaluation results are shown in Table 1.

[Cure sheet adhesion prevention]
a) Curing sheet adhesion prevention property (5 ° C 40% RH)
A joint having a width of 30 mm, a depth of 10 mm and a length of 100 mm was prepared on a slate plate by using a 10 mm square backer. The joint was filled with a curable composition, and the excess was scraped off with a spatula to make the surface flat and used as a test piece.

  The test body was immediately cured for 5 days in an environment (indoor) of 5 ° C. and 40% RH. A curing sheet (polymasker (cloth tape + polyethylene sheet), manufactured by Otsuka Brush Manufacturing Co., Ltd.) was attached to the surface of the curable composition after curing so as to be orthogonal to the joint longitudinal direction. One day after the application, the curing sheet was peeled off and the peeling condition was visually confirmed. At this time, when the surface of the curable composition was touched with a finger, the surface was cured, but the inside was not cured.

b) Curing sheet adhesion prevention (23 ° C 50% RH)
A joint having a width of 30 mm, a depth of 10 mm and a length of 100 mm was prepared on a slate plate by using a 10 mm square backer. The joint was filled with a curable composition, and the excess was scraped off with a spatula to make the surface flat and to give a test specimen.

The test body was immediately cured in an environment (room) of 23 ° C. and 50% RH for 2 days or 3 days. A curing sheet (polymasker (cloth tape + polyethylene sheet), manufactured by Otsuka Brush Manufacturing Co., Ltd.) was attached to the surface of the curable composition after curing so as to be orthogonal to the joint longitudinal direction. One day after the application, the curing sheet was peeled off and the peeling condition was visually confirmed. At this time, when the surface of the curable composition was touched with a finger, the surface was cured, but the inside was not cured.
The curing sheet adhesion preventive property was evaluated as follows.
Rating:
⊚: The curing sheet does not adhere to the surface of the curable composition and peels off cleanly.
◯: The curing sheet adheres slightly to the surface of the curable composition, but peels off cleanly.
Δ: When the curing sheet partially adheres to the surface of the curable composition and is peeled off, the surface layer of the curable composition is pulled and there is a design defect.
X: The curing sheet adheres to the surface of the curable composition and cannot be peeled off unless strongly pulled. When the curing sheet is peeled off, most of the surface layer of the curable composition is pulled and there is a design problem.

[Prevention of pollution]
a) Black silica sand contamination A 10 mm square backer was placed on a slate plate to prepare joints of 20 mm width × 20 mm depth × 100 mm length. The joint was filled with a curable composition, and the excess was scraped off with a spatula to make the surface flat and used as a test piece.

The test body was immediately cured for 10 days in an environment (room) at 23 ° C. and 50% RH. The surface of the curable composition after curing was sprinkled with black silica sand (8 black, manufactured by Keimubu Cera Co., Ltd.), the test piece was immediately turned over, and the bottom of the slate plate was tapped by hand to drop excess black silica sand. The state of black silica sand (dirt) remaining on the surface of the curable composition was visually observed, and the stain resistance during curing was evaluated as follows.
Rating:
○: The surface of the curable composition was in a clean state with almost no adhesion of black silica sand.
×: A large amount of black silica sand adhered to the surface of the curable composition, and the surface was blackened.

b) Outdoor exposure contamination A square backer of 10 mm was placed on a slate plate to prepare joints of width 20 mm x depth 20 mm x length 100 mm. The joint was filled with a curable composition, and the excess was scraped off with a spatula to make the surface flat and to give a test specimen.

The test body was immediately cured in an environment (indoor) of 23 ° C. and 50% RH for 7 days, and then the test body was placed near an intersection having a large amount of outdoor traffic so as to be perpendicular to the ground and exposed for 30 days. The test body was about 1 m above the ground, and the surface of the curable composition was oriented toward the road. After 30 days of outdoor exposure, the surface of the curable composition was visually observed for the state of contamination, and the contamination prevention property was evaluated as follows.
Rating:
◯: The curable composition was in a clean state with almost no dust or dirt adhering to the surface.
Δ: A small amount of dust adhered to the surface of the curable composition, but was in a clean state.
X: A large amount of dust and dirt adhered to the surface of the curable composition and was in a dirty state.

[durability]
The durability of the curable composition was evaluated by "5.17 Durability test (Durability category 8020)" of JIS A 1439 (2010) "Testing method for building sealing materials". The test body was an H-type test body, and the adherend used was a mortar whose surface had been pretreated with a moisture-curable urethane-based primer (OP-2019, manufactured by Auto Chemical Industry Co., Ltd.).

<Evaluation B of Curable Composition>
Using the curable compositions of Examples 7 to 10, the following evaluations were performed in addition to the evaluation A of the curable composition described above. The evaluation results are shown in Table 2.

[Cure sheet adhesion prevention]
a) Curing sheet adhesion prevention property (5 ° C 40% RH)
A joint having a width of 30 mm, a depth of 10 mm and a length of 100 mm was prepared on a slate plate by using a 10 mm square backer. The joint was filled with a curable composition, and the excess was scraped off with a spatula to make the surface flat and to give a test specimen.

  The test body was immediately cured in an environment (indoor) at 5 ° C. and 40% RH for 1 day or 3 days. A curing sheet (polymasker (cloth tape + polyethylene sheet), manufactured by Otsuka Brush Manufacturing Co., Ltd.) was attached to the surface of the curable composition after curing so as to be orthogonal to the joint longitudinal direction. One day after the application, the curing sheet was peeled off and the peeling condition was visually confirmed. At this time, when the surface of the curable composition was touched with a finger, the surface was cured, but the inside was not cured.

b) Curing sheet adhesion prevention (23 ° C 50% RH)
A joint having a width of 30 mm, a depth of 10 mm and a length of 100 mm was prepared on a slate plate by using a 10 mm square backer. The joint was filled with a curable composition, and the excess was scraped off with a spatula to make the surface flat and used as a test piece.

The test body was immediately cured in an environment (room) at 23 ° C. and 50% RH for 1 day. A curing sheet (polymasker (cloth tape + polyethylene sheet), manufactured by Otsuka Brush Manufacturing Co., Ltd.) was attached to the surface of the curable composition after curing so as to be orthogonal to the joint longitudinal direction. One day after the application, the curing sheet was peeled off and the peeling condition was visually confirmed. At this time, when the surface of the curable composition was touched with a finger, the surface was cured, but the inside was not cured.
The curing sheet adhesion preventive property was evaluated as follows.
Rating:
⊚: The curing sheet does not adhere to the surface of the curable composition and peels off cleanly.
◯: The curing sheet adheres slightly to the surface of the curable composition, but peels off cleanly.
Δ: When the curing sheet partially adheres to the surface of the curable composition and is peeled off, the surface layer of the curable composition is pulled and there is a design defect.
X: The curing sheet adheres to the surface of the curable composition and cannot be peeled off unless strongly pulled. When the curing sheet is peeled off, most of the surface layer of the curable composition is pulled and there is a design problem.

  From the results of Examples 1 to 10 and Comparative Examples 1 to 3 described above, the curable composition of the present invention is excellent in durability after curing and also excellent in anti-staining property in outdoor exposure, and the curing sheet has a curable composition. It can be seen that the protective sheet has excellent anti-adhesion properties, that is, it does not adhere to the surface of the object and peels off cleanly. Further, from the results of Examples 7 to 10, it can be seen that even after one day at 5 ° C. 40% RH and 23 ° C. 50% RH, that is, even in the early stage of curing of the composition, the curing sheet adhesion preventive property is excellent.

  As described above, the curable composition of the present invention is a sealing material composition and a waterproof material composition because the composition after curing has excellent durability as well as excellent anti-staining property in outdoor exposure and excellent anti-curing sheet adhesion property. It can be suitably used as an adhesive composition and a coating material composition. Moreover, the curable composition of the present invention can be suitably used for construction and civil engineering.

Claims (9)

An isocyanate group-containing urethane prepolymer obtained by reacting an organic isocyanate compound and an active hydrogen-containing compound, and a silane compound represented by the following general formula (1) and / or containing a partial hydrolysis-condensation product of a silane compound ,
The curable composition, wherein the active hydrogen-containing compound contains a polyoxyalkylene-based triol, a polyoxyalkylene-based diol, and a polyoxyalkylene-based monool.
R _4-m Si- (OR ¹ ) _m (1)
(In the formula (1), R represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and when R is plural, they may be the same or different. R ¹ is 1 having 1 or more carbon atoms. is a valence of the hydrocarbon group, at least one (OR ¹⁾ good be different even for the same when it. (OR ¹⁾ is plural alkoxy group having 2 to 6 carbon atoms .m Is an integer of 1 to 4.)   The polyoxyalkylene-based triol has a number average molecular weight of 1,000 to 30,000, the polyoxyalkylene-based diol has a number average molecular weight of 1,000 to 30,000, and the polyoxyalkylene-based monool has a number-average molecular weight of 1,000 to 30,000. The curable composition according to claim 1, which has a number average molecular weight of 1,000 to 30,000.   The curable composition according to claim 1 or 2, wherein the isocyanate group-containing urethane prepolymer has a branch density of 0.03 mmol / g or more.   Content of the said polyoxyalkylene type | system | group monool is 5 to 30 mass% in the said isocyanate group content urethane prepolymer, The curable composition as described in any one of Claims 1-3 characterized by the above-mentioned. object.   The curable composition according to any one of claims 1 to 4, wherein the isocyanate group-containing urethane prepolymer has a photoreactive unsaturated bond in the molecule. Further characterized by containing oxazolidine compounds, curable composition according to any one of claims 1-5. Furthermore, at least one or more selected from a curing accelerating catalyst, a plasticizer, a weather resistance stabilizer, a filler, a thixotropic agent, an adhesion improver, a storage stability improver (dehydrating agent), a colorant and an organic solvent. characterized in that it contains an additive, the curable composition according to any one of claims 1-6. The curable composition is characterized in that it is a building or curable composition for civil engineering, curable composition according to any one of claims 1-7. The curable composition, sealant composition, waterproofing material composition, characterized in that an adhesive composition or a coating material composition, curable composition according to any one of claims 1-8 object.