JP7007698B2 - Curable composition - Google Patents

Description

The present invention relates to a curable composition having excellent stain prevention properties, curing sheet adhesion prevention properties, and liquid dripping prevention properties.

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 is excellent in workability, adhesiveness, and the like. The polyurethane resin can relatively freely adjust the physical characteristics of the rubber after curing from low modulus to high modulus (high elongation to low elongation). However, when a curable composition containing a polyurethane resin is designed in the low to medium modulus range, stickiness (tack) may remain on the surface after curing. In this case, dust and dirt are likely to adhere to the surface of the curable composition, and the surface is contaminated, causing design defects. In particular, 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 is highly sticky (tack), so that a large amount of dust and dirt adheres to the curable composition. The surface of the object is contaminated.

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 place where the curable composition is used. Further, when the topcoat paint is applied to the surface of the curable composition or its peripheral members after the curable composition is used, the curing sheet is cured even if the curable composition is in the middle of curing in order to shorten the construction period. It may be affixed to the surface of. In this case, the curing sheet adheres to the surface of the curable composition mainly due to the stickiness (tack) on the surface of the curable composition, and when the curing sheet is peeled off after applying the topcoat paint, the surface layer portion of the curable composition May be pulled off by the drop clothes. If the surface layer of the curable composition is peeled off, that part must be repaired. Therefore, it is required to improve the adhesion prevention property of the curing sheet of the curable composition.

As a method for preventing contamination due to stickiness on the surface of the curable composition, a curable composition containing an isocyanate group-containing urethane prepolymer and a silane compound is known (for example, Patent Document 1 and Patent Document 2). The curable compositions described in these patent documents are excellent in preventing the surface of the curable composition from being contaminated by dust and dirt by improving the stickiness of the surface of the curable composition. The anti-adhesion property of the curing sheet has not been investigated.

Further, attempts have been made to add a balloon to the curable composition to reduce the weight and reduce the work load on the user (for example, Patent Document 3). When a balloon is added to the curable composition, a phenomenon (liquid dripping) in which the curable composition gradually leaks from the tip of the nozzle after ejection with a dedicated gun may occur, and it is necessary to improve it.

Japanese Unexamined Patent Publication No. 2008-201980 Japanese Unexamined Patent Publication No. 2009-07382 Japanese Unexamined Patent Publication No. 2008-285581

An object of the present invention is to provide a curable composition having excellent stain prevention property, curing sheet adhesion prevention property and liquid dripping prevention property.

As a result of diligent studies to solve the above requirements, the present inventors have found an isocyanate group-containing urethane prepolymer, surface-treated calcium carbonate having a heat loss of 50 to 150 mg / g, and a hollow body having an average particle size of less than 40 μm. It has been found that the curable composition contained therein is excellent in the antifouling property on the surface of the curable composition, the anti-adhesion property of the curing sheet and the anti-dripping property, and has completed the present invention. That is, the present invention relates to a curable composition having the aspects shown in the following (1) to (9).
(1) A curable composition comprising an isocyanate group-containing urethane prepolymer, a surface-treated calcium carbonate having a heat loss of 50 to 150 mg / g, and a hollow body having an average particle size of less than 40 μm.
(2) The curable composition according to (1), wherein the isocyanate group-containing urethane prepolymer has a branching density of 0.03 mmol / g or more.
(3) The curable composition according to (1) or (2), wherein the isocyanate group-containing urethane prepolymer has a photoreactive unsaturated bond in the molecule.
(4) Any of (1) to (3), wherein the blending amount of the hollow body having an average particle size of less than 40 μm is 0.1 to 5% by mass of the entire curable composition. The curable composition according to description.
(5) The curability according to any one of (1) to (4), which further contains a silane compound represented by the following general formula (1) and / or a partially hydrolyzed condensate of the silane compound. Composition.
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 there are a plurality of Rs, they may be the same or different. R ¹ is 1 having 1 or more carbon atoms. Although it is a valent hydrocarbon group, at least one of (OR ¹ ) is an alkoxy group having 2 to 6 carbon atoms. When there are a plurality of (OR ¹ ), they may be the same or different. Is an integer from 1 to 4.)
(6) The curable composition according to any one of (1) to (5), which further contains an oxazolidine compound.
(7) Further, at least one selected from a curing accelerating catalyst, a plasticizer, a weather resistance stabilizer, a filler, a rocking denaturing agent, an adhesiveness improving agent, a storage stability improving agent (dehydrating agent), a colorant and an organic solvent. The curable composition according to any one of (1) to (6), which contains an additive of more than one species.
(8) The curable composition according to any one of (1) to (7), wherein the curable composition is a curable composition for construction or civil engineering.
(9) The curing according to any one of (1) to (8), wherein the curable composition is a sealing material composition, a waterproof material composition, an adhesive composition or a coating material composition. Sex composition.

The curable composition of the present invention is excellent in antifouling property and anti-adhesion property of a curing sheet in outdoor exposure. Further, since the curable composition can be reduced in weight, the work load on the user can be reduced, the work load during transportation and the economic burden can be reduced, and the liquid dripping prevention property is also excellent. Further, the curable composition of the present invention can be used as both a one-component curable composition and a two-component curable composition, and therefore has a wide range of applications.

The curable composition of the present invention is an isocyanate group-containing urethane prepolymer (hereinafter, it may be simply referred to as "urethane prepolymer" including an isocyanate group-containing urethane prepolymer having a photoreactive unsaturated bond introduced later). It is characterized by containing a surface-treated calcium carbonate having a heat loss of 50 to 150 mg / g and a hollow body having an average particle size of less than 40 μm. Hereinafter, each component will be described in detail.

The isocyanate group-containing urethane prepolymer acts as a curing component in the curable composition of the present invention and imparts good adhesion to the adherend surface to the cured composition.

The isocyanate group-containing urethane prepolymer is a resin having one or more isocyanate groups, and the isocyanate group reacts with an active hydrogen (group) -containing compound to form a urethane bond, a urea bond, or the like, and is cross-linked and cured.

The isocyanate group-containing urethane prepolymer is such that the organic isocyanate compound and the active hydrogen-containing compound have an isocyanate group / active hydrogen molar ratio of preferably 1.2 to 10/1, more preferably 1.2 to 5/1. It can be produced by reacting all at once or sequentially in a range so that the isocyanate group remains in the urethane prepolymer. 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. Further, when 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-containing urethane prepolymer preferably has an isocyanate group content of 0.3 to 15% by mass, 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. 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 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 preferably 1,500 to 10,000. Is preferable. 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. 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).

As a method for producing an isocyanate group-containing urethane prepolymer, specifically, an organic isocyanate compound and an active hydrogen-containing compound are charged in a reaction vessel made of glass or stainless steel, and the reaction catalyst or the organic solvent is present or absent. Below, there is a method of reacting with stirring at 50 to 120 ° C. 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.

Examples of the organic isocyanate compound include organic polyisocyanate. The organic polyisocyanate is a compound having two or more isocyanate groups in the compound, and specifically, a toluene polyisocyanate such as 2,4-toluene diisocyanate or 2,6-toluene diisocyanate, 4,4'-. Diphenylmethane polyisocyanate such as diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 1,2-phenylenediocyanate, 1,3-phenylenediocyanate, 1,4-phenylenediocyanate, 2,4,6 -Phenylene polyisocyanate such as trimethylphenyl-1,3-diisocyanate, 2,4,6-triisopropylphenyl-1,3-diisocyanate, naphthalene polyisocyanate such as 1,4-naphthalenediocyanate, 1,5-naphthalenediocyanate, etc. Fragrances such as chlorophenylene-2,4-diisocyanate, 4,4'-diphenylether diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate Polyisocyanate can be mentioned. In addition, 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-cyclohexamethylene diisocyanate, isophorone diisocyanate, and hydrogenation Examples thereof include alicyclic polyisocyanates such as toluene diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Further, polypeptide isocyanates such as polymethylene polyphenyl polyisocyanate and crude toluene diisocyanate can be mentioned. Further, modified isocyanates obtained by modifying these organic polyisocyanates and having one or more uretdione bond, isocyanurate bond, allophanate bond, burette bond, uretonimine bond, carbodiimide bond, urethane bond or urea bond can be mentioned. All of these can be used alone or in combination of two or more.

Of these, an aliphatic polyisocyanate, an aromatic aliphatic polyisocyanate, an alicyclic polyisocyanate, and a modified isocyanate 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 an organic polyisocyanate and an 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-isopropylphenylmonoisocyanate and p-benzyloxyphenylmonoisocyanate.

An active hydrogen-containing compound is a compound having one or more active hydrogens (groups) in the compound. Specific examples thereof include high molecular weight polyols, high molecular weight polyamines, low molecular weight polyols, low molecular weight amino alcohols, low molecular weight polyamines, high molecular weight monools, and low molecular weight monools. These can be used alone or in combination of two or more.

Examples of the polymer polyol include polyoxyalkylene-based polyols, polyester polyols, polycarbonate polyols, hydrocarbon-based polyols, poly (meth) acrylate-based polyols, and animal and plant-based polyols. Of these, polyoxyalkylene-based polyols and poly (meth) acrylate-based polyols are preferable. In the present invention, "(meth) acrylate" means "acrylate and / or methacrylate".

The number average molecular weight of the polymer polyol is preferably 1,000 to 30,000, more preferably 1,000 to 20,000.

Examples of the polyoxyalkylene-based polyol include polyoxyalkylene-based triols and polyoxyalkylene-based diols.

In the present invention, the "system" of the polyoxyalkylene-based triol and the polyoxyalkylene-based diol is 50% by mass or more, more 80% by mass or more, and particularly 90% by mass or more of the portion of the molecule excluding the hydroxyl group. If it is composed of polyoxyalkylene, it means that the remaining portion may be modified with ester, urethane, polycarbonate, polyamide, poly (meth) acrylate, polyolefin or the like. Most preferably, 95% by mass or more of the molecule excluding the hydroxyl group is composed of polyoxyalkylene.

The polyoxyalkylene-based triol and the polyoxyalkylene-based diol can be obtained by ring-opening addition polymerization of an alkylene oxide with an initiator in the presence of a polymerization catalyst. The total degree of unsaturation of the polyoxyalkylene-based triol and the polyoxyalkylene-based diol is preferably 0.1 meq / g or less, more preferably 0.07 meq / g or less, and particularly preferably 0.04 meq / g or less.

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

As the initiator, a compound having 2 to 3 active hydrogen (groups) (hydroxyl groups or amino groups capable of reacting with an alkylene oxide) in the molecule is used. A small amount of a compound having 4 active hydrogens (groups) in the molecule can also be used in combination with these.

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.

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 hydrogens include dihydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol, bisphenol A, and bisphenol F.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-epoxybutane, and 2,3-epoxybutane. Of these, the combined use of propylene oxide, ethylene oxide, propylene oxide and ethylene oxide is preferable, and the combined use of propylene oxide, propylene oxide and ethylene oxide is more preferable.

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

In the present invention, the "oxyethylene propylene" contains an oxyethylene group (-CH ₂ CH ₂ O-) and an oxypropylene group (-CH (CH ₃ ) CH ₂ O-) in the molecule.

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

Examples of the polyester polyol 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 and the like. Polycarboxylic acids; one or more of these acid anhydrides or alkyl esters such as methyl esters and ethyl esters, 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, neopentylglycol, 1,8-octanediol, One or more of 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, pentaerythritol, etc. Examples thereof include polyester polyols obtained by the reaction with. In addition to these polycarboxylic acids, acid anhydrides, and low molecular weight polyols, low molecular weight polyamines such as butyrenidamine, hexamethylenediamine, xylylenediamine, and isophoronediamine, and low molecular weight polyamines such as monoethanolamine and diethanolamine. Examples thereof include polyesteramide polyols obtained by reacting with one or more of molecular amino alcohols.

As the polycarbonate polyol, a dehydroxylation reaction between the low molecular weight polyols used in the synthesis of the polyester polyol described above and phosgen, or a transesterification reaction between the low molecular weight polyols described above and diethylene carbonate, dimethyl carbonate, diethyl carbonate, or diphenyl carbonate. The ones that can be obtained from.

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 a radical polymerization initiator. Examples thereof include those copolymerized in the presence or absence.

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

Examples of animal and plant-based polyols include castor oil-based polyols and silk fibroin.

Any of the above-mentioned polymer polyols can be used alone or in combination of two or more.

Further, the polymer monool can be used in combination with the above-mentioned polymer polyol. The number average molecular weight of the polymer monool is preferably 1,000 to 30,000, more preferably 1,000 to 20,000.

When a polymer polyol and a polymer monool are used in combination, the combination thereof is preferably a polymer triol and a polymer diol and a polymer monool, or a polymer triol and a polymer monool.

As the polymer monool, polyoxyalkylene-based monool is preferable.

In the present invention, the "system" of the polyoxyalkylene-based monool is composed of 50% by mass or more, further 80% by mass or more, particularly 90% by mass or more of the portion excluding the hydroxyl group in the molecule. If so, it means that the remaining portion may be modified with an ester, urethane, polycarbonate, polyamide, poly (meth) acrylate, polyolefin or the like. Most preferably, 95% by mass or more of the molecule excluding the hydroxyl group is composed of polyoxyalkylene.

The polyoxyalkylene-based monool is obtained by ring-opening addition polymerization of an alkylene oxide with an initiator in the presence of a polymerization catalyst. The total degree of unsaturation of the polyoxyalkylene-based monool is preferably 0.1 meq / g or less, more preferably 0.07 meq / g or less, and particularly preferably 0.04 meq / g or less.

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

As an initiator for producing a polyoxyalkylene-based monool, a compound having 1 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, Monohydric phenols such as nonylphenol; secondary amines such as dimethylamine and diethylamine can be mentioned.

When the polymer monool is used in combination, the content of the polymer monool in the isocyanate group-containing urethane prepolymer is preferably 5 to 30% by mass with respect to the total amount of the urethane prepolymer. When the content of the polymer monool in the urethane prepolymer is within the above range, the curable composition has excellent durability (for example, the durability of JIS A 5758). In particular, as the branching density of the urethane prepolymer is increased, the physical properties of the curable composition after curing tend to be high modulus and low elongation, and the durability tends to decrease. By setting the oar content in the above range, the cured composition of the curable composition has excellent durability even if the branching density of the urethane prepolymer is increased.

The isocyanate group-containing urethane prepolymer can also introduce a photoreactive unsaturated bond into the urethane prepolymer for the purpose of imparting weather resistance. The urethane prepolymer having a photoreactive unsaturated bond acts as a curing component in the curable composition of the present invention, and at the same time, imparts good adhesion to the adherend surface and excellent weather resistance to the cured composition. 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 unsaturated bonds 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 into which a photoreactive unsaturated bond has been introduced reacts with the active hydrogen-containing compound and is cross-linked and cured. In addition, the photoreactive unsaturated bond of the isocyanate group-containing urethane prepolymer into which a photoreactive unsaturated bond has been introduced undergoes a polymerization reaction when exposed to light, and a cured film having excellent weather resistance is formed on the surface of the curable composition. To form. It is considered that this cured film imparts excellent weather resistance to the curable composition. As the photoreactive unsaturated bond, an unsaturated bond derived from a (meth) acryloyl group is preferable because it has a high effect of imparting weather resistance.

As a method of introducing a photoreactive unsaturated bond into an isocyanate group-containing urethane prepolymer,
(B) Organic isocyanate compounds, high molecular weight active hydrogen-containing compounds (number average molecular weight of 1,000 or more), and low-molecular-weight active hydrogen-containing compounds having active hydrogen and photoreactive unsaturated bonds in the molecule (number). (Average molecular weight less than 1,000) is reacted with the total amount of active hydrogen under the condition of excess isocyanate group;
(B) An organic isocyanate compound and a polymer (number average molecular weight of 1,000 or more) active hydrogen-containing compound having an active hydrogen and a photoreactive unsaturated bond in the molecule (for example, a mono (meth) of polyoxyalkylene triol. ) A method obtained by reacting acrylate, an alkylene oxide adduct of (meth) acrylic acid, a polybutadiene polyol) with the total amount of active hydrogen under the condition of excess isocyanate group; and (c) an organic isocyanate compound and an intramolecular method. 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 1,000 or more). ) With the active hydrogen-containing compound in the condition of excess isocyanate group with respect to the total amount of active hydrogen;
Can be mentioned. The method (a) described above is preferable in terms of availability of raw materials and ease of reaction. In the present invention, "(meth) acrylic acid" means "acrylic acid and / or methacrylic acid".

In the reaction of introducing a photoreactive unsaturated bond into an isocyanate group-containing urethane prepolymer, the raw materials may be charged and reacted in a batch, or the raw materials may be charged and reacted in sequence. The molar ratio (isocyanate group / active hydrogen) of the isocyanate group of the organic isocyanate compound and the active hydrogen-containing compound (including a compound having an active hydrogen and a photoreactive unsaturated bond) is preferably 1.2 to 10/1. Further, 1.2 to 5/1 is preferable. The isocyanate group content in the isocyanate group-containing urethane prepolymer into which a photoreactive unsaturated bond has been introduced is preferably 0.3 to 15% by mass, more preferably 0.5 to 5% by mass. When the isocyanate group content is less than 0.3% by mass, the molecular weight becomes too large, the viscosity increases, and the workability deteriorates. In addition, since the number of cross-linking points in the urethane prepolymer is reduced, 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 into which the photoreactive unsaturated bond has been introduced is preferably 0.01 mmol / g or more, more preferably 0.03 to 1 mmol / g. In particular, 0.05 to 0.5 mmol / g is preferable.

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

Examples of the active hydrogen-containing compound having a hydroxyl group and a (meth) acryloyl group include 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 ( Monohydroxymono (meth) acrylates such as meth) acrylates, hydroxyheptyl (meth) acrylates and hydroxyoctyl (meth) acrylates, trifunctional or higher alkylene polyols such as glycerin, trimethylolpropane and pentaerythritol, and (meth) acrylic acid. Monohydrokipoly (meth) acrylates such as glycerin di (meth) acrylate, trimethyl proprani (meth) acrylate, pentaerythritol tri (meth) acrylate, and glycerin mono, which are monoesters or polyesters such as diesters and triesters. Polyhydrokimono (meth) acrylates such as (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, and polyhydrochipoly (meth) acrylates such as pentaerythritol di (meth) acrylate. Can be mentioned. In addition to these, monohydroxymono (meth) such as diethylene glycol, dipropylene glycol, polyoxyethylene polyol, polyoxypropylene polyol, and polyols obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to bisphenol A and bisphenol F. ) Acrylate, polyhydroxymono (meth) acrylate, polyhydroxypoly (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate and other hydroxyalkyl (meth) acrylate active hydrogen, ethylene oxide, propylene oxide , Butylene oxide and other compounds to which an alkylene oxide is added and having a hydroxyl group, and a caprolactone modified product of hydroxyethyl acrylate having a hydroxyl group and the like can also be mentioned. These can be used alone or in combination of two or more. Of these, monohydroxypoly (meth) acrylates and dihydroxypoly (meth) acrylates are preferable in that the viscosity of the urethane prepolymer can be kept low and the effect of imparting weather resistance can be enhanced.

The surface-treated calcium carbonate will be described. Surface-treated calcium carbonate imparts rocking denaturation to the curable composition, and is used for the purpose of preventing sagging and slump when the curable composition is used on a vertical surface or an inclined surface, and the curable composition is bead coated. , Used for the purpose of maintaining the applied shape when applied with a shaving iron or the like. Further, the surface-treated calcium carbonate is a curable composition by using the surface-treated calcium carbonate having a heat loss of 200 to 500 ° C. of 50 to 150 mg / g at a heating rate of 15 ° C./min in combination with the above-mentioned urethane prepolymer. Is excellent in preventing adhesion of the curing sheet. Further, when used in combination with a silane compound and / or a partially hydrolyzed condensate of a silane compound described later, the curable composition is further excellent in preventing adhesion to the curing sheet. To the extent that the object of the present invention can be achieved, surface-treated calcium carbonate having a heat loss of 50 to 150 mg / g and surface-treated calcium carbonate other than surface-treated calcium carbonate having a heat loss of 50 to 150 mg / g can be used in combination. ..

Examples of the surface-treated calcium carbonate include fatty acid surface-treated calcium carbonate. Fatty acid surface treatment Calcium carbonate is obtained by treating the surface 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.

Fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, beef stearate, palm kernel fatty acid, partially cured palm fatty acid, extremely hardened palm fatty acid, palm fatty acid, partially hardened palm fatty acid, extremely hardened palm fatty acid, Examples thereof include palm fatty acid, palm stearic acid, beef fatty acid, partially hardened beef fatty acid, extremely hardened beef fat fatty acid, soybean fatty acid, partially hardened soybean fatty acid, extremely hardened soybean fatty acid, naphthenic acid, avietinic acid, and neoavietic acid. Examples of the metal salt include sodium salt, potassium salt, calcium salt and aluminum salt, and examples of the organic salt include ammonium salt.

Commercially available products of fatty acid surface-treated calcium carbonate include Maruo Calcium's Sealets 200, Calfine 200, Calfine 200M, Calfine 500, Calfine N-40, Calfine N-350; , White Gloss Flower CCR, White Gloss Flower CCR-S, White Gloss Flower CCR-B, VIGOT-10, VIGOT-15, Viscolite-SV, Viscolite-OS, Viscolite EL-20; NCC # 3010, NCC # 1010 manufactured by Nitto Powder Industry Co., Ltd. Can be mentioned. All of 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 it has a high effect of imparting shake denaturation.

The 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. The particle size of the fatty acid surface-treated calcium carbonate can be determined as the primary particle size measured by an electron microscope. The BET specific surface area of the fatty acid surface-treated calcium carbonate is preferably 5 to 200 m ² / g, more preferably 10 to 60 m ² / g. If the particle size is less than 0.01 μm or the BET specific surface area is more than 200 m ² / g, the viscosity of the obtained curable composition becomes high and the workability deteriorates, which is not preferable. If the particle size exceeds 1.0 μm or the BET specific surface area is less than 5 m ² / g, the effect of imparting sway denaturation decreases, which is not preferable.

The heat loss of the fatty acid surface-treated calcium carbonate is preferably 50 to 150 mg / g, more preferably 50 to 120 mg / g, because the curable composition has good property of preventing adhesion to the curing sheet. Fatty acid surface treatment The heat loss of calcium carbonate can be determined by thermogravimetric analysis (TG). Specifically, for example, it can be obtained by the following measurement method.

[Measuring method]
10 mg of fatty acid surface-treated calcium carbonate is weighed in 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 Co., Ltd.). At this time, the weight reduced in the range of 200 to 500 ° C. is measured, and the heat loss (mg / g) per 1 g of the fatty acid surface-treated calcium carbonate is determined.

The amount of the surface-treated calcium carbonate used is preferably 1 to 200 parts by mass, more preferably 5 to 150 parts by mass with respect to 100 parts by mass of the isocyanate group-containing urethane prepolymer.

A hollow body having an average particle size of less than 40 μm will be described. Hollow bodies with an average particle size of less than 40 μm reduce the specific weight of the curable composition to reduce the weight, thereby reducing the work load on the user and the work load and economic burden during transportation. .. Further, when the curable composition is used on a vertical surface or an inclined surface, it has an effect of preventing the curable composition from sagging or slipping off during curing. In the present invention, the average particle size of the hollow body can be obtained as a cumulative particle size of 50% by laser diffraction / scattering type particle size distribution measurement. A hollow body having an average particle size of less than 40 μm is preferably 35 μm or less, and particularly preferably 10 to 35 μm, in terms of the balance between weight reduction and liquid dripping prevention of the curable composition.

Examples of the hollow body having an average particle size of less than 40 μm include an inorganic balloon and an organic balloon.

Examples of the inorganic balloon include a glass balloon, a shirasu balloon, a silica balloon, and a ceramic balloon.

Examples of the organic balloon include a resin balloon. Resin balloons include urea resin, phenol resin, polystyrene resin, vinylidene chloride resin, vinylidene chloride and acrylonitrile copolymer (resin), acrylonitrile and methacrylonitrile copolymer (resin), vinylidene chloride, acrylonitrile and divinylbenzene. Examples thereof include balloons made of various resins of the copolymer (resin) of the above.

As the inorganic balloon and the organic balloon, a balloon in which the surface of the particles is coated with an inorganic substance having an average particle size of 5 μm or less can also be used. A balloon coated with an inorganic substance having an average particle size of 5 μm or less facilitates dispersibility when preparing a curable composition, and can also suppress the scattering of the balloon. Examples of this inorganic substance include calcium carbonate, fatty acid surface-treated calcium carbonate, titanium oxide, silicon oxide, talc, and clay.

Both of these inorganic balloons and organic balloons can be used alone or in combination of two or more.

The true specific gravity of the hollow body having an average particle size of less than 40 μm is preferably 0.05 to 0.7 g / cm ² , and more preferably 0.05 to 0.5 g / cm ² .

The blending amount of the hollow body having an average particle size of less than 40 μm is preferably 0.1 to 5% by mass with respect to the entire curable composition.

A hollow body having an average particle size of less than 40 μm can be used in combination with a hollow body having an average particle size of 40 μm or more as long as the object of the present invention is not impaired. Examples of the hollow body having an average particle size of 40 μm or more include the above-mentioned inorganic balloons and organic balloons having an average particle size of 40 μm or more. Further, when a hollow body having an average particle size of 100 μm or more is used in combination, the curable composition is imparted with a matte property and a grainy feeling, and the designability can be improved.

The curable composition of the present invention may further 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 can be combined with a urethane prepolymer and surface-treated calcium carbonate having a heat loss of 50 to 150 mg / g to prevent contamination and prevent adhesion of a curing sheet to the curable composition. It imparts a sexual effect. This is because when the curable composition is cured by water such as moisture, the silane compound and / or the partially hydrolyzed condensate of the silane compound migrates (bleeds) to the surface of the curable composition from the middle of curing, resulting in moisture. It is considered that this is due to reducing the stickiness of the surface of the curable composition by forming a hydrophilic film on the surface of the curable composition by being hydrolyzed by water such as and condensing while dealcoholizing. 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 antifouling property is improved. Further, even if dust or dust adheres to the surface of the curable composition, the dust or dust can be removed relatively easily by spraying running water such as rain or 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 there are a plurality of Rs, they may be the same or different. R ¹ is 1 having 1 or more carbon atoms. Although it is a valent hydrocarbon group, at least one of (OR ¹ ) is an alkoxy group having 2 to 6 carbon atoms. When there are a plurality of (OR ¹ ), they may be the same or different. Is an integer from 1 to 4.)

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

The (OR ¹ ) is an alkoxy group, and when m is 1, (OR ¹ ) is an alkoxy group other than the 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 an alkoxy group having 2 or more carbon atoms such as an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a pentoxy group, a hexoxy group and a phenoxy group.

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

The partially hydrolyzed condensate of a silane compound is a multimer obtained by partially hydrolyzing the alkoxy group of the above-mentioned silane compound in the presence or absence of a solvent and condensing the silane compound linearly or three-dimensionally. .. The partially hydrolyzed condensate of the silane compound is preferably a 2 to 20-mer from the viewpoint of transferability (bleeding) to the surface of the curable composition and film formation property after transfer to the surface of the curable composition.

Specific examples of the partially hydrolyzed condensate of the silane compound include ethyl silicate 40 (average pentamer), ethyl silicate 48 (average tetramer), and Corcote Co., Ltd., which contain a partially hydrolyzed condensate of tetraethoxysilane. EMS-485 (average 10-mer) containing a partially hydrolyzed condensate of diethoxydimethoxysilane, manufactured by Corcote; MKC containing a condensate of a partially hydrolyzed condensate of tetramethoxysilane partially butoxydated with butanol. Examples thereof include silicate MS58B15, MS58B30, MS51, MS56, M57, MS56S, manufactured by Mitsubishi Chemical Corporation; All of 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 to be used is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the isocyanate group-containing urethane prepolymer. .. If the amount used is less than 0.01 parts by mass, the effect of preventing contamination of the surface of the curable composition and the effect of preventing adhesion of the curing sheet are small. When the amount used exceeds 20 parts by mass, the amount of alcohol generated by hydrolyzing the silane compound and / or the partial hydrolysis condensate 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 can further contain an oxazolidine compound. The oxazolidine compound is a compound having one or more, preferably 1 to 6 oxazolidine rings, which are heterocycles of saturated 5-membered rings containing an oxygen atom and a nitrogen atom. The oxazolidine compound reacts with water such as moisture and is hydrolyzed, and the oxazolidine ring produces (regenerates) a secondary amino group and an alcoholic hydroxyl group, thereby functioning as a latent curing agent for the isocyanate group-containing urethane prepolymer. 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. At this time, carbon dioxide gas is also generated, and bubbles due to the carbon dioxide gas are generated in the cured product to deteriorate the appearance and cure. Problems such as breakage of objects and deterioration of adhesiveness may occur. On the other hand, when a curable composition using an isocyanate group-containing urethane prepolymer and an oxazolidine compound in combination is reacted with water, the water reacts preferentially with the oxazolidine compound, and the oxazolidine ring of the oxazolidine compound becomes a secondary amino group. Generates an alcoholic hydroxyl group (active hydrogen group). Next, since the generated active hydrogen group (particularly the secondary amino group) reacts preferentially with the isocyanate group, the generation of carbon dioxide gas due to the reaction between water and the isocyanate group is suppressed, and the curable composition is foamed during curing. Can be prevented.

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

Further, the oxazolidine compound is blended with a curable composition containing an isocyanate group-containing urethane prepolymer and a silane compound and / or a partially hydrolyzed condensate of the silane compound to generate cracks on the surface of the curable composition. Has the effect of preventing. Cracks on the surface of the curable composition cause the silane compound and / or the partially hydrolyzed condensate of the silane compound to bleed onto the surface of the curable composition and hydrolyze as the curable composition cures. Since the formed cured film is hard, if the cured film is displaced, it is presumed that the displacement cannot be followed and cracks occur. When the oxazolidine compound is blended, the cured film of the silane compound and / or the partially hydrolyzed condensate of the silane compound is made flexible by the action of the secondary amino group generated by hydrolysis of the oxazolidin compound and the alcoholic hydroxyl group. It is presumed that this will prevent the occurrence of cracks.

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 the hydroxyl group of a compound having a hydroxyl group and an oxazolidin ring with the isocyanate group of an organic polyisocyanate or the carboxyl group of an organic carboxylic acid compound. Of these oxazolidine compounds, urethane bond-containing oxazolidine compounds are preferable because they are easy to produce.

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 the hydroxyl group and the oxazolidine ring, 1 mol or more, preferably 1 to 1.5 mol, more preferably 1 mol, more preferably 1 to 1.5 mol of the carbonyl group of the aldehyde compound or the ketone compound is made with respect to 1 mol of the secondary amino group of the alkanolamine. Is used, and a method of performing a dehydration condensation reaction while heating and refluxing in a solvent such as toluene or xylene to remove by-produced water can be mentioned. Excess 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-butyl aldehyde, isobutyl aldehyde, barrel aldehyde, isobarrel aldehyde, 2-methylbutyl aldehyde, n-hexyl aldehyde, 2-methylpentyl aldehyde, n-octyl aldehyde, 3,5. , 5-Trimethylhexylaldehyde and other aliphatic aldehyde compounds; examples thereof include aromatic aldehyde compounds such as benzaldehyde, methylbenzaldehyde, trimethylbenzaldehyde, ethylbenzaldehyde, isopropylbenzaldehyde, isobutylbenzaldehyde, methoxybenzaldehyde, dimethoxybenzaldehyde and trimethoxybenzaldehyde. All of these can be used alone or in combination of two or more.

Of these, diethanolamine is preferable as the alkanolamine, and the ketone compound or the aldehyde compound is preferable because it is easy to produce a compound having a hydroxyl group and an oxazolidine ring and is excellent in foaming prevention property when the curable composition is cured. Of these, aldehyde compounds are preferable, and isobutyl aldehyde, 2-methylpentyl aldehyde, and benz aldehyde are more preferable.

Compounds having a hydroxyl group and an oxazolidine ring include 2-isopropyl-3- (2-hydroxyethyl) oxazolidine, 2- (1-methylbutyl) -3- (2-hydroxyethyl) oxazolidine, and 2-phenyl-3- (2). -Hydroxyethyl) Oxazolidine can be mentioned.

As the urethane bond-containing oxazolidine compound, the isocyanate group of the organic polyisocyanate compound and the hydroxyl group of the compound having a hydroxyl group and the oxazolidine ring have an isocyanate group / hydroxyl group molar ratio of 0.9 / 1 to 1.2 / 1, preferably 0. Preferable examples thereof are those obtained by reacting at a temperature of 50 to 120 ° C. in the presence or absence of an organic solvent, which is used so as to be .95 / 1 to 1.05 / 1.

Examples of the organic polyisocyanate used for producing the urethane bond-containing oxazolidine compound include the same organic polyisocyanates used for producing the urethane prepolymer described above. Of these, aromatic aliphatic 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 oxazolidin ring with a lower alkyl ester of a dicarboxylic acid or a polycarboxylic acid.

The oxazolidinesilyl ether compound includes the above-mentioned compounds having a hydroxyl group and an oxazolidin ring, trimethoxysilane, tetramethoxysilane, triethoxysilane, dimethoxydimethylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, and 3-glycidoxypropyltri. It is obtained by a dealcohol reaction with an alkoxysilane such as methoxysilane and 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.

Each of these oxazolidine compounds can 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 the 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 above-mentioned urethane bond-containing oxazolidine compound, 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. In this case, in order to achieve the object of the present invention. It can be considered that it does not have. 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 blending amount is 0.1 to 1 mol of the active hydrogen of the secondary amino group produced (regenerated) by hydrolysis of the oxazolidine compound with respect to 1 mol of the isocyanate group of the urethane prepolymer. It is preferably 0.3 to 1 mol, more preferably 0.5 to 1 mol, and particularly preferably 0.5 to 1 mol. If the amount of active hydrogen of the secondary amino group produced (regenerated) by hydrolysis of the oxazolidine compound is less than 0.1 mol, the prevention of foaming is insufficient, which is not preferable.

The curable composition of the present invention may contain various additives in addition to the above-mentioned components, if necessary, as long as the object of the present invention is not impaired. Additives are added to the curable composition and used to improve various performances such as viscosity adjustment, curing acceleration, and adhesiveness of the curable composition. Specific examples thereof include a curing accelerating catalyst, a plasticizer, a weather resistance stabilizer, a filler, a rocking denaturing agent, an adhesiveness improving agent, a storage stability improving agent (dehydrating agent), a colorant and an organic solvent. All of these can be used alone or in combination of two or more.

The curing acceleration catalyst is used to promote cross-linking and curing of the isocyanate group-containing urethane prepolymer by reacting with water such as moisture. When the oxazolidine compound is blended in the curable composition, it is used to promote 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 acceleration catalyst can also be used as a reaction catalyst in the production of the above-mentioned urethane prepolymer. 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 acceleration catalyst include metal-based catalysts and amine-based catalysts.

Examples of the metal-based catalyst include a salt of a metal and an organic acid, a salt of an organic metal and an organic acid, and a metal chelate compound. Examples of the salt of the metal and the organic acid include salts of various metals such as tin, bismuth, zirconium, zinc and manganese with organic acids such as octyl acid, neodecanoic acid, stearic acid and naphthenic acid. Specific examples thereof include tin octylate, tin naphthenate, bismuth octylate, and zirconium octylate. Salts of organic metals and organic acids include dibutyltin dioctate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimaleate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin diversatete, and reaction of dibutyltin diverseate with phthalates. Things can be mentioned. Examples of the metal chelate compound include dibutyltin bis (acetylacetonet), EXCESTAR C-501 manufactured by Asahi Glass Co., Ltd., zirconium tetrakis (acetylacetonate), titanium tetrakis (acetylacetonate), and aluminum tris (acetylacetone). Nart), Aluminum Tris (Ethylacet Acetate), Acetylacetone Cobalt, Acetylacetone Iron, Acetylacetone Copper, Acetylacetone Magnesium, Acetylacetone Bismus, Acetylacetone Nickel, Acetylacetone Zinc, Acetylacetone Manganese.

Examples of the amine-based catalyst include tertiary amines. Examples of 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.

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

Of 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, and a salt of tin and an organic acid, and bismuth are preferable because the curable composition is excellent in curability. Salts with organic acids, salts with organic tin and organic acids, salts with organic bismuth and organic acids, tin chelate compounds, and bismuth chelate compounds are preferred.

The amount of the curing acceleration catalyst used is preferably 0.005 to 5 parts by mass, particularly 0.005 to 2 parts by mass with respect to 100 parts by mass of the isocyanate group-containing urethane prepolymer.

In addition to the above-mentioned metal catalysts and amine catalysts, organic carboxylic acid catalysts, phosphoric acid ester catalysts, p-toluenesulfonyl monoisocyanates, and reactants of p-toluenesulfonyl monoisocyanate and water can be used. The organic carboxylic acid catalyst, the phosphoric acid ester catalyst, the p-toluenesulfonyl monoisocyanate, and the reaction product of the p-toluenesulfonyl monoisocyanate and water are the oxazolidine rings of the oxazolidine compound when the oxazolidine compound is blended in the curable composition. It promotes the hydrolysis of ester. By promoting the hydrolysis of the oxazolidine ring, the generated secondary amino group and alcoholic hydroxyl group (active hydrogen group) react with the isocyanate group of the urethane prepolymer, and the curing of the curable composition is promoted.

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

Examples of the phosphoric acid ester-based catalyst include a normal phosphoric acid ester compound and a phosphite ester compound. Examples of the orthophosphoric acid ester compound include acidic phosphoric acid ester compounds such as ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate and oleyl acid phosphate, and examples of the hypophosphite compound include triethyl phosphate and the like. Sub-acid triester compounds such as triphenylphosphite, tris (nonylphenyl) phosphite, tridecylphosphite, diphenylmono (2-ethylhexyl) phosphite, diphenylmonodecylphosphite, dilaurylhydrogenphosphite, diorail Examples thereof include phosphite diester compounds such as hydrogen phosphite and diphenylhydrogen phosphite.

The reaction product of p-toluenesulfonyl monoisocyanate and water may be obtained by reacting p-toluenesulfonyl monoisocyanate with water in advance before blending into the curable composition of the present invention. Water may be added and reacted while p-toluenesulfonyl monoisocyanate is blended in the curable composition, or water 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 characteristics of the rubber after curing of the curable composition. Specifically, phthalates such as dioctyl phthalate, diisononyl phthalate, dibutyl phthalate, and butyl benzyl phthalate; aliphatic carboxylic acid esters such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate, and butyl oleate. Low molecular weight plasticizers such as the above; polyoxyalkylene-based triols, polyoxyalkylene-based diols, and polyoxyalkylene-based monools similar to those that can be used for the synthesis of the above-mentioned isocyanate group-containing urethane prepolymers are converted into esters and ethers. Alternatively, esterified plasticizers with a high molecular weight of 1,000 or more; plasticizers with a high molecular weight of 1,000 or more that do not react with isocyanate groups such as polystyrenes such as poly-α-methylstyrene and polystyrene. Agents are mentioned. All of 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, more preferably 2 to 50 parts by mass, based on 100 parts by mass of the isocyanate group-containing urethane prepolymer.

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

Examples of hindered amine-based photostabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bisdecanediate (2,2,6,6-tetramethyl-1 (octyloxy) -4. -Piperidyl) ester, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, 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 Low molecular weight compounds with a molecular weight of less than 1,000, such as 6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine; dimethyl 1- (2-hydroxyethyl) succinate-4- (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 Adecastab LA-63P and LA-68LD manufactured by ADEKA, can be mentioned.

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

Examples of the UV absorber include benzotriazole-based UV absorbers such as 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole; 2- (4,6-diphenyl-1, 3,5-Triazine-2-yl) -5-[(hexyl) oxy] -triazine-based UV absorbers such as phenol; benzophenone-based UV absorbers such as octabenzone; 2,4-di-tert-butylphenyl-3 , 5-Di-tert-butyl-4-hydroxybenzoate and the like are benzoate-based UV absorbers.

Of these, hindered amine-based photostabilizers, hindered phenol-based antioxidants, and mixtures thereof are preferable because they are highly effective in 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 isocyanate group-containing urethane prepolymer.

The filler is used as a bulking agent for the curable composition and for the purpose of reinforcing the physical properties of the cured product. Examples include inorganic fillers and organic fillers. Inorganic fillers include heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, mica, kaolin, zeolite, graphite, diatomaceous clay, white clay, clay, talc, anhydrous silicic acid, quartz, aluminum powder, zinc powder, hydroxylated. Inorganic powder-like fillers such as calcium, magnesium carbonate, and alumina; examples thereof include inorganic fibrous fillers such as glass fibers and carbon fibers. Examples of the organic filler include organic powder fillers such as wood flour, walnut flour, rice husk flour, pulp powder, rubber powder, and thermoplastic or thermosetting resin powder. Further, flame-retardant fillers such as magnesium hydroxide and aluminum hydroxide can be mentioned. All of 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 isocyanate group-containing urethane prepolymer.

The shaking modification imparting agent imparts shaking modification to the curable composition in the same manner as the above-mentioned surface-treated calcium carbonate, and has the purpose of preventing the generation of sagging and slump when the curable composition is used on a vertical surface or an inclined surface. Or, it is used for the purpose of maintaining the coating shape when the curable composition is applied by bead application, comb-mesh iron, or the like. Examples of the shaking denaturing agent include an inorganic shaking denaturing agent and an organic shaking denaturing agent. Examples of the inorganic rock denaturing agent include fine powder silica such as hydrophilic and hydrophobic colloidal silica in addition to the above-mentioned surface-treated calcium carbonate. Examples of the organic shaking denaturing agent include fatty acid amide. All of these can be used alone or in combination of two or more.

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, and zircoaluminate-based, or partial hydrolysis condensates thereof. Of these, a silane-based coupling agent or a partially hydrolyzed condensate thereof is preferable because it has excellent adhesiveness.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, and 3-mercaptopropyltrimethoxysilane. 3-Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) Examples thereof include compounds having an alkoxysilyl group of -3-aminopropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and the like and having a molecular weight of 500 or less. Further, a compound having a molecular weight of 200 to 3,000, which is a partially hydrolyzed condensate of one or more of these silane-based coupling agents, can be mentioned. All of 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 thereof include vinyltrimethoxysilane, calcium oxide, and p-toluenesulfonyl isocyanate (PTSI), which react with water present in the curable composition and act as a dehydrating agent. All of 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 to the cured product. Specific examples thereof include inorganic pigments such as titanium oxide and iron oxide, organic pigments such as copper phthalocyanine, and carbon black. All of 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 such as casting and coating. The organic solvent can be used without particular limitation as long as it has good compatibility with other components in the curable composition and does not react with other components. Specifically, a carbonate solvent such as dimethyl carbonate, a ketone solvent such as acetone or methyl ethyl ketone, an ester solvent such as ethyl acetate or butyl acetate, an aliphatic solvent such as n-hexane, and an alicyclic solvent such as cyclohexane. Examples thereof include solvents, aromatic solvents such as toluene and xylene, and organic solvents such as petroleum distillate solvents such as mineral spirit and industrial gasoline. All of these can be used alone or in combination of two or more. These organic solvents may be used in the synthesis of urethane prepolymers or in the preparation of curable compositions.

Since the curable composition of the present invention is cured by reacting with water such as moisture in the air, it can be used as a one-component moisture-curable composition. It can also be used as a two-component reaction curable composition using the curable composition of the present invention as a main component and an active hydrogen-containing compound such as a polyamine or a polyol as a curing agent. It is preferable to use it as a one-component moisture-curable composition because it does not require the trouble of mixing the main agent and the curing agent, does not cause curing defects due to mixing mistakes or insufficient mixing, and has excellent workability.

When the curable composition of the present invention is used, the materials (members) to be constructed include mortar, concrete, ALC (Autoclaved Lightweight Concrete), glass, marble, mikage stone, siding, tile, roof tile, and brick. Inorganic materials such as iron, copper, stainless steel, galvanium steel plate, totan, aluminum, titanium and other metal materials, 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 can be mentioned.

The method for producing the curable composition of the present invention is not particularly limited, but specifically, an isocyanate group-containing urethane prepolymer, a surface-treated calcium carbonate having a heat loss of 50 to 150 mg / g, and an average particle size of less than 40 μm. Hollow body, and if necessary, a silane compound and / or a partially hydrolyzed condensate of the silane compound, an oxazolidine compound, and an additive made of glass, stainless steel, iron, etc. It can be manufactured by stirring and mixing in a batch or continuous manner under dry air or a dry nitrogen stream.

Since the curable composition of the present invention is thickened and cured by water such as moisture, it is preferable to pack it in a container capable of blocking water such as moisture and store it in a sealed manner. The container is not particularly limited as long as it can block water such as humidity. Specific examples thereof include metal and resin pail cans, aluminum and resin bags, and paper and resin cartridges.

Examples of the present invention are 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)
717.5 g of polyoxypropylene diol (number average molecular weight 3,300, Excelol 3021, manufactured by Asahi Glass Co., Ltd.), polyoxy, while flowing nitrogen gas through a stirrer, thermometer, nitrogen seal tube, and reaction vessel with heating / cooling device. 160.0 g of propylene triol (number average molecular weight 4,000, Triol-MN-4000, manufactured by Mitsui Chemicals, Inc.) was charged, and 122.5 g of isophorone diisocyanate (molecular weight 222.3, manufactured by Ebonic Japan) was added while stirring, and dibutyltin. 0.2 g of dilaurate (Neostan U-100, manufactured by Nitto Kasei Co., Ltd.) was charged, 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-1 was synthesized. The obtained isocyanate group-containing urethane prepolymer PU-1 was a transparent viscous liquid at room temperature with an isocyanate group content of 2.1% by mass measured by titration. The branch density (theoretical value) of the urethane prepolymer PU-1 is 0.04 mmol / g.

[Synthesis Example 2] (Synthesis of Isocyanate Group-Containing Urethane Prepolymer PU-2)
620.4 g of polyoxypropylene diol (number average molecular weight 3,300, Excelol 3021, manufactured by Asahi Glass Co., Ltd.), polyoxy, while flowing nitrogen gas through a stirrer, thermometer, nitrogen seal tube, and reaction vessel with heating / cooling device. 160.0 g of propylene triol (number average molecular weight 4,000, Triol-MN-4000, manufactured by Mitsui Chemicals, Inc.), 100.0 g of polyoxypropylene monool (number average molecular weight 3,080, Preminol 1003, manufactured by Asahi Glass Co., Ltd.) Add 119.6 g of isophorone diisocyanate (molecular weight 222.3, manufactured by Ebonic Japan) and 0.2 g of dibutyltin dilaurate (Nitto Kasei Co., Ltd., Neostan U-100) while charging and stirring, and heat to 75 to 85 ° C. Was 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-2 was synthesized. The obtained isocyanate group-containing urethane prepolymer PU-2 was a transparent viscous liquid at room temperature with an isocyanate group content of 2.1% by mass measured by titration. The branch density (theoretical value) of the urethane prepolymer PU-2 is 0.04 mmol / g.

[Synthesis Example 3] (Synthesis of Isocyanate Group-Containing Urethane Prepolymer PU-3)
581.8 g of polyoxypropylene diol (number average molecular weight 3,300, Excelol 3021, manufactured by Asahi Glass Co., Ltd.) while flowing nitrogen gas through a stirrer, thermometer, nitrogen seal tube, and reaction vessel with heating / cooling device, polyoxy 160.0 g of propylene triol (number average molecular weight 4,000, Triol-MN-4000, manufactured by Mitsui Chemicals, Inc.), 100.0 g of polyoxypropylene monool (number average molecular weight 3080, Preminol 1003, manufactured by Asahi Glass Co., Ltd.), penta Add 30.0 g of erythritol triacrylate (molecular weight 298) and add isophoron diisocyanate (molecular weight 222.3, manufactured by Ebonic Japan) 128.2 g and dibutyltin dilaurate (Neostan U-100, manufactured by Nitto Kasei) while stirring. 2 g was charged, 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 obtained isocyanate group-containing urethane prepolymer PU-3 was a transparent viscous liquid at room temperature with an isocyanate group content of 2.1% by mass measured by titration. The branch density (theoretical value) of the urethane prepolymer PU-3 is 0.04 mmol / g, and the content of the acryloyl group (theoretical value) is 0.3 mmol / g.

[Synthesis Example 4] (Synthesis of Urethane Bond-Containing Oxazolidine Compound O-1)
In a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube, ester tube, and heating / cooling device, 435.0 g of diethanolamine (molecular weight 105) and 183.0 g of toluene were charged, and isobutyraldehyde (molecular weight 72.1) was added while stirring. 328.0 g was charged, heated while flowing nitrogen gas, and the reflux dehydration reaction was continued at 110 to 150 ° C., and by-produced water (74.5 g) 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 unreacted isobutyraldehyde with toluene to obtain N-hydroxyethyl-2-isopropyloxazolidine, which is an intermediate reaction product.

Next, 348.0 g of hexamethylene diisocyanate (molecular weight 168) was further 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. The reaction end point was set at 0% by 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 a 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 heater, a cooling device, and a nitrogen seal tube while nitrogen gas was flowed, and dried at 100 to 110 ° C. in advance while stirring. 20 g of heavy calcium carbonate (Whiten B, manufactured by Shiraishi Calcium Co., Ltd.) dried in the machine to reduce the water content to 0.05% by mass or less, fatty acid surface-treated calcium carbonate A (Calfine N-40, heat loss) 100 g of 95.0 mg / g (manufactured by Maruo Calcium), 10 g of titanium oxide, and 10 g of diisononyl phthalate (DINP) were charged and mixed until the contents became uniform. Next, 1 g of a hindered amine-based light stabilizer (ADECASTAB LA-63P, manufactured by ADEKA) was added to 5 g of dimethyl carbonate, and a hindered phenol-based antioxidant {pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-). 4-Hydroxyphenyl) propionate]} (Irganox 1010, manufactured by BASF), 2 g of a partially hydrolyzed condensate of a silane compound (polybutoxymethoxysiloxane, MKC silicate MS58B30, manufactured by Mitsubishi Chemical Corporation), synthesized. 12 g of urethane bond-containing oxazolidine compound O-1 obtained in Example 4, 0.03 g of dibutyltin dilaurate (Neostan U-100, manufactured by Nitto Kasei Co., Ltd.), hollow body A (EMC-20B, average particle size 27 μm) of less than 40 μm. 2.6 g of the resin balloon (manufactured by Sankyo Seiko Co., Ltd.) was charged and further mixed until the contents became uniform. Then, the foam was defoamed under reduced pressure at 50 to 100 hPa, filled in a container, and sealed to prepare a curable composition.

[Example 2] to [Example 15] and [Comparative Example 1] to [Comparative Example 9]
Each component was blended in the compositions shown in Tables 1 and 2, and the same operations as in Example 1 were carried out to prepare curable compositions of Examples 2 to 15 and Comparative Examples 1 to 9. The components shown in Tables 1 and 2 are as follows, and the unit is g.
-Isocyanate group-containing urethane prepolymer PU-1 (Synthesis Example 1)
-Isocyanate group-containing urethane prepolymer PU-2 (Synthesis Example 2)
-Isocyanate group-containing urethane prepolymer PU-3 (Synthesis Example 3)
・ Heavy calcium carbonate (Whiten B, manufactured by Shiraishi Calcium)
・ Fatty acid surface treatment Calcium carbonate A (Calfine N-40, heat loss 95.0 mg / g, manufactured by Maruo Calcium Co., Ltd.)
・ Fatty acid surface treatment Calcium carbonate B (Shiraishi CCR-S, heat loss 34.4 mg / g, manufactured by Shiraishi Kogyo Co., Ltd.)
-Hindered phenolic antioxidant {pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]} (Irganox 1010, manufactured by BASF)
・ Hindered amine-based light stabilizer (ADEKA STAB LA-63P, manufactured by ADEKA)
-Partial hydrolysis condensate of silane compound (polybutoxymethoxysiloxane, MKC silicate MS58B30, manufactured by Mitsubishi Chemical Corporation)
-Urethane bond-containing oxazolidine compound O-1 (Synthesis Example 4)
・ Acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
・ Dibutyl phthalate dilaurate (Neostan U-100, manufactured by Nitto Kasei Co., Ltd.)
Hollow body A of less than 40 μm (EMC-20B, resin balloon with average particle size of 27 μm, manufactured by Sankyo Seiko Co., Ltd.)
Hollow body B of less than 40 μm (Glass Bubbles S22, glass balloon with average particle size of 35 μm, manufactured by 3M Japan Ltd.)
-45 μm hollow body (EMC-40AS, resin balloon with average particle size 45 μm, manufactured by Sankyo Seiko Co., Ltd.)
100 μm hollow body (Dieform V105, resin balloon with average particle size 100 μm, manufactured by Dainichiseika Kogyo Co., Ltd.)

<Evaluation A of curable composition>
The curable compositions of Examples 1-9 and Comparative Examples 1-9 were used for the following evaluations. The evaluation results are shown in Table 1.

[Drop Clothes Adhesion Prevention]
a) Anti-adhesion of the curing sheet (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 using a 10 mm square backer. The joint was filled with a curable composition, and the excess was scraped off with a spatula to flatten the surface to prepare a test piece.

The test piece was immediately cured in an environment (indoor) at 5 ° C. and 40% RH for 3 or 5 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 longitudinal direction of the joint. One day after the application, the curing sheet was peeled off, and the peeling condition was visually confirmed. When the surface of the curable composition was touched at this time, the surface was cured, but the inside was not cured.

b) Anti-adhesion of the curing sheet (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 using a 10 mm square backer. The joint was filled with a curable composition, and the excess was scraped off with a spatula to flatten the surface to prepare a test piece.

The specimen was immediately cured in an environment (indoor) at 23 ° C. and 50% RH for 1 or 2 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 longitudinal direction of the joint. One day after the application, the curing sheet was peeled off, and the peeling condition was visually confirmed. When the surface of the curable composition was touched at this time, the surface was cured, but the inside was not cured.
The adhesion prevention property of the curing sheet was evaluated as follows.
evaluation:
⊚: The curing sheet does not adhere to the surface of the curable composition and peels off cleanly.
◯: The curing sheet slightly adheres to the surface of the curable composition, but peels off cleanly.
Δ: The curing sheet partially adheres to the surface of the curable composition, and when it 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 it is pulled strongly. When the curing sheet is peeled off, most of the surface layer of the curable composition is pulled and there is a design defect.

[Pollution prevention]
a) Black silica sand contamination A joint having a width of 20 mm, a depth of 20 mm and a length of 100 mm was prepared on a slate plate using a 10 mm square backer. The joint was filled with a curable composition, and the excess was scraped off with a spatula to flatten the surface to prepare a test piece.

The test piece was immediately cured in an environment (indoor) at 23 ° C. and 50% RH for 10 days. Black silica sand (8 Black, manufactured by KMEW Buecera) was sprinkled on the surface of the curable composition after curing, the test piece was immediately turned over, and the bottom of the slate plate was tapped by hand to remove excess black silica sand. The state of the black silica sand (dirt) remaining on the surface of the curable composition was visually observed, and the antifouling property during curing was evaluated as follows.
evaluation:
◯: A clean state with almost no adhesion of black silica sand on the surface of the curable composition.
X: A state in which a large amount of black silica sand adheres to the surface of the curable composition and becomes black and dirty.

b) Outdoor exposure contamination By stacking a 10 mm square backer on a slate plate, joints having a width of 20 mm, a depth of 20 mm, and a length of 100 mm were prepared. The joint was filled with a curable composition, and the excess was scraped off with a spatula to flatten the surface to prepare a test piece.

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

[Prevention of liquid dripping]
The paper tube cartridge was filled with 320 ml of the curable composition and the bottom was sealed with a plunger. A plastic nozzle having a discharge inner diameter of 8 mmΦ at the tip was attached to a paper tube cartridge, and about 50 ml of the curable composition was discharged with a dedicated cartridge gun, and then left as it was on a horizontal table. The state in which the curable composition drips from the tip of the nozzle due to the residual pressure in the paper tube cartridge was visually observed for 10 minutes, and the liquid dripping prevention property of the curable composition was evaluated as follows.
evaluation:
⊚: The curable composition does not drip from the tip of the nozzle.
◯: The curable composition drips a little from the tip of the nozzle, but the following work can be performed without wiping the curable composition at the tip of the nozzle.
X: The curable composition drips greatly from the tip of the nozzle, and the curable composition at the tip of the nozzle stains the table. The following operations cannot be performed unless the curable composition is wiped off.

<Evaluation B of curable composition>
Using the curable compositions of Examples 10 to 15, the following evaluations were performed in addition to the evaluation A of the curable compositions described above. The evaluation results are shown in Table 2.

[Drop Clothes Adhesion Prevention]
a) Anti-adhesion of the curing sheet (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 using a 10 mm square backer. The joint was filled with a curable composition, and the excess was scraped off with a spatula to flatten the surface to prepare a test piece.

The test piece was immediately cured in an environment (indoor) at 5 ° C. and 40% 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 longitudinal direction of the joint. One day after the application, the curing sheet was peeled off, and the peeling condition was visually confirmed. When the surface of the curable composition was touched at this time, the surface was cured, but the inside was not cured.

From the results of Examples 1 to 15, the curable composition of the present invention has excellent antifouling property in outdoor exposure, and the curing sheet does not adhere to the surface of the curable composition and is peeled off cleanly. Also turns out to be excellent. Further, since the curable composition has good liquid dripping prevention property after being extruded from the cartridge and does not require wiping work, the operator can use the curable composition intermittently. Furthermore, from the results of Examples 10 to 15, the curable composition of the present invention has a property of preventing adhesion of a curing sheet even after 1 day at 5 ° C. and 40% RH, that is, even at an early stage of curing of the composition at a low temperature. It turns out that it is excellent.

On the other hand, the curable compositions of Comparative Examples 1 to 9 have poor adhesion prevention property to the curing sheet and cannot be peeled off cleanly unless surface-treated calcium carbonate having a heat loss of 50 to 150 mg / g is used. In addition, if a hollow body of 40 μm or more is used, the liquid dripping prevention property after extruding the curable composition from the cartridge is poor, wiping work is required, and the workability when the curable composition is used intermittently is poor. Become.

As described above, since the curable composition of the present invention is excellent in stain prevention property, curing sheet adhesion prevention property and liquid dripping prevention property in outdoor exposure, it is therefore a sealing material composition, a waterproof material composition, an adhesive composition and a coating. It can be suitably used as a material composition. Further, the curable composition of the present invention can be suitably used for construction and civil engineering.

Claims (7)

An isocyanate group-containing urethane prepolymer, a fatty acid surface-treated calcium carbonate having a heat loss of 50 to 150 mg / g , a silane compound represented by the following general formula (1) and / or a partially hydrolyzed condensate of a silane compound, and an average particle size. Contains a hollow body of less than 40 μm ,
The blending amount of the fatty acid surface-treated calcium carbonate is 1 to 200 parts by mass with respect to 100 parts by mass of the isocyanate group-containing urethane prepolymer, and the blending amount of the hollow body is 0.1 to 5 mass by mass with respect to the entire curable composition. %, A curable composition.
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 there are a plurality of Rs, they may be the same or different. R ¹ is 1 having 1 or more carbon atoms. Although it is a valent hydrocarbon group, at least one of (OR ¹ ) is an alkoxy group having 2 to 6 carbon atoms. When there are a plurality of (OR ¹ ), they may be the same or different. Is an integer from 1 to 4.) The curable composition according to claim 1, wherein the isocyanate group-containing urethane prepolymer has a branching density of 0.03 mmol / g or more. The curable composition according to claim 1 or 2, wherein the isocyanate group-containing urethane prepolymer has a photoreactive unsaturated bond in the molecule. The curable composition according to any one of claims 1 to 3 , further comprising an oxazolidine compound. Further, at least one selected from a curing accelerating catalyst, a plasticizer, a weather-resistant stabilizer, a filler, a rocking denaturing agent, an adhesiveness improving agent, a storage stability improving agent (dehydrating agent), a colorant and an organic solvent. The curable composition according to any one of claims 1 to 4 , which comprises an additive. The curable composition according to any one of claims 1 to 5 , wherein the curable composition is a curable composition for construction or civil engineering. The curable composition according to any one of claims 1 to 6 , wherein the curable composition is a sealing material composition, a waterproof material composition, an adhesive composition or a coating material composition. ..