JP2008201980A - Curable composition, sealing material and waterproof agent for coated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition excellent in pollution controlling effect and weatherability, and a sealing material and waterproof agent for a coated film. <P>SOLUTION: The curable composition comprises (A) an urethane prepolymer containing an isocyanate group, (B) an alkoxy silane compound of an alkoxy group excluding a methoxy group, represented by general formula (1): R<SB>4-n</SB>SiX<SB>n</SB>and/or a partial hydrolysis condensate thereof and (C) a curing accelerator catalyst. In the formula (1), R is a 1-6C monovalent hydrocarbon group, and multiple Rs may be the same or different; X is an alkoxy group and multiple Xs may be the same or different and at least one is an alkoxy group excluding a methoxy group; and n is an integer of 1-4. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a curable composition, a sealing material, and a waterproof coating material, which are cured by moisture in the atmosphere and become a rubber-like elastic body having an excellent anti-contamination effect.

Conventionally, polyurethane resin has been used as a moisture curable resin component for waterproofing sealants for buildings, civil engineering, automobiles, and other curable compositions such as adhesives and paints. Widely used because of its superiority.
However, polyurethane resin has the advantage that the tensile properties of rubber after curing can be adjusted relatively freely from low modulus to high modulus (high elongation to low elongation), but it is used for sealing materials and waterproofing coating films. Therefore, when designed in the low to medium modulus range, the curable composition containing polyurethane resin remains tacky (adhesive) on the surface after curing, making it easy for dust and dirt to adhere, and contaminating the surface blackish The problem of end up occurs. In particular, when a curable composition such as a sealant is applied outdoors, such as on outer wall joints or rooftops, the remaining tack is severe when it is not completely cured immediately after application. When this happens, contamination due to dust adhesion will occur violently.
As a technique for solving the contamination on the surface of the cured product, polyisocyanate-terminated prepolymer derived from an aliphatic or alicyclic diisocyanate monomer is blended with a photocurable substance or an unsaturated compound capable of reacting with oxygen. Isocyanate compositions have been proposed (see Patent Documents 1 and 2). However, this technology can obtain a certain level of anti-staining effect, but the anti-staining effect in the middle of curing is not recognized, and the prevention of contamination over a long period is still insufficient. And the curable composition which has the further antifouling performance over the long term after hardening is calculated | required.
Also, a one-component moisture-curable polyurethane composition in which a urethane prepolymer having a specific amount of isocyanate group is blended with a silicate ester represented by a specific structural formula or a condensate thereof, or an inorganic filler surface-treated with these. Has been proposed (see Patent Document 3). However, the purpose of this technology is excellent adhesion to concrete, mortar, etc., and no mention is made of prevention of contamination.
JP 2002-37832 A JP 2002-37846 A JP 2002-12645 A

  The present invention is a rubber-like elastic body which is cured by moisture in the atmosphere or the like and has excellent physical properties, and in particular, after curing, a relatively soft rubber-like elastic body having a low modulus to a medium modulus (high elongation to medium elongation). In this case, in addition to exhibiting an anti-contamination effect promptly even during the low temperature period of winter as well as at room temperature, even during curing after construction, and exhibiting an excellent anti-contamination effect over a long period after curing, It is an object of the present invention to provide a curable composition, a sealing material and a waterproof coating film having remarkably excellent weather resistance.

  As a result of intensive studies to achieve the above object, an alkoxysilane compound having an alkoxy group other than a methoxy group and / or a partial hydrolysis thereof in a curable composition comprising an isocyanate group-containing urethane prepolymer and a curing accelerating catalyst. By blending the condensate, the resulting curable composition exhibits an excellent anti-contamination effect both during curing and over a long period after curing, and when a curing accelerating catalyst is present in the curable composition. In general, the weather resistance after curing is lowered, but surprisingly, by adding an alkoxysilane compound having an alkoxy group other than the methoxy group and / or a partially hydrolyzed condensate thereof, the curing can be achieved. The present invention was completed by finding that the product has extremely excellent weather resistance. That is, this invention is shown by the following (1)-(17).

(1) Isocyanate group-containing urethane prepolymer (A), an alkoxysilane compound having an alkoxy group other than a methoxy group represented by the following general formula (1) and / or a partial hydrolysis-condensation product (B) thereof, and a curing accelerating catalyst A curable composition comprising (C).
R _4-n SiX _n (1)
[In the formula (1), R represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and when R is plural, they may be the same or different. X represents an alkoxy group, and when X is plural, they may be the same or different, but at least one is an alkoxy group other than a methoxy group. n is an integer of 1-4. ]
(2) The curable composition according to (1), further including a weather resistance stabilizer (D).
(3) The curable composition according to (1) or (2), wherein the alkoxy group other than the methoxy group is an ethoxy group.
(4) The curable composition according to (1) or (2), wherein the alkoxysilane compound having an alkoxy group other than the methoxy group is tetraethoxysilane.
(5) The curable composition according to (1) or (2), wherein the alkoxysilane compound having an alkoxy group other than the methoxy group is ethoxymethoxysilane.
(6) The curable composition according to any one of (1) to (5), wherein the isocyanate group of the isocyanate group-containing urethane prepolymer (A) is an isocyanate group derived from an aliphatic polyisocyanate compound.
(7) The curable composition according to any one of (1) to (6), wherein the curing accelerating catalyst (C) is a metal chelate compound.
(8) The curable composition according to any one of (1) to (7), further including an additive (E).
(9) An exposed joint sealant comprising the curable composition according to any one of (1) to (8).
(10) A siding sealant comprising the curable composition according to any one of (1) to (8).
(11) A sealing material for exterior wall joints comprising the curable composition according to any one of (1) to (8).
(12) A sealing material for sash surroundings, comprising the curable composition according to any one of (1) to (8).
(13) A sealant for stone joints, comprising the curable composition according to any one of (1) to (8).
(14) A sealing material for ceramics material joints, comprising the curable composition according to any one of (1) to (8).
(15) A sealing material for indoor joints, comprising the curable composition according to any one of (1) to (8).
(16) A synthetic resin sheet end treatment sealing material comprising the curable composition according to any one of (1) to (8).
(17) A polyurethane-based waterproofing membrane comprising the curable composition according to any one of (1) to (8).

  For the first time according to the present invention, it becomes a rubber-like elastic body excellent in various physical properties by being cured by moisture in the atmosphere and the like, and after curing, a relatively soft rubber-like elasticity having a low modulus to a medium modulus (high elongation to medium elongation). Even in the case of body, in addition to exhibiting an excellent anti-contaminating effect quickly at the low temperature of winter as well as in the middle of curing after construction, and in the long term after curing Thus, it has become possible to provide a curable composition, a sealing material and a waterproof coating film having remarkably excellent weather resistance.

The present invention will be described in detail below.
The isocyanate group-containing urethane prepolymer (A) in the present invention is one in which an isocyanate group reacts with moisture such as moisture to form a urea bond to be crosslinked and cured, and an active hydrogen compound and an organic isocyanate are combined with active hydrogen ( Group) and obtained under the condition of excess isocyanate group, and becomes a curing component in the curable composition of the present invention.
Specifically, the active hydrogen compound and the organic isocyanate have a total isocyanate group / active hydrogen (group) molar ratio of 1.3 to 10 / 1.0, more preferably 1.5 to 3.0 / 1. It can be preferably produced by reacting simultaneously or sequentially within a range of 0.0. When the molar ratio is less than 1.3 / 1.0, the number of crosslinking points of the urethane prepolymer (A) obtained is too small, the elongation and tensile strength after curing of the curable composition are lowered, and rubber elastic properties. If the molar ratio exceeds 10 / 1.0, the amount of carbon dioxide generated when reacting with moisture increases and causes foaming, which is not preferable.
Further, the isocyanate group content of the isocyanate group-containing urethane prepolymer (A) is preferably 0.3 to 15.0 mass%, particularly preferably 0.5 to 5.0 mass%. When the isocyanate group content is less than 0.3% by mass, there are few crosslinking points in the prepolymer, so that sufficient adhesiveness cannot be obtained. When the isocyanate group content exceeds 15.0% by mass, the number of crosslinking points in the prepolymer increases and the rubber elasticity deteriorates, and the amount of carbon dioxide generated by the reaction with moisture increases and the cured product foams. It is not preferable in terms.
As a production method, for example, a method in which an active hydrogen compound and an organic isocyanate are charged in a reaction vessel made of glass or stainless steel and reacted at 50 to 120 ° C. in the presence or absence of a reaction catalyst or an organic solvent described later. Is mentioned. At this time, when the isocyanate group reacts with moisture, the resulting urethane prepolymer (A) is thickened. Therefore, the reaction is preferably performed in a state where moisture is blocked, such as nitrogen gas replacement or under a nitrogen gas stream.
The isocyanate group-containing urethane prepolymer (A) is used as a one-component moisture-curing type by reaction curing with moisture (humidity) in the atmosphere at room temperature.

Examples of the active hydrogen compound include polymeric polyols, amino alcohols, polyamines, and the like.
Examples of the polymer polyol include polyoxyalkylene polyols, polyester polyols, polyester amide polyols, polyether / ester polyols, polycarbonate polyols, poly (meth) acrylic polyols, hydrocarbon polyols, and the like. The number average molecular weight is 500 or more. , Preferably 1,000 or more.
In the present invention, the number average molecular weight and the weight average molecular weight are numerical values in terms of polystyrene measured by gel permeation chromatography (GPC).
Examples of the polyoxyalkylene-based polyol include those obtained by ring-opening addition polymerization of alkylene oxide, and those obtained by ring-opening addition polymerization of alkylene oxide in an initiator such as a compound containing two or more active hydrogens.
Examples of the initiator include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, diglycerin and the like. Low molecular weight polyhydric alcohols, sorbitol, sucrose, glucose, lactose, low molecular weight polyhydric alcohols such as glucose, lactose, sorbitan, low molecular weight polyphenols such as bisphenol A and bisphenol F, low molecular weight such as ethylenediamine and butylenediamine Polyamines, low molecular amino alcohols such as monoethanolamine and diethanolamine, low molecular polycarboxylic acids such as adipic acid and terephthalic acid, and at least one of these is alkylene oxide Polyoxyalkylene polyol having a low molecular weight obtained by reacting the like.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, and a mixture thereof.
Specifically, polyoxyalkylene polyols are specifically polyoxyethylene polyol, polyoxypropylene polyol, polytetramethylene ether polyol, poly (oxyethylene) -poly (oxypropylene) -random or block copolymer polyol, poly (Oxypropylene) -poly (oxybutylene) -random or block copolymer polyols and the like, and these various polyols and organic polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. There may also be mentioned those having a hydroxyl group at the molecular end by reacting with an isocyanate group in excess of the hydroxyl group.
The polyoxyalkylene polyol preferably has a number average molecular weight of 500 to 100,000, more preferably 1,000 to 30,000, and particularly preferably 1,000 to 20,000 for reasons such as good workability. The average number of alcoholic hydroxyl groups per molecule is 2 or more, more preferably 2 to 4, and most preferably 2 to 3.
Further, the polyoxyalkylene-based polyol is obtained by using a catalyst such as a double metal cyanide complex, and has a total unsaturation of 0.1 meq / g or less, further 0.07 meq / g or less, particularly 0.04 meq / g. The following are preferable, and those having a molecular weight distribution (ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) = Mw / Mn) of 1.6 or less, particularly 1.0 to 1.3 are preferable.
In the present invention, the polyoxyalkylene-based polyol is composed of 50% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more of the portion excluding 1 mol of hydroxyl group in the molecule. Means that the remaining part may be modified with urethane, ester, polycarbonate, polyamide, polyacrylate, polyolefin, etc., but in the present invention, 95% by mass or more of the molecule excluding the hydroxyl group Most preferred are polyols consisting of oxyalkylenes.
Examples of polyester polyols and polyester amide polyols include, for example, known dicarboxylic acids such as succinic acid, adipic acid, and terephthalic acid, their acid esters, acid anhydrides, and the like, and initiators for the synthesis of the above polyoxyalkylene polyols. Examples thereof include compounds obtained by a dehydration condensation reaction with a compound containing two or more active hydrogens to be used. Further examples include lactone polyester polyols obtained by cleavage polymerization of cyclic ester (ie, lactone) monomers such as ε-caprolactone.
Examples of the polyether ester polyol include compounds produced from the polyoxyalkylene polyol and the dicarboxylic acid, acid anhydride and the like.
Examples of the polycarbonate polyol include a dehydrochlorination reaction between low molecular polyhydric alcohols used in the production of the polyoxyalkylene polyol and phosgene, or transesterification with diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and the like. The compound obtained from reaction etc. is mentioned.
Examples of the poly (meth) acrylic polyol include those obtained by copolymerizing a hydroxyethyl (meth) acrylate containing a hydroxyl group with another (meth) acrylic acid alkyl ester monomer.
Examples of the hydrocarbon polyol include polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, hydrogenated polyisoprene polyol, chlorinated polyethylene polyol, and chlorinated polypropylene polyol.
Examples of the polyol further include low molecular weight polyhydric alcohols having a number average molecular weight of less than 500, which are listed as raw materials for producing the polyoxyalkylene polyol.
Examples of amino alcohols include monoethanolamine, diethanolamine, N-methyldiethanolamine, N-methyldipropanolamine, and N-phenyldiethanolamine.
Examples of the polyamine include high-molecular polyamines such as polyoxyalkylene polyamines having a number average molecular weight of 500 or more and a polyoxyalkylene polyol terminal having an amino group, such as a terminal diaminated product of polypropylene glycol.
Examples of the polyamine further include low molecular weight polyamines having a number average molecular weight of less than 500, such as ethylenediamine, hexamethylenediamine, isophoronediamine, diaminodiphenylmethane, and diethylenetriamine.
Any of these may be used alone or in combination of two or more.
Among these, since the viscosity of the resulting isocyanate group-containing urethane prepolymer (A) is low and the physical properties after curing are good, the viscosity of the resulting curable composition is low and the workability is good, and after curing From the viewpoint of high rubber elastic properties and adhesiveness, polymer polyols are preferred, polyoxyalkylene polyols are more preferred, and polyoxypropylene polyols are particularly preferred. In addition, for the modification of the isocyanate group-containing urethane prepolymer (A), high molecular monoalcohols such as polyoxyalkylene monoalcohol, butyl alcohol, octadecyl monoalcohol, and low molecular monoalcohol can be used.

  Specific examples of the organic isocyanate include organic polyisocyanates and mixtures of organic polyisocyanates and organic monoisocyanates, with organic polyisocyanates being preferred.

  The organic monoisocyanate may contain one isocyanate group in the molecule, and the organic group other than the isocyanate group is preferably a hydrophobic organic group that does not contain moisture-curable functional groups such as moisture. Specifically, aliphatic monoisocyanates such as n-butyl monoisocyanate, n-hexyl monoisocyanate, n-tetradecyl monoisocyanate, n-hexadecyl monoisocyanate, octadecyl monoisocyanate, n-chloroethyl monoisocyanate, chlorophenyl monoisocyanate Isocyanate, 3,5-dichlorophenyl monoisocyanate, p-fluorophenyl monoisocyanate, 2,4-difluorophenyl monoisocyanate, o-trifluoromethylphenyl monoisocyanate, p-nitrophenyl monoisocyanate, p-isopropylphenyl monoisocyanate, 2 , 6-diisopropyl monoisocyanate, aromatic monoisocyanates such as p-benzyloxyphenyl monoisocyanate, etc. - such as methacryloyloxyethyl isocyanate. These can be used alone or in admixture of two or more.

An organic polyisocyanate is a compound containing two or more isocyanate groups in the molecule. Specifically, for example, an aromatic polyisocyanate having an isocyanate group bonded to an aromatic carbon, and an isocyanate group having an aliphatic carbon. Aliphatic polyisocyanates bonded to the above, and aromatic polyisocyanates include toluene diisocyanates such as 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2 , 4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, etc., diphenylmethane diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, etc. Enylene diisocyanates, 2,4,6-trimethylphenyl-1,3-diisocyanate, 2,4,6-triisopropylphenyl-1,3-diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, etc. Naphthalene diisocyanates, chlorophenylene-2,4-diisocyanate, 4,4'-diphenyl ether diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'- And diisocyanate. Examples of the aliphatic polyisocyanate include 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,4,4-trimethyl-1, 6-hexamethylene diisocyanate, decamethylene diisocyanate, lysine diisocyanate and other aliphatic polyisocyanates, o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate and other aromatic aliphatic polyisocyanates, 1,4-cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate Like alicyclic polyisocyanates such. Furthermore, organic polyisocyanates such as polymethylene polyphenyl polyisocyanate and crude toluene diisocyanate can also be used.
In addition, modified isocyanates containing one or more uretdione bonds, isocyanurate bonds, allophanate bonds, burette bonds, uretonimine bonds, carbodiimide bonds, urethane bonds, urea bonds and the like obtained by modifying these organic polyisocyanates can also be used.
These can be used alone or in combination of two or more.
Among these, the aliphatic polyisocyanate, and further the araliphatic group, in that the viscosity of the isocyanate group-containing urethane prepolymer (A) is lowered and the workability of the resulting curable composition can be improved. Polyisocyanates, particularly xylylene diisocyanate, are preferred.

In the synthesis of the isocyanate group-containing urethane prepolymer (A), zinc, tin, lead, zirconium, bismuth, cobalt, manganese, such as bismuth tris (2-ethylhexanoate), tin octylate, zirconium octylate, etc. , Salts of metals such as iron and organic acids such as octylic acid and naphthenic acid, organometallic compounds such as salts of organic metals and organic acids such as dibutyltin dilaurate and dioctyltin dilaurate, triethylenediamine, triethylamine, tri-n -A urethanation reaction catalyst such as a short-chain tertiary amine such as butylamine or a salt thereof can be used, and among these, an organometallic compound is preferable.
Further, a known organic solvent can also be used.

Next, the alkoxysilane compound having an alkoxy group other than a methoxy group and / or a partial hydrolysis condensate (B) thereof in the present invention will be described.
This component (B) is blended with the curable composition comprising the isocyanate group-containing urethane prepolymer (A), so that when the curable composition is exposed to moisture, it is not only after curing but also from the stage during curing. The surface of the cured product can be easily washed away by running water such as rain or shower even if a small amount of dust does not adhere to the surface, and the surface of the cured product has excellent anti-contamination properties. This is because the curable composition is cured by moisture, and the component (B) migrates (bleeds) to the surface of the curable composition being cured, undergoes hydrolysis by moisture, and condenses while dealcoholizing. This is presumably due to the formation of a hydrophilic film.
Furthermore, for the purpose of accelerating the curing of the curable composition comprising the isocyanate group-containing urethane prepolymer (A), when the curing accelerating catalyst (C) described later is blended, the cured product surface is exposed to sunlight, oxygen, When exposed to rainwater or the like, since the curing accelerating catalyst (C) also acts as a catalyst for breaking the urethane bond after curing, the weather resistance of the cured product is usually lowered. By mixing this with a curable composition comprising an isocyanate group-containing urethane prepolymer (A) and a curing accelerating catalyst (C), the surface after curing of the resulting curable composition is remarkably excellent. It is possible to give the effect of having weather resistance. This is because, as described above, the component (B) quickly forms a hydrophilic film on the surface of the cured product, becomes a barrier layer, and prevents direct exposure of sunlight, rainwater, etc. to the inside of the cured product. Inferred.

Specifically, the alkoxysilane compound having an alkoxy group other than the methoxy group and / or the partially hydrolyzed condensate thereof (B) component has an alkoxy group other than the methoxy group shown in the following general formula (1). Examples thereof include alkoxysilane compounds and / or partial hydrolysis condensates thereof. Here, the alkoxysilane compound may have at least one alkoxy group other than a methoxy group.
R _4-n SiX _n (1)
[In the formula (1), R represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and when R is plural, they may be the same or different. X represents an alkoxy group, and when X is plural, they may be the same or different, but at least one is an alkoxy group other than a methoxy group. n is an integer of 1-4. ]
R is a monovalent hydrocarbon having 1 to 6 carbon atoms having no reactive functional group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, and phenyl group. Of these, a methyl group is preferred.
Examples of X include alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group, and the reaction between the hydrolysis rate and the isocyanate group of the urethane prepolymer (A) of the corresponding alcohol generated. At least one of them must be an alkoxy group other than a methoxy group, and all of them must be an ethoxy group, or an ethoxy group and a methoxy group, in terms of balance between speed and high antifouling effect and weathering effect. The combination of is preferable. When all alkoxy groups are methoxy groups, the reaction rate of the methanol generated by hydrolysis with the isocyanate groups of the isocyanate group-containing urethane prepolymer (A) is high, resulting in insufficient curing, and an effect of preventing contamination. Is not preferred because it is not exhibited.
Further, one or more of the alkoxysilane compounds represented by the formula (1) are partially 2 or more molecules, preferably 2 to 20 molecules, more preferably 2 to 15 molecules, linearly or three-dimensionally. Hydrolyzed and condensed multimers can also be used, and the method of use may be an alkoxysilane compound (monomer) alone, a partial hydrolysis condensate of an alkoxysilane compound alone, or an alkoxysilane compound. A combination of (monomer) and a partially hydrolyzed condensate of an alkoxysilane compound may be used.
More specifically, examples of the compound represented by the general formula (1) include tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltriethoxysilane, methyltripropoxysilane, and methyltriisopropoxy. Monomers such as silane, methyltributoxysilane, dimethoxydiethoxysilane, and monomethoxytriethoxysilane can be used, and these can be used alone or in combination of two or more thereof. Tetraethoxysilane, dimethoxydiethoxysilane, and these partially hydrolyzed condensates are preferable in that they have a high antifouling effect and a high weathering effect.
The amount of the component (B) used is 0.01 to 100 parts by weight, more preferably 0.1 to 30 parts by weight, and particularly 0.1 to 10 parts by weight with respect to 100 parts by weight of the isocyanate group-containing urethane prepolymer (A). Part is preferred. If it is less than 0.01 parts by mass, the effect of imparting contamination prevention is small, and if it exceeds 100 parts by mass, the amount of alkyl alcohol generated by hydrolysis increases and reacts with the isocyanate group of component (A) to cause poor curing. Therefore, it is not preferable.

Next, the curing accelerating catalyst (C) will be described.
This component (C) serves to promote the reaction between the isocyanate group of the isocyanate group-containing urethane prepolymer (A) and moisture and promote the curing of the curable composition by being blended with the curable composition. At the same time, hydrolysis and condensation reactions are promoted, and even when the curable composition is in the course of curing, it also functions as a catalyst that promptly exhibits the effect of preventing surface contamination.
Specific examples of the component (C) include a salt of a metal and an organic acid, a salt of an organic metal and an organic acid, a metal chelate compound, a tertiary amine, and the like. Examples thereof include salts of various organic acids such as tin octylate, tin naphthenate, bismuth octylate and zirconium octylate with various metals such as tin, bismuth, zirconium, zinc and manganese. As salts of organic metal and organic acid, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimaleate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin diversate, reaction of dibutyltin oxide and phthalate Such as things. Examples of metal chelate compounds include dibutyltin bis (acetylacetonate), tin chelate EXCESTAR C-501 manufactured by Asahi Glass Co., zirconium tetrakis (acetylacetonate), titanium tetrakis (acetylacetonate), aluminum tris (acetylacetate). Natto), aluminum tris (ethyl acetoacetate), acetylacetone cobalt, acetylacetone iron, acetylacetone copper, acetylacetone magnesium, acetylacetone bismuth, acetylacetone nickel, acetylacetone zinc, acetylacetone manganese and the like. 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), N-methylmorpholine, N-ethylmorpholine, and salts of these tertiary amines and organic carboxylic acids.
These can be used alone or in combination of two or more.
Of these, the effect of promoting the hydrolysis and condensation of alkoxysilane is high, and therefore the effect of imparting antifouling performance during curing is high, so that a salt of a metal and an organic acid, an organic metal and an organic acid, and And metal chelate compounds are preferred, metal chelate compounds are more preferred, and dibutyltin bis (acetylacetonate) is particularly preferred.
The component (C) has a curing rate of 0.001 to 10 parts by mass with respect to 100 parts by mass of the isocyanate group-containing urethane prepolymer (A), in terms of the effect of imparting anti-contamination performance during curing. It is particularly preferable to blend 0.01 to 2 parts by mass.

In the present invention, a weather stabilizer (D) can be further blended.
The weather resistance stabilizer (D) improves the weather resistance of the curable composition by preventing oxidation, photodegradation and thermal degradation after curing of the isocyanate group-containing urethane prepolymer (A) in the resulting curable composition. It is used to make it.
However, the weather resistance stabilizer (D), for example, when the curable composition is used as a sealing material, and the inside of the joint has a sufficient thickness such as a thickness of 3 mm or more, the weather resistance to the cured product. The sealing material is often applied at both ends of the joint, with the sealing material protruding slightly from the joint, and the thickness of the protruding portion of the sealing material is as thin as 1 mm or less. Thus, when the thickness after curing is thin as described above, the effect of imparting weather resistance to the cured product is reduced as compared to when it is thick. This is because when the thickness of the cured product is thin, the concentration drop due to volatilization of the weather stabilizer (D) occurs early.
At this time, when an alkoxysilane compound having an alkoxy group other than the methoxy group and / or a partially hydrolyzed condensate (B) component thereof is blended in the curable composition, even when the cured product is as thin as 1 mm or less, It has sufficiently high weather resistance. This is because the component (B) migrates (bleeds) to the surface of the cured product and undergoes hydrolysis and condensation by moisture such as moisture, so that an extremely thin film is formed. This film becomes a barrier, such as sunlight and rainwater. The effect of improving the weather resistance by preventing direct exposure to water and the volatilization of the weather stabilizer (D) are prevented by this coating, and since the concentration of the weather stabilizer (D) does not decrease, the weather resistance is enhanced. This is probably due to the synergy of the effects.
Accordingly, the present invention also provides a curable composition comprising the isocyanate group-containing urethane prepolymer (A) and the curing accelerating catalyst (C), or further containing a weathering stabilizer (D). A method for imparting excellent stain resistance and weather resistance to the curable composition by blending with an alkoxysilane compound having an alkoxy group other than the methoxy group and / or a partially hydrolyzed condensate thereof (B) But there is.
Specific examples of the weather stabilizer (D) include hindered amine light stabilizers, hindered phenol antioxidants, ultraviolet absorbers, etc., and hindered amine light stabilizers in terms of high weather resistance imparting effect. A hindered phenolic antioxidant is preferable, and a combined use of a hindered amine light stabilizer and a hindered phenolic antioxidant is particularly preferable.

Examples of the hindered amine light stabilizer include bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl. ] Butyl malonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 4-benzoyloxy- Examples include 2,2,6,6-tetramethylpiperidine. In addition to Sanyo LS-292, trade names manufactured by Sankyo Co., Ltd., trade names Adeka Stub series LA-52, LA-57, LA-62, LA-67, LA-77, LA- 82, LA-87 and other low molecular weight hindered amine light stabilizers of less than 1,000, also LA-63P, LA-68LD or Ciba Specialty Chemicals' product names CHIMASSORB series 119FL, 2020FDL, 944FD, 944LD And high molecular weight hindered amine light stabilizers having a molecular weight of 1,000 or more.
Examples of the hindered phenol antioxidant include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-). tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], benzenepropanoic acid Examples include 3,5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, and the like.
Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers such as 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, and 2- (4,6-diphenyl- Triazine-based UV absorbers such as 1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, benzophenone-based UV absorbers such as octabenzone, 2,4-di-tert-butylphenyl Examples include benzoate-based ultraviolet absorbers such as -3,5-di-tert-butyl-4-hydroxybenzoate.

  The weathering stabilizer (D) is preferably blended in an amount of 0.01 to 10 parts by weight, particularly 0.1 to 5 parts by weight, per 100 parts by weight of the isocyanate group-containing urethane prepolymer (A).

  In the present invention, additives (E) other than the components (B), (C) and (D) can be further blended. Examples of the additive (E) include fillers, thixotropic agents, storage stability improvers (dehydrating agents), colorants, designability imparting agents, and the like. It is used for the purpose of improving the stability, coloring, and imparting design properties such as matting of the surface of the cured product and provision of irregularities (providing roughness).

  As the filler, for example, mica, kaolin, zeolite, graphite, diatomaceous earth, white clay, clay, talc, slate powder, silicic anhydride, fine silica powder, aluminum powder, zinc powder, precipitated silica and other synthetic silica, heavy Inorganic powder fillers such as calcium carbonate, light calcium carbonate, magnesium carbonate, alumina, calcium oxide, and magnesium oxide, inorganic fillers such as fiber fillers such as glass fiber and carbon fiber, or the surface thereof as fatty acid Fillers treated with organic materials, wood flour, walnut flour, rice husk flour, pulp powder, cotton chips, rubber powder, polyamide resin, polyester resin, polyurethane resin, silicone resin, vinyl chloride resin, vinyl acetate resin, polyethylene and Polyolefin resin such as polypropylene, acrylic resin, epoxy resin In addition to organic fillers such as phenolic resins, urea resins, melamine resins and other thermoplastic resins or thermosetting resin powders, flame retardant imparting fillers such as magnesium hydroxide and aluminum hydroxide are also mentioned, The thing with a particle size of 0.01-1,000 micrometers is preferable.

Examples of the thixotropic agent include inorganic thixotropic agents such as colloidal silica and the above-mentioned fatty acid-treated calcium carbonate, and organic thixotropic agents such as organic bentonite and fatty acid amide.
Of these, fatty acid-treated calcium carbonate is preferred because of its high thixotropic effect.

  Storage stability improvers include calcium oxide, p-toluenesulfonyl isocyanate, etc. that react with moisture present in the composition.

  Examples of the colorant include inorganic pigments such as titanium oxide and iron oxide, organic pigments such as copper phthalocyanine, and carbon black.

The design-imparting agent can be used to assist in delustering the surface of the cured product by blending it into the curable composition, or it can be used to erase the surface luster and give the appearance of natural rough rocks. In particular, examples of the material that imparts mattness include various waxes such as beeswax, carnauba wax, montan wax, paraffin wax, and stearamide. And higher aliphatic compounds.
Examples of the material that removes the gloss of the surface and imparts irregularities include granular materials and balloons, etc. The granular materials are the same as those mentioned as the filler, and large particles having a particle size of 50 μm or more are mentioned. It is done.
The balloon is a hollow substance, and the shape thereof is not only spherical, but also various shapes such as a cubic shape, a rectangular shape, and a confetti shape, and those in which the balloon is slightly broken to such an extent that the unevenness imparting effect on the curable composition is not lost. However, the spherical shape is preferred because of the good workability of the curable composition. Specifically, for example, inorganic balloons such as glass balloons, shirasu balloons, silica balloons, ceramic balloons, organic balloons such as phenol resin balloons, urea resin balloons, polystyrene balloons, polyethylene balloons, saran balloons, or inorganic compounds and organic Examples thereof include a composite balloon in which a system compound is mixed or laminated.
Also, those coated or surface-treated with these balloons can be used. For example, inorganic balloons surface-treated with the silane coupling agent, etc., organic balloons with calcium carbonate, talc, titanium oxide, etc. Examples of coatings are also included.
Of these, from the viewpoint of the effect of imparting designability, granular materials and / or balloons are preferable, and granular inorganic fillers and / or inorganic balloons are more preferable, especially coarse heavy calcium carbonate and / or ceramics. A balloon is preferred.
The particle size of the granular material and / or balloon is preferably 50 μm or more, and more preferably 100 to 1,000 μm, from the viewpoint of the effect of providing designability.

  The total blending amount of the filler, thixotropic agent, storage stability improver (dehydrating agent), colorant and designability-imparting agent is 0 to 500 with respect to 100 parts by mass of the isocyanate group-containing urethane prepolymer (A). Part by mass, particularly 10 to 300 parts by mass is preferred.

  In the present invention, each additive (E) component can be used alone or in combination of two or more.

In the present invention, a plasticizer can be used in combination. The plasticizer is used to improve workability by reducing the viscosity of the curable composition, or to adjust rubber elastic physical properties after curing. Examples of the plasticizer include dibutyl phthalate, Non-aromatic dibasic substances such as heptyl phthalate, dioctyl phthalate, di (2-ethylhexyl) phthalate, diisononyl phthalate (DINP), butyl benzyl phthalate, butyl phthalyl butyl glycolate, etc., dioctyl adipate, dioctyl sebacate, etc. Low molecular weight plasticizers having a molecular weight of less than 500, such as phosphate esters such as acid esters, tricresyl phosphate, tributyl phosphate, and halogenated aliphatic compounds such as chlorinated paraffins. As a plasticizer, for example, dicar Polyester plasticizers such as polyesters from bonic acids and glycols, etherified or esterified derivatives of polyethylene glycol or polypropylene glycol, addition polymerization of ethylene oxide or propylene oxide to saccharide polyhydric alcohols such as sucrose, Examples include polyethers such as etherified or esterified saccharide-based polyethers, polystyrenes such as poly-α-methylstyrene, and low-viscosity (meth) acrylic acid ester-based copolymers. These can be used alone or in combination of two or more thereof, and among these, DINP is preferable in that the plasticizer is relatively difficult to migrate to the cured product surface.
The amount of the plasticizer used is preferably 1 to 100 parts by mass and more preferably 10 to 60 parts by mass with respect to 100 parts by mass of the isocyanate group-containing urethane prepolymer (A).

Since the curable composition of the present invention has a low viscosity, it is not necessary to use an organic solvent, or even if it is used, it requires only a very small amount and does not release an environmentally hazardous substance, so it is highly safe.
Examples of the organic solvent include conventionally known organic solvents such as aliphatic solvents such as n-hexane, alicyclic solvents such as cyclohexane and methylcyclohexane, aromatic solvents such as toluene and xylene, and the like. Any substance that does not react with the components can be used. From the viewpoint of safety, the organic solvent is preferably used in the curable composition so as to be less than 10% by mass, further less than 5% by mass, and further less than 1% by mass, and most preferably 0% by mass. Do not use it.
The method for producing the curable composition of the present invention is not particularly limited. For example, the isocyanate group-containing urethane prepolymer (A) and an alkoxysilane compound having an alkoxy group other than a methoxy group and / or a portion thereof. A hydrolysis condensate (B), a curing accelerating catalyst (C), a weathering stabilizer (D), and further an additive (E) or a plasticizer, selected as required, made of stainless steel or iron It can be produced by stirring and mixing in a patch or continuous manner under various conditions such as normal pressure, reduced pressure, pressurized pressure, or under a nitrogen stream. Examples of the agitation and mixing device include a planetary mixer, a kneader, an agitator, a nauta mixer, and a line mixer.
Since the produced curable composition is thickened and cured by moisture, it is preferably stored in a container that can block moisture, sealed and stored in order to maintain the storage stability of the contents. The container may be anything as long as it can block moisture, and examples include various kinds of containers such as drum cans, metal or synthetic resin pail cans and bag-like containers, and paper or synthetic resin cartridge-like containers. . In use, the container filled with the curable composition is opened, and the construction object is filled or applied using a manual or electric extrusion gun or a coating device.

  The curable composition of the present invention can be used as a two-component curable composition using the curable composition of the present invention as a main agent and a polyol, polyamine or the like as a curing agent. However, it is troublesome to mix the main agent and the curing agent. It is preferable to use it as a one-component moisture-curing type in that there is no fear of curing failure due to measurement error or mixing failure.

Next, the use of the curable composition of this invention is demonstrated.
The curable composition of the present invention can be widely used as a sealing material, an adhesive, a waterproofing film for a building or civil engineering structure, etc., but the curable composition is excellent even during curing and for many years after curing. The curable composition is applied in a place where the surface after curing is easily exposed to dust and exposed to sunlight and rainwater, in order to maximize the features of pollution prevention performance and remarkably excellent weather resistance. It is preferable to make it a use.
In particular, a siding sealant, a building exterior wall sealant, a sash sealant, a stone joint sealant, a ceramic material joint sealant, and an indoor joint sealant, each comprising the curable composition of the present invention. It is suitable to be used as a sealing material for treating a sheet end of a synthetic resin or a polyurethane-based coating film waterproofing material.
Note that joints that are directly exposed to the indoor environment or particularly the outdoor environment without hardening a coating on the surface of the sealing material as described later are collectively referred to as exposure joints. Therefore, it is preferable to use it as a sealing material for exposed joints comprising the curable composition of the present invention.
More specifically, in construction such as detached houses and apartment houses, a method called a ceramic or metal-based siding is applied to form an outer wall, which is widely used. The joints must be filled with a sealing material for waterproofing. At this time, if the siding has been painted in advance with a natural stone or tiled design, the sealing material used was pre-colored in a color that matches the surface color. Thereafter, the surface of the cured sealant is not directly overcoated, but is directly exposed to the outdoor environment, increasing the chance of exposure to dust and exposure to sunlight. By filling and applying the sealing material for siding of the present invention to the joint formed by such siding, it is possible to maintain a filling joint of a clean siding outer wall excellent in weather resistance without contamination for many years. Become.
In addition, in low-to-mid and high-rise building buildings, the surface of the joints that have been filled with and applied with a sealant is rarely overcoated, and as before, the hardened sealant is directly exposed to the outdoor environment and dust There will be more opportunities for contact and exposure to sunlight. Filling the joint formed on the outer wall of such a building with the sealing material for building outer wall joints of the present invention, it has been possible to provide a clean joint outer wall filling joint with excellent weather resistance without contamination for many years. Can be maintained.
In addition, the sash that forms the window of the building needs to be waterproofed by filling with a sealing material, but the surface after curing the sealing material is not overcoated. It will be exposed to the outdoor environment, and there will be more opportunities to come in contact with dust and sun light. By filling and applying the sealing material for the sash area of the present invention to the joint formed around the sash of such a building, the filling joint around the clean sash having excellent weather resistance without contamination is maintained for many years. It becomes possible to do.
In addition, for example, in the joints of walls made of stone plates such as marble, indoors and outdoors, such as the walls of subways and inside and outside walls of buildings, the surface of the sealing material filled for makeup or waterproofing is Since the top coat is not applied, the cured sealant has an opportunity to come into contact with dust or to be exposed to sunlight or the like as described above. By filling and constructing joints made of such stone plates with the joint material for stone joints of the present invention, it is possible to maintain a clean filled stone joint with excellent weather resistance without contamination for many years. It becomes.
In addition, for example, in joints such as outer walls and fences formed by sticking ceramic materials such as bricks and tiles, the surface of the sealing material filled for makeup or waterproofing is not overcoated, Similarly, the hardened sealant has more opportunities to come into contact with dust and to be exposed to sunlight. By filling and applying the sealing material for ceramics material joints of the present invention to joints formed with such ceramics materials, it has been possible to produce clean and filled ceramics material joints with excellent weather resistance without contamination for many years. Can be maintained over a long period of time.
In addition, for example, in a room of a building, a sealing material may be filled for waterproofing or makeup purposes in indoor joints formed between the periphery of the bathtub and the inner wall and between the built-in furniture and the inner wall. However, in this case as well, the surface of the cured sealant is not overcoated, and there is little opportunity to be exposed to sunlight in the room, but there are many opportunities for contact with dust, and there are many cases of contamination. By filling and constructing the indoor joint sealing material of the present invention in such an indoor joint, it becomes possible to maintain a clean and filled indoor joint for many years.
There is also a method of forming a floor by attaching a synthetic resin sheet such as a vinyl chloride sheet on the rooftop of a building, indoor floor, etc. In this method, in order to process the terminal of the bonded sheet, It is necessary to fill and apply a sealing material along. Also in this case, the surface of the hardened sealing material is not overcoated, and there are many opportunities to come in contact with dust or to be exposed to sunlight, not only outdoors but also indoors. By filling and constructing the synthetic resin sheet terminal sealing material of the present invention in the terminal of such a synthetic resin sheet, a clean synthetic resin sheet terminal excellent in weather resistance without contamination is maintained for many years. It becomes possible.
In addition, there is a method of waterproofing the surface of the building by installing a waterproof coating on the rooftop or veranda floor of the building. Increased exposure. By applying and applying the polyurethane coating waterproof material of the present invention to such rooftops and veranda floors, etc., to maintain a clean surface waterproof rooftop and veranda floor with excellent weather resistance without contamination for many years Is possible.
In addition, the sealing material and the waterproofing coating material for various applications are usually filled and applied after applying a primer to the substrate to be bonded surface in order to improve adhesion to the substrate made of siding, stone plate, concrete, etc. It is preferable to
In addition, the curable composition of the present invention is applied as a sealing material or a urethane film waterproofing material, so that it follows the displacement of the base, so that the design of the physical properties after curing has an elongation of 300% or more, preferably 500%. above, and 50% tensile stress 50 N / cm ² or less, preferably of 30 N / cm ² or less, even as a large soft rubber elastic elongation of, exhibit excellent antifouling performance and weather resistance.

Hereinafter, the present invention will be described in more detail with reference to examples.
Here, as an example of the curable composition, a one-component moisture-curable waterproofing film and a one-component moisture-curable sealing material are shown, but the present invention is not limited thereto.

[Synthesis of isocyanate group-containing urethane prepolymer]
Synthesis example 1
While flowing nitrogen gas through a reaction vessel equipped with a stirrer, thermometer, nitrogen introduction tube and heating / cooling device, 600 g of polyoxypropylenediol (Asahi Glass Co., Ltd., Exenol-3021, number average molecular weight 3,300) Mole: 0.364) and 400 g (OH mole: 0.300) of polyoxypropylene triol (Mitsui Chemical Polyurethanes, Ttiol-MN-4000, number average molecular weight 4,000) were charged and stirred, xylylene diisocyanate (Mitsui Chemical Polyurethanes, Takenate 500, molecular weight 188) 125 g (NCO mol: 1.33) (R value (NCO mol / OH mol) = 2.0) and xylene 280 g, dibutyltin dilaurate (manufactured by Nitto Kasei Corporation, Neostan U-100) 0.16 g is added, and then heated to 70-80 ° C. for 2 hours. And 拌, isocyanate group content is completed the reaction when it becomes less than the theoretical value (1.99 wt%) were prepared isocyanate group-containing urethane prepolymer PU-1.
This isocyanate group-containing urethane prepolymer PU-1 was a viscous liquid transparent at room temperature with a measured isocyanate group content of 1.95% by mass and a viscosity of 18,000 mPa · s / 25 ° C. by titration.

[Preparation of black toner]
Preparation Example 1
A stainless steel cylindrical container was charged with 70 g of diisononyl phthalate (DINP) and 30 g of thermal black previously dried in a dryer at 100 to 110 ° C. to a water content of 0.1% by mass or less. The resulting mixture was stirred and dispersed uniformly to prepare a black toner.

(Preparation of yellow toner)
Preparation Example 2
A container similar to Preparation Example 1 was charged with 70 g of diisononyl phthalate (DINP) and 30 g of yellow iron oxide that had been previously dried in a dryer at 100 to 110 ° C. to a water content of 0.1% by mass or less. The mixture was stirred using a high-speed stirrer and uniformly dispersed to prepare a yellow toner.

[Preparation of red toner]
Preparation Example 3
A container similar to Preparation Example 1 was charged with 70 g of diisononyl phthalate (DINP) and 30 g of red iron oxide previously dried in a dryer at 100 to 110 ° C. to a water content of 0.1% by mass or less. The mixture was stirred using a high-speed stirrer and uniformly dispersed to prepare a red toner.

Example 1
200 g of the isocyanate group-containing urethane prepolymer PU-1 obtained in Synthesis Example 1 was charged into a kneading vessel equipped with a stirrer, a heating device, a cooling device, and a nitrogen introduction tube while flowing nitrogen gas, and each of them was previously 100 to 110 ° C. while stirring. 60 g of heavy calcium carbonate dried in a drier to a water content of 0.05% by mass or less, 220 g of fatty acid surface-treated calcium carbonate (Shiraishi Kogyo Co., Ltd., Shiruka Hana CCR), 20 g of titanium oxide, diisononyl phthalate ( (DINP) 100 g was sequentially charged and mixed until the contents were uniform. Next, 20 g of a hindered phenol antioxidant (manufactured by Ciba Specialty Chemicals, IRGANOX 1010, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]) is preliminarily 80 g. 3.0 g of a 20% by weight DMC solution of a hindered phenol antioxidant prepared by dissolving in dimethyl carbonate (DMC) and 20 g of a hindered amine light stabilizer (ADEKA, LA-63P) in advance of 80 g. 3.0, 20 g% DMC solution of a hindered amine light stabilizer prepared by dissolving in DMC, 2.0 g of p-toluenesulfonyl isocyanate, 3.0 g of tetraethoxysilane (Colcoat, ethyl silicate 28) And dibutyltin bis (acetylacetona G) were charged and 0.02 g, and further mixed until the contents became homogeneous. Next, the mixture was degassed under reduced pressure at 50 to 100 hPa, filled in a container and sealed to prepare a one-pack type moisture curable sealing material S-1.
The obtained one-component moisture-curable sealing material S-1 was a white non-flowing pasty liquid at room temperature.

Example 2
In Example 1, without using tetraethoxysilane, instead of using 3.0 g of a partially hydrolyzed condensate of tetraethoxysilane (Colcoat Co., ethyl silicate 40) on average, it was used in the same manner. A one-component moisture-curable sealing material S-2 was prepared.
The obtained one-pack type moisture curable sealing material S-2 was a white paste-like liquid that did not flow at room temperature.

Example 3
In Example 1, the same procedure was carried out except that 2.0 g of tetraethoxysilane was used and, on average, 2.0 g of a partial hydrolysis-condensation product of five molecules of tetraethoxysilane (Colcoat Co., ethyl silicate 40) was used. Thus, a one-pack type moisture curable sealing material S-3 was prepared.
The obtained one-component moisture-curable sealing material S-3 was a white non-flowing paste-like liquid at room temperature.

Example 4
In Example 1, without using tetraethoxysilane, instead of using 6.0 g of a partially hydrolyzed condensate of 5 molecules of tetraethoxysilane (Colcoat Co., ethyl silicate 40) on average, the same procedure was used. A one-component moisture curable sealing material S-4 was prepared.
The obtained one-component moisture-curable sealing material S-4 was a white non-flowing pasty liquid at room temperature.

Example 5
In Example 1, tetraethoxysilane was not used, but instead, an average of about 10 molecules of a partial hydrolysis condensate of tetraethoxysilane (Colcoat Co., ethyl silicate 48) was used in the same manner. Thus, a one-pack type moisture curable sealing material S-5 was prepared.
The obtained one-component moisture-curable sealing material S-5 was a white non-flowing paste-like liquid at room temperature.

Example 6
In Example 1, 60 g of fatty acid surface-treated calcium carbonate was used, and tetraethoxysilane was not used. Instead, an average partial hydrolysis-condensation product of about 10 molecules of diethoxydimethoxysilane (manufactured by Colcoat, EMS- One-pack type moisture-curable coating film waterproofing material S-6 was prepared in the same manner except that 3.0 g of 485) was used.
The obtained one-pack moisture-curable coating film waterproofing material S-6 was a white fluid fluid viscous liquid at room temperature.

Comparative Example 1
In Example 1, a one-component moisture-curable sealing material (Comparative S-1) was prepared in the same manner except that tetraethoxysilane was not used.
The obtained one-pack type moisture curable sealant (Comparative S-1) was a white non-flowing paste-like liquid at room temperature.

Comparative Example 2
In Example 1, without using tetraethoxysilane, instead of using 3.0 g of tetramethoxysilane (manufactured by Tama Chemical Industry Co., Ltd., normal methyl silicate monomer), a one-component moisture-curable sealing material was used. (Comparison S-2) was prepared.
The obtained one-pack type moisture curable sealant (Comparative S-2) was a white non-flowing paste-like liquid at room temperature.

Comparative Example 3
In Example 1, tetraethoxysilane was not used, but instead, an average of 4 molecules of a partial hydrolysis condensate of tetramethoxysilane (manufactured by Colcoat, methyl silicate 51) was used in the same manner. A liquid type moisture curable sealant (Comparative S-3) was prepared.
The obtained one-pack type moisture curable sealing material (Comparative S-3) was a white non-flowing pasty liquid at room temperature.

Comparative Example 4
In Example 1, except that tetraethoxysilane was not used, instead of using 3.0 g of a partial hydrolysis condensate of an average of 7 molecules of tetramethoxysilane (manufactured by Colcoat, methyl silicate 53A), A liquid moisture curable sealant (Comparative S-4) was prepared.
The obtained one-component moisture-curing sealant (Comparative S-4) was a white non-flowing pasty liquid at room temperature.

Example 7
The black toner 1 obtained in Preparation Example 1 was charged with 300 g of the one-component moisture-curable sealing material S-1 obtained in Example 1 while flowing nitrogen gas into the same kneading container as in Example 1, and stirred. .2 g, 7.4 g of the yellow toner obtained in Preparation Example 2, and 2.0 g of the red toner obtained in Preparation Example 3 were added and mixed until uniform. Subsequently, it was degassed under reduced pressure at 50 to 100 hPa, filled into a paper cartridge-like container, sealed, and a one-component moisture-curing siding sealant S-7 colored in a range brown color was prepared.

Example 8
In Example 7, without using the one-component moisture-curable sealant S-1 obtained in Example 1, 300 g of the one-component moisture-curable sealant S-2 obtained in Example 2 was used instead. In the same manner, a one-component moisture-curing siding sealant S-8 colored in a range brown color was prepared.

Example 9
While supplying nitrogen gas to the same kneading container as in Example 1, 300 g of the one-component moisture-curing sealant S-3 obtained in Example 3 was charged, and the black toner obtained in Preparation Example 1 was stirred while stirring. 5.3 g was added and mixed until uniform. Subsequently, it was degassed under reduced pressure at 50 to 100 hPa, filled into a paper cartridge-like container and sealed, and a one-component moisture-curing building exterior wall jointing sealant S-9 colored gray was prepared.

Example 10
In Example 9, 300 g of the one-component moisture curable sealant S-4 obtained in Example 4 was used instead of using the one-component moisture-curable sealant S-3 obtained in Example 3. In the same manner, a one-component moisture-curing sash sealing material S-10 colored in gray was prepared.

Example 11
In Example 9, the sealing material S-3 obtained in Example 3 was not used, but 300 g of the sealing material S-5 obtained in Example 5 was used instead, and the black toner obtained in Preparation Example 1 was used in 2. In the same manner except that 1 g was used, a one-component moisture-curing stone joint sealant S-11 colored in a light gray color was prepared.

Comparative Example 5
In Example 7, instead of using the one-component moisture-curable sealant S-1 obtained in Example 1, instead of using the one-component moisture-curable sealant (Comparative S-1) obtained in Comparative Example 1. A one-component moisture-curing siding sealant (Comparative S-5) was prepared in the same manner except that 300 g was used.

Comparative Example 6
In Example 7, without using the one-component moisture-curable sealant S-1 obtained in Example 1, instead of using the one-component moisture-curable sealant (Comparative S-2) obtained in Comparative Example 2. A one-component moisture-curing siding sealant (Comparative S-6) colored in a brown color was similarly prepared except that 300 g was used.

Comparative Example 7
In Example 9, instead of using the one-component moisture-curable sealant S-3 obtained in Example 3, the one-component moisture-curable sealant (Comparative S-3) obtained in Comparative Example 3 was used instead. A one-component moisture-curing building exterior wall jointing sealant (Comparative S-7) colored in gray was prepared in the same manner except that 300 g was used.

Comparative Example 8
In Example 10, instead of using the one-component moisture-curable sealant S-4 obtained in Example 4, the one-component moisture-curable sealant (Comparative S-4) obtained in Comparative Example 4 was used instead. A one-pack type moisture-curing sash sealing material (Comparative S-8) colored in gray was prepared in the same manner except that 300 g was used.

Comparative Example 9
In Comparative Example 8, except that 2.1 g of the black toner obtained in Preparation Example 1 was used, a stone sealant (Comparative S-9) colored light gray was prepared.

〔performance test〕
Using the one-component moisture-curing sealant or the one-component moisture-curing coating waterproofing material obtained in Examples 1 to 6 and Comparative Examples 1 to 4, the following contamination during curing, after curing, and outdoors Tables 1 and 2 show the results of the test, the tensile adhesion test, the weather resistance test of the thin film (0.2 mm), and the weather resistance test of the thick film (5 mm), together with the raw material composition, and Examples 7 to 11 Tables 3 and 4 show the results of outdoor contamination tests using the one-component moisture-curable sealing materials obtained in Comparative Examples 5 to 9 together with the raw material compositions.
Test method (a) Contamination test in the middle of curing A slate plate cut into a strip shape of 5 mm thickness x 20 mm width is arranged in a rectangular frame shape on the surface of a 5 mm thick slate plate, and bonded using an adhesive. Then, a joint having a depth of 5 mm, a width of 20 mm, and a length of 150 mm is prepared, and this joint is filled with a one-component moisture-curable sealing material or a one-component moisture-curable coating film waterproofing material, and an extra sealing material or waterproofing The specimen was scraped off with a spatula and the surface was flattened.
The required number of specimens were prepared and immediately placed in a room adjusted to 23 ° C. and 50% relative humidity and cured. After 1 day, black silica sand (particle size 70 to 110 μm) was sprinkled on the surface of the test specimen, and the test specimen was immediately turned over, and the bottom surface was lightly tapped by hand to remove excess black silica sand. The state of the black silica sand (dirt) remaining on the surface was visually observed, and the contamination during curing was evaluated according to the following criteria.
In addition, although the surface of the sealing material or waterproofing material after 1 day passed is hardening, the inside was unhardened.
Judgment criteria ○: Black silica sand is hardly adhered to the surface and the surface is clean.
X: A large amount of black silica sand adheres to the surface and is dirty.
(B) Contamination test after curing In the contamination test during curing, a contamination test after curing was conducted in the same manner except that black quartz sand was sprinkled on the surface of the test specimen after 7 days of curing. Evaluation was made according to the criteria.
The sealing material or waterproofing material after 7 days of curing was cured to the inside.
Judgment criteria ○: Black silica sand is hardly adhered to the surface and the surface is clean.
X: A large amount of black silica sand adheres to the surface and is dirty.
(C) Contamination test outdoors The required number of specimens similar to those prepared in the contamination test during curing are prepared, and immediately in the direction where the surface of the joint faces the road, near the intersection where there is a lot of traffic, It was installed with its length direction vertical. After 1 month, the test specimen was removed, the state of contamination due to dust adhering to the surface of the test specimen was visually observed, and the outdoor contamination was evaluated according to the following criteria.
Judgment criteria ○: Dust adhesion is hardly observed on the surface, and the surface is clean.
X: A large amount of dust adheres to the surface and is dirty.
(D) Tensile adhesiveness The specimen after curing was subjected to a tensile test according to 4.21 tensile adhesiveness of JIS A 1439 (1997, revised 2002) “Testing method of sealing material for building”, and 50% tensile stress (M50). ) (N / cm ² ), maximum tensile stress (Tmax) (N / cm ² ), and elongation at maximum load (Emax) (%).
In addition, the test body made the mortar into the to-be-adhered body, it processed with the primer (The auto-chemical industry company make, OP-2531), and the sealing material or the coating-film waterproofing material was casted, and it produced.
(E) Weather resistance test of thin film (0.2 mm) Two masking tapes with a thickness of 0.1 mm and a width of 12 mm are laminated on the surface of a slate plate with a thickness of 5 mm and attached in a square frame shape. Apply a material or waterproofing coating material, scrape off any excess with a spatula, flatten the surface, and apply it to a thickness of 0.2 mm x width 30 mm x length 100 mm, immediately at 23 ° C, 50% relative humidity The specimen was placed in a room adjusted for 7 days and cured and cured to obtain a test specimen.
4. Specimen was measured according to JIS K 6266 (1996, Confirmation 2001) “Testing method for weather resistance of vulcanized rubber and thermoplastic rubber”. In an open frame carbon arc lamp type weather resistance test, light irradiation was performed using a sunshine weatherometer under conditions of SA method (black panel temperature 63 ° C., irradiation for 102 minutes, irradiation for 18 minutes and water spray). . After 100 hours of irradiation, 300 hours of irradiation, and 500 hours of irradiation, the appearance change of the surface of the test specimen was visually observed, and the weather resistance at the time of thin film (0.2 mm) was evaluated according to the following criteria.
Judgment criteria ○: No or little cracking (crack) on the specimen surface.
X: The specimen surface has many cracks.
(F) Weather resistance test of thick film (5 mm) In the weather resistance test of the thin film (0.2 mm), a foamed polyethylene backup material having a thickness of 5 mm x width of 12 mm is attached in a square frame shape, and a sealing material or a waterproof coating film Except for using a specimen with a coating thickness of 5 mm as the test specimen, light irradiation was performed in the same manner, and the appearance change of the specimen surface after 1000 hours, 1500 hours, 2000 hours was observed visually. Then, the weather resistance at the time of thick film (5 mm) was evaluated according to the following criteria.
Judgment criteria ○: No or little cracking (crack) on the specimen surface.
X: The specimen surface has many cracks.
(G) Contamination test outdoors using various adherends The length of a test specimen prepared by the following method is immediately near the intersection where traffic is heavy, with the joint surface facing the road. Installed with the direction vertical. In the case of a test body using a sash, the joint was installed with the length direction of the joint horizontally. After 1 month, the test specimen was removed, the state of contamination due to dust adhering to the surface of the test specimen was visually observed, and the outdoor contamination using various adherends was evaluated according to the following criteria.
Judgment criteria ○: Dust adhesion is hardly observed on the surface, and the surface is clean.
X: A large amount of dust adheres to the surface and is dirty.
1) Preparation of test specimens of Examples 7 and 8 and Comparative Examples 5 and 6 On the surface of a 5 mm thick plywood, a siding of a surface color name range brown as an adherend (manufactured by Kubota Matsushita Electric Industrial Co., Ltd., Neolock Sera) 16 and a thickness of 16 mm) are cut into a size of 300 mm in length and 300 mm in width, and are arranged and fixed at intervals of 12 mm to produce a joint having a width of 12 mm, and a foamed polyethylene having a thickness of 2 mm is formed on the joint. The back-up material made was made into a joint having a width of 12 mm, a depth of 10 mm, and a length of 300 mm. After the joint was cleaned with a brush, masking tape was applied to both sides of the joint, and a primer (manufactured by Auto Chemical Industry Co., Ltd., OP-2531) was applied with a brush to both sides to be the sealing material application surface and left for 30 minutes. . After the required number was prepared, the sealing materials for siding colored in the range brown color obtained in Examples 7 and 8 and Comparative Examples 5 and 6 were filled, respectively, and the excess sealing material was scraped off with a spatula to flatten the surface. The test piece was peeled off from the masking tape.
In addition, the joint surface of this test body matched the siding surface color and became a beautiful filling joint.
2) Production of specimens of Example 9 and Comparative Example 7 Two mortar plates molded in a thickness of 10 mm × length and width of 300 mm as an adherend are arranged on a surface of a plywood having a thickness of 5 mm with an interval of 12 mm. A joint having a width of 12 mm was prepared, and a backup material made of foamed polyethylene having a thickness of 2 mm was loaded into the joint to obtain a joint having a width of 12 mm, a depth of 8 mm, and a length of 300 mm. After the joint was cleaned with a brush, masking tape was applied to both sides of the joint, and a primer (manufactured by Auto Chemical Industry Co., Ltd., OP-2531) was applied with a brush to both sides to be the sealing material application surface and left for 30 minutes. . After the required number was prepared, the building exterior wall sealing material colored in gray obtained in Example 9 and Comparative Example 7 was filled, and the excess sealing material was scraped off with a spatula to flatten the surface. The peeled material was used as a test specimen.
In addition, the joint surface of this test body matched the mortar surface color, and became a beautiful filling joint.
3) Preparation of specimens of Example 10 and Comparative Example 8 The upper horizontal part of the outer frame part of a commercially available sash (manufactured by Sankyo Tateyama Aluminum Co., Ltd., single sash, Madio S, hot brown color) is cut out to a length of 300 mm. Was prepared as one adherend, and this was fixed to the surface of a 5 mm thick plywood with screws. A commercially available siding plate (thickness 16 mm) as the other adherend, cut out in a 300 mm length and width, is fixed to the upper side of the outer frame with a 12 mm gap from the top of the sash through a square plate attached to the plywood. Then, a joint having a width of 12 mm was produced between the sash outer frame and the siding. A 2 mm thick foamed polyethylene backup material is loaded on the bottom of the joint. After the joint is cleaned with a brush, masking tape is applied to both sides of the joint, and a primer (manufactured by Auto Chemical Industries, OP-2531) is attached. It apply | coated with the brush on both sides used as the adhesion surface of a sealing material, and was left to stand for 30 minutes. A necessary number of these were prepared, filled with the dark gray colored sealing material obtained in Example 10 and Comparative Example 8, respectively, the excess sealing material was scraped off with a spatula, and the surface was flattened. The test piece was peeled off.
In addition, the joint surface of this test body matched the sash surface color, and became a beautiful filling joint.
4) Preparation of specimens of Example 11 and Comparative Example 9 On the surface of a plywood having a thickness of 5 mm, two commercially available marble plates cut into a thickness of 10 mm × length and width of 300 mm were separated by 12 mm. The joint was opened and fixed with an adhesive to prepare a joint having a width of 12 mm, and a backup material made of foamed polyethylene having a thickness of 2 mm was loaded into the joint to obtain a joint having a width of 12 mm × depth of 8 mm × length of 300 mm. After the joint was cleaned with a brush, masking tape was applied to both sides of the joint, and a primer (manufactured by Auto Chemical Industry Co., Ltd., OP-2531) was applied with a brush to both sides to be the sealing material application surface and left for 30 minutes. . After the required number was prepared and filled with the gray sealant sealing material obtained in Example 11 and Comparative Example 9 and scraped off the excess sealing material with a spatula, the masking tape was applied. The peeled material was used as a test specimen.
The joint surface of this test body was a clean filling joint that matched the marble surface color.

  In addition, also about the sealing material for ceramics material joints, the sealing material for indoor joints, and the sealing material for resin sheet terminal processing prepared using the sealing material S-1 obtained in Example 1, bricks, white decorative plywood, PVC As a result of filling and filling the corresponding joints made using the indoor wall sheet made of vinyl chloride and the waterproof sheet made of polyvinyl chloride, it became a clean filling joint without contamination. Moreover, also about the waterproofing membrane colored in gray prepared using the waterproofing membrane S-6 obtained in Example 6, the slate plate treated with a primer (manufactured by Auto Chemical Industry Co., Ltd., OP-2531). As a result of coating and applying to the surface, a clean waterproof coating without contamination could be obtained.

  The curable composition of the present invention exhibits an excellent anti-contamination effect from the middle of curing to the long term after curing, and has a remarkably excellent weather resistance, and therefore, paints, adhesives, sealing materials, etc. in the fields of architecture, civil engineering Although it can be used for various applications, it can be used for various purposes such as a sealing material for exposed joints where the surface after curing is particularly susceptible to direct exposure to dust, in order to maximize the effects of the present invention. It is suitably used as a sealing material or a coating film waterproofing agent.

Claims (17)

Isocyanate group-containing urethane prepolymer (A), an alkoxysilane compound having an alkoxy group other than the methoxy group represented by the following general formula (1) and / or a partial hydrolysis condensate (B) thereof, and a curing accelerating catalyst (C) A curable composition characterized by comprising:
R _4-n SiX _n (1)
[In the formula (1), R represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and when R is plural, they may be the same or different. X represents an alkoxy group, and when X is plural, they may be the same or different, but at least one is an alkoxy group other than a methoxy group. n is an integer of 1-4. ]   The curable composition according to claim 1, further comprising a weather resistance stabilizer (D).   The curable composition according to claim 1 or 2, wherein the alkoxy group other than the methoxy group is an ethoxy group.   The curable composition according to claim 1 or 2, wherein the alkoxysilane compound having an alkoxy group other than the methoxy group is tetraethoxysilane.   The curable composition according to claim 1 or 2, wherein the alkoxysilane compound having an alkoxy group other than the methoxy group is ethoxymethoxysilane.   The curable composition as described in any one of Claims 1-5 whose isocyanate group of the said isocyanate group containing urethane prepolymer (A) is an isocyanate group derived from an aliphatic polyisocyanate compound.   The curable composition according to any one of claims 1 to 6, wherein the curing accelerating catalyst (C) is a metal chelate compound.   Furthermore, the curable composition as described in any one of Claims 1-7 which mix | blends an additive (E).   It consists of a curable composition as described in any one of Claims 1-8, The sealing material for exposed joints characterized by the above-mentioned.   It consists of a curable composition as described in any one of Claims 1-8, The sealing material for siding characterized by the above-mentioned.   A sealing material for building outer wall joints, comprising the curable composition according to any one of claims 1 to 8.   It consists of a curable composition as described in any one of Claims 1-8, The sealing material for sash surroundings characterized by the above-mentioned.   A sealant for stone joints, comprising the curable composition according to any one of claims 1 to 8.   A sealing material for ceramics material joints, comprising the curable composition according to any one of claims 1 to 8.   A sealing material for indoor joints, comprising the curable composition according to any one of claims 1 to 8.   A sealing material for sheet end treatment made of synthetic resin, comprising the curable composition according to any one of claims 1 to 8. It consists of a curable composition as described in any one of Claims 1-8, The polyurethane-type coating-film waterproofing material characterized by the above-mentioned.