JP2009073882A - Moisture-curable composition and moisture-curable sealing material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a moisture-curable composition and a sealing material causing no minute crack on the surface after curing even when its composition is designed to form a comparatively soft rubber type elastic body having a low-middle modulus, rapidly exhibiting pollution preventing effect over the surface halfway of curing after application at ordinary temperatures and moreover at low temperatures in winter, and exhibiting pollution preventing performance over a long period after the curing. <P>SOLUTION: The moisture-curable composition and the sealing material comprise (A) an isocyanate group-containing urethane prepolymer, (B) a silane compound represented by a formula R<SB>4-n</SB>SiX<SB>n</SB>(wherein R is a 1-6C monovalent hydrocarbon group or Rs are same or different 1-6C monovalent hydrocarbon groups, X is an alkoxy group or Xs are same or different alkoxy groups, at least one of which is an alkoxy group except a methoxy group, and n is an integer of 1-4), and/or (C) a partial hydrolysis-condensation product of the above silane compound, and (D) an oxazolidine compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a moisture curable composition and a moisture curable sealing material which are cured by moisture (humidity) 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 used in moisture curable compositions such as waterproof sealants for buildings, civil engineering, and automobiles, adhesives, paints, etc. It is 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 modulus to medium modulus range, the moisture curable composition containing polyurethane resin remains tacky (adhesive) on the surface after curing, making it easy for dust and dirt to adhere to the surface. The problem of blackish contamination occurs. In particular, when a moisture-curing composition such as a sealing material is applied outdoors, such as on outer wall joints or rooftops, the remaining tack is severe at the stage where it is not fully cured immediately after construction. When dust is spilled, contamination due to dust adhesion is severe.
In the field of water-based resin coatings, as a technique for exhibiting low pollution performance, a low-contamination agent for water-based paints, which is a modified condensate of alkoxysilane having a polyoxyalkylene group and an alkoxy group, and a synthetic resin emulsion. As a curing agent for the main component including a low-contamination water-based coating composition added with a specific amount and a hydroxyl group-containing synthetic resin emulsion, a polyoxyalkylene group and an isocyanate group-containing water-dispersible polyisocyanate compound, a polyoxyalkylene group and an alkoxy group A method using a modified condensate of alkoxysilane having a solvent having a specific solubility parameter has been proposed (see Patent Documents 1 and 2). These are techniques for improving the compatibility of the alkoxysilane compound and improving the dispersion stability and improving the stain resistance with respect to the water-based paint. The hardened coating film is hard and originally has little contamination.
However, in the field of non-aqueous curable compositions, and when cured products such as moisture curable sealing materials and waterproofing coatings are relatively soft in the low modulus to medium modulus (low hardness to medium hardness) region Therefore, there is no effective technique for imparting good antifouling properties to cured products, and there is a need for a curable composition having excellent antifouling performance even during curing and for a long period after curing. ing.
The present inventors previously proposed a moisture curable composition comprising a urethane prepolymer and a specific alkoxysilane compound as a means for solving these problems. However, this moisture curable composition later has excellent anti-contamination performance because it has no dust adhering to the surface after curing, but it has been found that fine cracks (hair cracks) are generated on the surface. Occurred.
International Publication No. WO99 / 05228 JP 2005-325169 A

  Accordingly, in view of the above-mentioned problems, the present invention has a fine structure on the surface after curing even when the composition is designed to be a relatively soft rubber-like elastic body having a low modulus to a medium modulus (high elongation to medium elongation) after curing. Moisture curing with excellent anti-contamination performance over a long period of time after curing without causing any cracks, quickly exhibiting surface contamination prevention effects from the middle of curing after construction, even at low temperatures in winter as well as normal temperatures An object is to provide a mold composition and a moisture-curing sealant.

As a result of diligent studies to solve the above problems, by blending an oxazolidine compound with a moisture curable composition comprising an isocyanate group-containing urethane prepolymer and a specific alkoxysilane compound, fine cracks are formed on the surface after curing. The present inventors have found that the surface of the cured product can be prevented from being contaminated without being generated, thereby completing the present invention.
That is, this invention is shown by the following (1)-(14).

〔但し、（３）式中、Ｒは炭素数１〜６の１価の炭化水素基を表し、Ｒが複数のときは同じであっても異なっていてもよい。Ｒ^２は炭素数１以上の１価の炭化水素基を表し、Ｒ^３は炭素数２〜４の２価の脂肪族炭化水素基を表し、Ｒ^４は炭素数１〜６の１価の炭化水素基を表す。〔Ｏ−（Ｒ^３Ｏ）_ｈ−Ｒ^２〕はオキシアルキレン基含有アルコキシ基であり、複数のときは同じであっても異なっていてもよい。ｈは１以上の整数である。（ＯＲ^４）は複数のときは同じであっても異なっていてもよい。ｊは１〜４の整数であり、ｋは１〜４のｋ≦ｊを満足する整数である。〕
（４） 前記シラン化合物（Ｂ）が、前記一般式（２）で表す、分子内に少なくとも１個の炭素数２以上のアルコキシ基を有するシラン化合物（Ｂ−１）と、前記一般式（３）で表す、分子内に少なくとも１個のオキシアルキレン基含有アルコキシ基を有するシラン化合物（Ｂ−２）との混合物である、前記（１）の湿気硬化型組成物。
（５） 前記炭素数２以上のアルコキシ基が、エトキシ基である、前記（２）又は（４）の湿気硬化型組成物。
（６） 前記シラン化合物（Ｂ−１）が、テトラエトキシシランである、前記（２）又は（４）の湿気硬化型組成物。
（７） 前記シラン化合物（Ｂ−２）が、下記一般式（４）で表す、アルコキシシラン化合物（ａ）と、下記一般式（５）で表す、オキシアルキレン基含有モノオール（ｂ）との反応生成物である、前記（３）又は（４）の湿気硬化型組成物。
Ｒ_４−ｊＳｉ（ＯＲ^４）_ｊ （４）
〔但し、（４）式中、Ｒは炭素数１〜６の１価の炭化水素基を表し、Ｒが複数のときは同じであっても異なっていてもよい。Ｒ^４は炭素数１〜６の１価の炭化水素基を表し、（ＯＲ^４）が複数のときは同じであっても異なっていてもよい。ｊは１〜４の整数である。〕
ＨＯ−（Ｒ^３Ｏ）_ｈ−Ｒ^２ （５）
〔但し、（５）式中、Ｒ^２は炭素数１以上の１価の炭化水素基を表し、Ｒ^３は炭素数２〜４の２価の脂肪族炭化水素基を表す。ｈは１以上の整数である。〕
（８） 前記オキシアルキレン基が、オキシエチレン基である、前記（３）、（４）又は（７）の湿気硬化型組成物。
（９） 前記アルコキシシラン化合物（ａ）が、テトラエトキシシランである、前記（７）の湿気硬化型組成物。
（１０） 前記オキシアルキレン基含有モノオール（ｂ）が、エチレングリコールモノメチルエーテルである、前記（７）の湿気硬化型組成物。
（１１） 前記オキシアルキレン基含有モノオール（ｂ）が、ジエチレングリコールモノメチルエーテルである、前記（７）の湿気硬化型組成物。
（１２） 前記オキサゾリジン化合物（Ｄ）が、ウレタン結合含有オキサゾリジン化合物である、前記（１）〜（１１）のいずれかの湿気硬化型組成物。
（１３） 更に添加剤（Ｅ）を配合する、前記（１）〜（１２）のいずれかの湿気硬化型組成物。
（１４） イソシアネート基含有ウレタンプレポリマー（Ａ）と、下記一般式（１）で表す、分子内に少なくとも１個のメトキシ基以外のアルコキシ基を有するシラン化合物（Ｂ）及び／又は該シラン化合物（Ｂ）の部分加水分解縮合物（Ｃ）と、オキサゾリジン化合物（Ｄ）とからなること、を特徴とする湿気硬化型シーリング材。
Ｒ_４−ｎＳｉＸ_ｎ （１）
〔但し、（１）式中、Ｒは炭素数１〜６の１価の炭化水素基を表し、Ｒが複数のときは同じであっても異なっていてもよい。Ｘはアルコキシ基を表し、その少なくとも１個はメトキシ基以外のアルコキシ基であり、Ｘが複数のときは同じであっても異なっていてもよい。ｎは１〜４の整数である。〕 (1) Isocyanate group-containing urethane prepolymer (A) and silane compound (B) having at least one alkoxy group other than methoxy group in the molecule and / or the silane compound (A) and represented by the following general formula (1) A moisture-curable composition comprising a partially hydrolyzed condensate (C) of B) and an oxazolidine compound (D).
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, at least one of which is an alkoxy group other than a methoxy group, and when X is plural, they may be the same or different. n is an integer of 1-4. ]
(2) Said (1) whose said silane compound (B) is a silane compound (B-1) which has at least 1 C2-C2 or more alkoxy group in a molecule | numerator represented by following General formula (2). Moisture curable composition.
R _4-m Si- (OR ¹ ) _m (2)
[In the formula (2), R represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and when R is plural, they may be the same or different. R ¹ is a monovalent hydrocarbon group having 1 or more carbon atoms, but at least one of (OR ¹ ) is an alkoxy group having 2 or more carbon atoms. When there are a plurality of (OR ¹ ), they may be the same or different. m is an integer of 1-4. ]
(3) In the above (1), the silane compound (B) is a silane compound (B-2) represented by the following general formula (3) and having at least one oxyalkylene group-containing alkoxy group in the molecule. Moisture curable composition.

[In the formula (3), R represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and when R is plural, they may be the same or different. R ² represents a monovalent hydrocarbon group having 1 or more carbon atoms, R ³ represents a divalent aliphatic hydrocarbon group having 2 to ⁴ carbon atoms, and R ⁴ represents a monovalent carbon group having 1 to 6 carbon atoms. Represents a hydrogen group. [O— (R ³ O) _h —R ² ] is an oxyalkylene group-containing alkoxy group, and when there are a plurality of them, they may be the same or different. h is an integer of 1 or more. (OR ⁴ ) may be the same or different when plural. j is an integer of 1 to 4, and k is an integer satisfying k ≦ j of 1 to 4. ]
(4) The silane compound (B-1) having at least one alkoxy group having 2 or more carbon atoms in the molecule, wherein the silane compound (B) is represented by the general formula (2), and the general formula (3) The moisture-curable composition according to (1), which is a mixture with a silane compound (B-2) having at least one oxyalkylene group-containing alkoxy group in the molecule.
(5) The moisture-curable composition according to (2) or (4), wherein the alkoxy group having 2 or more carbon atoms is an ethoxy group.
(6) The moisture-curable composition according to (2) or (4), wherein the silane compound (B-1) is tetraethoxysilane.
(7) The silane compound (B-2) is an alkoxysilane compound (a) represented by the following general formula (4) and an oxyalkylene group-containing monool (b) represented by the following general formula (5). The moisture-curable composition according to (3) or (4), which is a reaction product.
R _4-j Si (OR ⁴ ) _j (4)
[In the formula (4), R represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and when R is plural, they may be the same or different. R ⁴ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and when (OR ⁴ ) is plural, they may be the same or different. j is an integer of 1-4. ]
HO— (R ³ O) _h —R ² (5)
[In the formula (5), R ² represents a monovalent hydrocarbon group having 1 or more carbon atoms, and R ³ represents a divalent aliphatic hydrocarbon group having 2 to 4 carbon atoms. h is an integer of 1 or more. ]
(8) The moisture-curable composition according to (3), (4) or (7), wherein the oxyalkylene group is an oxyethylene group.
(9) The moisture-curable composition according to (7), wherein the alkoxysilane compound (a) is tetraethoxysilane.
(10) The moisture-curable composition according to (7), wherein the oxyalkylene group-containing monool (b) is ethylene glycol monomethyl ether.
(11) The moisture-curable composition according to (7), wherein the oxyalkylene group-containing monool (b) is diethylene glycol monomethyl ether.
(12) The moisture-curable composition according to any one of (1) to (11), wherein the oxazolidine compound (D) is a urethane bond-containing oxazolidine compound.
(13) The moisture-curable composition according to any one of (1) to (12), further including an additive (E).
(14) Isocyanate group-containing urethane prepolymer (A) and silane compound (B) having at least one alkoxy group other than methoxy group in the molecule and / or the silane compound represented by the following general formula (1) A moisture-curing sealant comprising the partial hydrolysis-condensation product (C) of B) and an oxazolidine compound (D).
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, at least one of which is an alkoxy group other than a methoxy group, and when X is plural, they may be the same or different. n is an integer of 1-4. ]

  For the first time according to the present invention, a rubber-like elastic body which is cured by moisture (humidity) and has excellent physical properties is obtained. Even in the case, it does not cause cracks on the surface after curing, and at the normal temperature as well as at low temperatures in winter, it exhibits the effect of preventing surface contamination immediately from the middle of curing after construction, and is excellent over a long period after curing. It has become possible to provide a moisture curable composition and a moisture curable sealing material having antifouling performance.

The present invention will be described in detail below.
In the present invention, the isocyanate group-containing urethane prepolymer (A) is one in which an isocyanate group reacts with moisture (humidity) in the atmosphere to form a urea bond to crosslink and cure, and an active hydrogen compound and an organic isocyanate are combined. It is obtained by reacting with active hydrogen (group) under an excess of isocyanate groups, and becomes a curing component in the moisture-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 resulting urethane prepolymer (A) has too few cross-linking points, and the moisture-curing composition is reduced in elongation and tensile strength, and rubber elasticity. If the physical properties and adhesiveness are poor and the molar ratio exceeds 10 / 1.0, the amount of carbon dioxide gas generated increases when reacting with moisture, which is not preferable.
Further, the isocyanate group content of the isocyanate group-containing urethane prepolymer (A) is preferably 0.3 to 15.0% by mass, more preferably 0.5 to 10% by mass, and particularly preferably 0.5 to 5.0% by mass. Is preferred. 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.

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. , 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.
Initiators include low molecular weight compounds such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, and diglycerin. Polyhydric alcohols; Low molecular weight polyhydric alcohols such as sorbitol, sucrose, glucose, lactose and sorbitan; Low molecular weight polyphenols such as bisphenol A and bisphenol F; Low molecular polyamines such as ethylenediamine and butylenediamine Low molecular weight amino alcohols such as monoethanolamine and diethanolamine; low molecular weight polycarboxylic acids such as adipic acid and terephthalic acid; alkylene oxide is reacted with at least one of them; Low molecular weight polyoxyalkylene polyol obtained Te are exemplified.
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.
Polyester polyols and polyester amide polyols are used as initiators for the synthesis of the known polyoxyalkylene polyols with dicarboxylic acids such as succinic acid, adipic acid and terephthalic acid, their acid esters and acid anhydrides. And a compound obtained by a dehydration condensation reaction with a compound containing two or more active hydrogens. 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.
As the polycarbonate polyol, a dehydrochlorination reaction between the low-molecular polyhydric alcohols used in the production of the polyoxyalkylene polyol and phosgene, or a transesterification reaction with diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, etc. The compound obtained from 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.
Any of these may be used alone or in combination of two or more.

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 moisture-curable composition obtained therefrom is low and the workability is good, and curing From the viewpoint of high rubber elastic properties and adhesion later, a polymer polyol is preferred, a polyoxyalkylene polyol is more preferred, and a polyoxypropylene polyol is 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 a moisture-moisture-curable functional group such as moisture. Specific examples include aliphatic monoisocyanates such as n-butyl monoisocyanate, n-hexyl monoisocyanate, n-tetradecyl monoisocyanate, n-hexadecyl monoisocyanate, octadecyl monoisocyanate, and n-chloroethyl monoisocyanate. It is done. These can be used alone or in admixture of two or more.

The organic polyisocyanate is a compound containing two or more isocyanate groups in the molecule. Specifically, the aromatic polyisocyanate in which the isocyanate group is bonded to the aromatic carbon, and the isocyanate group in the aliphatic carbon. Examples of the aromatic polyisocyanate include toluene diisocyanates such as 2,4-toluene diisocyanate and 2,6-toluene diisocyanate; 4,4′-diphenylmethane diisocyanate, 2, Diphenylmethane diisocyanates such as 4'-diphenylmethane diisocyanate and 2,2'-diphenylmethane diisocyanate; phenols such as 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate 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'-diisocyanate Etc. 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, Aliphatic polyisocyanates such as 6-hexamethylene diisocyanate, decamethylene diisocyanate and lysine diisocyanate; aromatic aliphatic polyisocyanates such as xylylene diisocyanates such as o-xylylene diisocyanate, m-xylylene diisocyanate and p-xylylene diisocyanate; 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.
Of these, aliphatic polyisocyanates are preferred, and aromatic fats are more preferable in that the viscosity of the resulting urethane prepolymer (A) can be lowered, and the weather resistance after curing of the resulting moisture-curable composition is good. Group polyisocyanate and alicyclic polyisocyanate are preferable, and isophorone diisocyanate is particularly preferable.

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 silane compound (B) having at least one alkoxy group other than methoxy group in the molecule and / or the partial hydrolysis condensate (C) of the silane compound (B) in the present invention will be described.
This component (B) and / or (C) is combined with the isocyanate group-containing urethane prepolymer (A), and when the resulting moisture-curable composition is exposed to moisture and cured, it is cured as well as cured. From the middle stage, no dust adheres to the surface, and even if a small amount adheres, it can be easily washed away with running water such as rain or shower, giving the effect of becoming a cured product surface with excellent anti-contamination properties . This is because the moisture curable composition is cured by moisture, and the component (B) and / or (C) is transferred (bleeded) to the surface of the moisture curable composition being cured and hydrolyzed by moisture. It is inferred that this is due to condensation with dealcoholization to form a hydrophilic film.
The component (B) and / or (C) may be a silane compound (B) alone having at least one alkoxy group other than a methoxy group in the molecule, or the silane compound (B). May be a multimer (partially hydrolyzed condensate) (C) in which a part of the alkoxy group is hydrolyzed and condensed with water, or the silane compound (B) and its part It means that the combination with a hydrolysis-condensation product (C) may be sufficient.

The silane compound (B) having at least one alkoxy group other than methoxy group in the molecule is a compound represented by the following general formula (1), and having at least one alkoxy group other than methoxy group in the molecule: It is.
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, at least one of which is an alkoxy group other than a methoxy group, and when X is plural, they may be the same or different. n is an integer of 1-4. ]
The R is a monovalent monovalent carbon 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, heptyl group, hexyl group and phenyl group. A hydrocarbon group is mentioned.
X is an alkoxy group, when n is 1, X is an alkoxy group other than a methoxy group, and when n is 2, 3, or 4, at least one is an alkoxy group other than a methoxy group. If all alkoxy groups are methoxy groups, the methanol generated by hydrolysis will be insufficiently cured due to the high reaction rate with the isocyanate groups of the isocyanate group-containing urethane prepolymer (A), and the effect of preventing contamination will be obtained. Since it is not exhibited, it is not preferable.

〔但し、（３）式中、Ｒは前記と同じ炭素数１〜６の１価の炭化水素基を表し、Ｒが複数のときは同じであっても異なっていてもよい。Ｒ^２は炭素数１以上の１価の炭化水素基を表し、Ｒ^３は炭素数２〜４の２価の脂肪族炭化水素基を表し、Ｒ^４は炭素数１〜６の１価の炭化水素基を表す。〔Ｏ−（Ｒ^３Ｏ）_ｈ−Ｒ^２〕はオキシアルキレン基含有アルコキシ基であり、複数のときは同じであっても異なっていてもよい。ｈは１以上の整数である。（ＯＲ^４）は複数のときは同じであっても異なっていてもよい。ｊは１〜４の整数であり、ｋは１〜４のｋ≦ｊを満足する整数である。〕
また、前記（Ｂ−１）成分と（Ｂ−２）成分の混合物も好適に使用できる。 Preferred 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, and an isopropoxy group, or an oxyalkylene group-containing alkoxy group. Therefore, the silane compound (B) represented by the general formula (1) is a silane compound (B-1) having at least one alkoxy group having 2 or more carbon atoms in the molecule represented by the following general formula (2) (that is, this) Can be divided into silane compounds (B-2) having at least one oxyalkylene group-containing alkoxy group in the molecule represented by the following general formula (3). it can.
(B-1): R _4-m Si- (OR ¹ ) _m (2)
[However, in the formula (2), R represents the same monovalent hydrocarbon group having 1 to 6 carbon atoms as described above, and when R is plural, they may be the same or different. R ¹ is a monovalent hydrocarbon group having 1 or more carbon atoms, but at least one of (OR ¹ ) is an alkoxy group having 2 or more carbon atoms. When there are a plurality of (OR ¹ ), they may be the same or different. m is an integer of 1-4. ]

[In the formula (3), R represents the same monovalent hydrocarbon group having 1 to 6 carbon atoms as described above, and when R is plural, they may be the same or different. R ² represents a monovalent hydrocarbon group having 1 or more carbon atoms, R ³ represents a divalent aliphatic hydrocarbon group having 2 to ⁴ carbon atoms, and R ⁴ represents a monovalent carbon group having 1 to 6 carbon atoms. Represents a hydrogen group. [O— (R ³ O) _h —R ² ] is an oxyalkylene group-containing alkoxy group, and when there are a plurality of them, they may be the same or different. h is an integer of 1 or more. (OR ⁴ ) may be the same or different when plural. j is an integer of 1 to 4, and k is an integer satisfying k ≦ j of 1 to 4. ]
Moreover, the mixture of the said (B-1) component and (B-2) component can also be used conveniently.

First, the silane compound (B-1) having at least one alkoxy group having 2 or more carbon atoms in the molecule represented by the general formula (2) will be described. Examples of R are the same as those in the general formula (1). The R ¹ O group is an alkoxy group having 2 or more carbon atoms when m is 1, and at least one is an alkoxy group having 2 or more carbon atoms when m is 2, 3 or 4. Specifically, as R ¹ , a monovalent hydrocarbon group having 1 to 6 carbon atoms 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. Preferred examples of the alkoxy group (R ¹ O group) include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a heptoxy group, a hexoxy group, and a phenoxy group.
More specifically, as the silane compound (B-1), tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyl Monomers such as tributoxysilane and dimethoxydiethoxysilane are exemplified. These can be used singly or in combination of two or more, among them, it is preferable that all in the molecule is an alkoxy group other than methoxy, in terms of high antifouling effect on the resulting moisture-curable composition, m is preferably 4, and the alkoxy group is preferably an ethoxy group. Therefore, most preferred is tetraethoxysilane.

Next, the silane compound (B-2) having at least one oxyalkylene group-containing alkoxy group in the molecule represented by the general formula (3) will be described. Examples of R are the same as those in the general formula (1). Specific examples of the R ⁴ O group include monovalent C 1-6 such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, heptoxy group, hexoxy group, and phenoxy group. The alkoxy group which consists of a hydrocarbon group is mentioned. The — [O— (R ³ O) _h —R ² ] group is an oxyalkylene group-containing alkoxy group, and the R ² group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, Examples thereof include monovalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms such as a butyl group and a hexyl group. Examples of the — (R ³ O) — group include carbons such as an oxyethylene group, an oxypropylene group, and an oxybutylene group. An oxyalkylene group composed of a divalent aliphatic hydrocarbon group of 2 to 4 is mentioned. The R ⁴ O group is preferably an ethoxy group, the R ² group is preferably a methyl group, and the — (R ³ O) — group is an oxy group in that the effect of imparting contamination prevention to the resulting moisture curable composition is high. An ethylene group is preferred. H is an integer of 1 or more, and h is preferably 1 or 2 for the same reason as described above.

前記一般式（４）で表すアルコキシシラン化合物（ａ）のＲは、前記一般式（１）のＲと同じものであり、Ｒとしては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ヘプチル基、ヘキシル基、フェニル基などの反応性の官能基を有しない炭素数１〜６の１価の炭化水素基が挙げられる。
Ｒ^４としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ヘプチル基、ヘキシル基、フェニル基などの炭素数１〜６の１価の炭化水素基が挙げられ、対応するアルコキシ基（ＯＲ⁴）として、それぞれメトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基、ヘプトキシ基、ヘキソキシ基、フェノキシ基などが挙げられる。
前記アルコキシシラン化合物（ａ）として、さらに具体的には、テトラメトキシシラン、ジメトキシジエトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトライソプロポキシシラン、テトラブトキシシラン、メチルトリエトキシシラン、メチルトリプロポキシシラン、メチルトリイソプロポキシシラン、メチルトリブトキシシラン等などの単量体が挙げられ、これらは単独又は２種以上を組み合わせて使用できるが、これらのうち、反応性が良好で、得られるオキシアルキレン基含有アルキルオキシ基を有するシラン化合物（Ｂ−２）の湿気硬化型組成物に対する汚染防止付与効果の高い点で、分子内のアルコキシ基の全てがメトキシ基以外のアルコキシ基であるのが好ましく、ｊは４が好ましく、アルコキシ基としてはエトキシ基が好ましい。したがってテトラエトキシシランが最も好ましい。
前記オキシアルキレン基含有モノオール（ｂ）としては、具体的には、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノプロピルエーテル、トリエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノプロピルエーテルなどが挙げられ、これらは単独又は２種以上組み合わせで使用できるが、これらのうち、得られる湿気硬化型組成物に対する汚染防止付与効果が高い点で、エチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテルが好ましい。
なお、前記アルコール置換反応は、ステンレス製やガラス製などの反応容器に、前記（ａ）成分と、前記（ｂ）成分を仕込み、反応触媒の存在下又は不存在下、反応溶媒の存在下又は不存在下に６０〜２００℃に加熱し、副生するアルコール（Ｒ^４ＯＨ）を反応系外に除去しながら置換反応を進める方法が挙げられる。 Moreover, as a method of obtaining this silane compound (B-2),
(I) A method of subjecting an alkoxysilane such as ethoxysilane to an alcohol substitution reaction with a compound having a hydroxyl group and an oxyalkylene group,
(B) A method of subjecting a halogenated silane such as tetrachlorosilane to an alcohol substitution reaction of a compound having a hydroxyl group and an oxyalkylene group alone or a mixture of alkyl monools such as ethanol,
However, the method (A) is preferred because it is easy to obtain and synthesize raw materials.
The method (a) will be specifically described. The alkoxysilane compound (a) represented by the following general formula (4) is subjected to an alcohol substitution reaction with the oxyalkylene group-containing monool (b) represented by the following general formula (5). Thus, by introducing an oxyalkylene group-containing alkoxy group, a silane compound (B-2) having at least one oxyalkylene group-containing alkyloxy group in the molecule represented by the general formula (3) can be obtained. . The alcohol substitution reaction is represented by the general formula (6).
(A): R _4-j Si (OR ⁴ ) _j (4)
[In the formula (4), R represents the same monovalent hydrocarbon group having 1 to 6 carbon atoms as described above, and when R is plural, they may be the same or different. R ⁴ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and when (OR ⁴ ) is plural, they may be the same or different. j is an integer of 1-4. ]
(B): HO— (R ³ O) _h —R ² (5)
[In the formula (5), R ² represents a monovalent hydrocarbon group having 1 or more carbon atoms in the general formula (3), and R ³ represents a divalent hydrocarbon group having 2 to 4 carbon atoms in the general formula (3). Represents an aliphatic hydrocarbon group. h is an integer of 1 or more. ]

R of the alkoxysilane compound (a) represented by the general formula (4) is the same as R in the general formula (1), and R includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group. , A monovalent hydrocarbon group having 1 to 6 carbon atoms and having no reactive functional group such as isobutyl group, heptyl group, hexyl group, and phenyl group.
Examples of R ⁴ include a monovalent hydrocarbon group having 1 to 6 carbon atoms 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 of the alkoxy group (OR ⁴ ) include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, heptoxy group, hexoxy group, and phenoxy group.
More specifically, as the alkoxysilane compound (a), tetramethoxysilane, dimethoxydiethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltriethoxysilane, methyltripropoxysilane And monomers such as methyltriisopropoxysilane, methyltributoxysilane, etc., and these can be used alone or in combination of two or more thereof. Among these, the reactivity is good, and the resulting oxyalkylene group It is preferable that all of the alkoxy groups in the molecule are alkoxy groups other than methoxy groups in terms of high antifouling effect on the moisture-curable composition of the silane compound (B-2) having an alkyloxy group. Is preferably 4. As the alkoxy group, Butoxy group is preferred. Therefore, tetraethoxysilane is most preferred.
Specific examples of the oxyalkylene group-containing monool (b) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol. Monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether , Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, etc., and these can be used alone or in combination of two or more thereof. Among these, the resulting moisture-curable composition Ethylene glycol monomethyl ether and diethylene glycol monomethyl ether are preferred in that they have a high anti-contamination effect.
In the alcohol substitution reaction, the component (a) and the component (b) are charged into a reaction vessel made of stainless steel or glass, and in the presence or absence of a reaction catalyst, in the presence of a reaction solvent or A method of proceeding the substitution reaction while heating to 60 to 200 ° C. in the absence and removing the by-produced alcohol (R ⁴ OH) out of the reaction system can be mentioned.

Next, the partial hydrolysis-condensation product (C) component of the silane compound (B) having at least one alkoxy group other than methoxy group in the molecule will be described. This is a small amount of water of less than ½ of the number of moles of the alkoxy group contained in one or more of the silane compound (B) in the presence or absence of a solvent. Is a multimer that is hydrolyzed and condensed linearly or three-dimensionally. The number of molecules to be condensed is preferably 2 to 20 molecules, particularly preferably 2 to 15 molecules, from the viewpoint of good film forming properties.
Moreover, the partial hydrolysis-condensation product (C) component of the said silane compound (B) is a partial hydrolysis-condensation product of a silane compound (B-1), and does not have an oxyalkylene group containing alkoxy group in a molecule | numerator (C- 1) and a partially hydrolyzed condensate of silane compound (B-2) (C-2) containing an oxyalkylene group in the molecule. The partial hydrolysis-condensation product (C-2) may be one obtained by introducing an oxyalkylene group-containing alkoxy group into the above (C-1) (C-2A), or an oxyalkylene group-containing alkoxy group. (C-2B) may be used which is obtained by partially hydrolyzing and condensing the monomer having (C-2A) from the viewpoint of easy availability of raw materials and ease of production.
In addition, as a commercial item of the partial hydrolysis-condensation product (C-1) of a silane compound (B-1), for example, ethyl silicate 40 (average) which is a partial hydrolysis-condensation product of tetraethoxysilane made by Colcoat Co. Pentamer), ethyl silicate 48 (average about 10-mer); EMS-485 (average about 10-mer), which is a partial hydrolysis-condensation product of diethoxydimethoxysilane, and the like. Although the above can be used in combination, a partially hydrolyzed condensate of tetraethoxysilane is preferred in that it has excellent film-forming properties and excellent antifouling performance and weather resistance.
In addition, in the component (B) and / or (C), as a preferable one, a small amount of a methoxy group exists as an impurity by selecting a raw material even if a compound consisting of all alkoxy groups other than a methoxy group is selected. If the amount of the methoxy group is 10% by mass or less, preferably 5% by mass or less of the component (B) and / or (C), the moisture-curable composition obtained is cured. No adverse effects such as a decrease in rubber elastic properties and a decrease in the effect of imparting contamination prevention.

  The amount of the component (B) and / or (C) 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 (A). . If it is less than 0.01 part by mass, the effect of imparting contamination prevention is small, and if it exceeds 20 parts by mass, the amount of monoalcohol generated by hydrolysis increases and reacts with the isocyanate group of component (A) to cause poor curing. It is not preferable.

Next, the oxazolidine compound (D) in the present invention will be described.
The oxazolidine compound (D) is a compound having one or more, preferably 2 to 6, oxazolidine rings in the molecule, which is a saturated 5-membered heterocyclic ring containing an oxygen atom and a nitrogen atom, and an isocyanate group-containing urethane prepolymer It functions as the latent curing agent (A). In addition, the oxazolidine compound (D) includes the isocyanate group-containing urethane prepolymer (A), a silane compound (B) having at least one alkoxy group other than a methoxy group in the molecule, and / or a silane compound ( When the moisture curable composition is cured by blending with the moisture curable composition comprising the partially hydrolyzed condensate (C) of B), the components (B) and / or (C) bleed on the surface. Thus, a cured film is formed, and the effect of preventing contamination is exhibited, while it has an effect of preventing defects that cause cracks on the surface of the cured product. Although the mechanism for preventing the occurrence of cracks is not clear, when the (B) and / or (C) components are hydrolyzed by moisture on the cured product surface and further condensed to form a film, the film is hard and brittle. In the same way, curing of the component (B) and / or (C) is caused by the action of the secondary amino group and alcoholic hydroxyl group produced by hydrolysis of the oxazolidine compound (D) bleed on the surface of the cured product. It is presumed that the film becomes flexible and prevents the occurrence of cracks.
The function of the oxazolidine compound (D) as a latent curing agent will be described. When the isocyanate group of the urethane prepolymer (A) reacts with moisture, it forms a urea bond and cures. In the cured product, bubbles due to carbon dioxide gas are generated, resulting in inconveniences such as deterioration in appearance, rupture of the cured product, and decrease in adhesiveness. ) Is exposed to moisture, the oxazolidine ring of the oxazolidine compound (D) is hydrolyzed by moisture to regenerate secondary amino groups and alcoholic hydroxyl groups before the moisture reacts with the isocyanate groups. These active hydrogens (groups) react with the isocyanate groups and cure without generating carbon dioxide gas. Foaming by carbon dioxide gas curable composition comprising prevented.
Specifically, the oxazolidine compound (D) is a urethane group (urethane bond) -containing oxazolidine obtained by reacting a hydroxyl group of a hydroxyl group-containing oxazolidine compound with an isocyanate group of an organic isocyanate compound or a carboxyl group of an organic carboxylic acid compound. Examples include compounds, ester group-containing oxazolidine compounds, and carbonate group-containing oxazolidine compounds, and urethane bond-containing oxazolidine compounds are preferred because they are easy to produce and have low viscosity.

Specifically, as the urethane bond-containing oxazolidine compound, the hydroxyl group of the hydroxyl group-containing oxazolidine compound and the isocyanate group of the organic isocyanate compound have an isocyanate group / hydroxyl molar ratio in the range of 0.9 to 1.2, preferably Examples thereof include those obtained by reacting at a temperature of 50 to 120 ° C. in the presence or absence of an organic solvent.
Examples of the organic isocyanate compound used for the synthesis of the urethane bond-containing oxazolidine compound include the same organic isocyanates used for the synthesis of the aforementioned isocyanate group-containing urethane prepolymer (A), and the crystallinity of the urethane bond-containing oxazolidine compound. In terms of low solubility and excellent solubility, aliphatic polyisocyanates are preferred, and at least one selected from the group consisting of isophorone diisocyanate and hexamethylene diisocyanate is preferred, and hexamethylene diisocyanate is particularly preferred.
Examples of the hydroxyl group-containing oxazolidine compound include N-hydroxyalkyloxazolidine obtained by a dehydration condensation reaction between a secondary amino group of alkanolamine and a carbonyl group of a ketone compound or an aldehyde compound.
As a method for synthesizing this hydroxyl group-containing oxazolidine compound, the carbonyl group of the aldehyde or ketone is 1.0 mol or more, preferably 1.0 to 1.5 times mol, relative to 1.0 mol of the secondary amino group of alkanolamine. More preferred is a method of using 1.0 to 1.2 moles and performing a dehydration bonding reaction while heating and refluxing in a solvent such as toluene and xylene to remove by-product water.
Examples of the alkanolamine include diethanolamine, dipropanolamine, N- (2-hydroxyethyl) -N- (2-hydroxypropyl) amine and the like. Examples of the ketone compound include acetone, diethyl ketone, isopropyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, isobutyl ketone, methyl tert-butyl ketone, diisobutyl ketone, cyclopentanone, and cyclohexanone. Examples of the aldehyde compound include acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, 2-methylbutyraldehyde, n-hexylaldehyde, 2-methylpentylaldehyde, n-octylaldehyde, 3, 5 Aliphatic aldehydes such as 1,5-trimethylhexylaldehyde; aromatic aldehydes such as benzaldehyde, methylbenzaldehyde, trimethylbenzaldehyde, ethylbenzaldehyde, isopropylbenzaldehyde, isobutylbenzaldehyde, methoxybenzaldehyde, dimethoxybenzaldehyde, and trimethoxybenzaldehyde.
Any of these may be used alone or in combination of two or more.
Among these, as the alkanolamine, it is easy to produce a hydroxyl group-containing oxazolidine compound, has excellent antifoaming properties when the resulting moisture curable composition is cured, and has the ability to prevent surface cracking. Diethanolamine is preferred, and aldehyde compounds are preferred among ketone compounds or aldehyde compounds, and isobutyraldehyde, 2-methylpentylaldehyde, and benzaldehyde are more preferred. Specific examples thereof include 2-isopropyl-3- (2-hydroxyethyl) oxazolidine, 2- (1-methylbutyl) -3- (2-hydroxyethyl) oxazolidine, 2-phenyl-3- (2-hydroxy And ethyl) oxazolidine.

  The ester group-containing oxazolidine compound can be obtained by a transesterification reaction between the hydroxyl group-containing oxazolidine compound described above and a lower alkyl ester of dicarboxylic acid or polycarboxylic acid.

The oxazolidine compound (D) has substantially no functional group that reacts with the isocyanate group of the isocyanate group-containing urethane prepolymer (A) at room temperature of 5 to 35 ° C. in the molecule. This “substantially free” means that, for example, a small amount of active hydrogen (group) may remain in the molecule due to the selection of the molar ratio in the synthesis of the above-mentioned urethane bond-containing oxazolidine compound. It means that it does not matter if it does not have to achieve the purpose.
The amount of the oxazolidine compound (D) used is such that the activity of the secondary amino group regenerated by hydrolysis of the oxazolidine compound (D) with respect to 1.0 mol of the isocyanate group in the isocyanate group-containing urethane prepolymer (A). It is preferable to use so that hydrogen may be 0.1 mol or more, and also 0.2-1.0 mol. If it is less than 0.1 mol, foaming prevention is insufficient, which is not preferable.

It is preferable to add an additive (E) to the moisture curable composition of the present invention.
Examples of the additive (E) include a weather resistance imparting agent, a filler, a thixotropic imparting agent, a storage stability improving agent (dehydrating agent), a colorant, a plasticizer, and a designability imparting agent. The compounds in the type can be appropriately selected according to the use, and can be used alone or in combination of two or more.

  The weather resistance imparting agent is blended to improve the weather resistance of the moisture curable composition of the present invention, and examples thereof include hindered amine light stabilizers, hindered phenol antioxidants, and UV absorbers. The hindered amine light stabilizer and the hindered phenol antioxidant are preferable in that the weather resistance imparting effect is high.

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 having a molecular weight of less than 1,000; 119FL, 2020FDL, 944FD, and 944LD of LA-63P, LA-68LD, and trade names CHIMASSORB series manufactured by Ciba Specialty Chemicals 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; 2- (4,6-diphenyl- 1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol and other triazine UV absorbers; benzophenone 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 weather resistance imparting agent 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).

The filler is blended for the purpose of reinforcing and increasing the moisture-curable composition of the present invention, and is mica, kaolin, zeolite, graphite, diatomaceous earth, white clay, clay, talc, slate powder, silicic anhydride, quartz. Fine powder, aluminum powder, zinc powder, synthetic silica such as precipitated silica, heavy calcium carbonate, light calcium carbonate, magnesium carbonate, alumina, calcium oxide, magnesium oxide and other inorganic powder fillers, glass fiber, carbon fiber, etc. Inorganic fillers such as fibrous fillers of the above; or fillers whose surfaces are treated with organic substances such as fatty acids; wood flour, walnut flour, rice husk flour, pulp flour, cotton chips, rubber powder, further polyamide resin, Polyester resin, polyurethane resin, silicone resin, vinyl chloride resin, vinyl acetate resin, polyethylene and polypropylene Polyolefin resin such as len, organic resin such as thermoplastic resin such as acrylic resin, epoxy resin, phenol resin, urea resin, melamine resin, or powder of heat and moisture curable resin, magnesium hydroxide and aluminum hydroxide The flame retardant imparting fillers such as, etc. are also mentioned, and those having a particle size of 0.01 to 1,000 μm are preferable.
In order to achieve the object, the filler is preferably 1 part by mass or more, further 5 to 300 parts by mass, particularly 10 to 200 parts by mass with respect to 100 parts by mass of the isocyanate group-containing urethane prepolymer (A).

The thixotropic agent and the storage stability improver (dehydrating agent) impart thixotropic properties to the moisture-curable composition of the present invention, respectively, so as to suppress flow and prevent dripping (no slump). It is used for the purpose of removing moisture and improving storage stability.
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.
The thixotropic agent is 0.1 parts by mass or more, further 1 to 300 parts by mass, particularly 10 to 200 parts by mass with respect to 100 parts by mass of the isocyanate group-containing urethane prepolymer (A). preferable.

  Examples of the storage stability improving agent (dehydrating agent) include calcium oxide and p-toluenesulfonyl isocyanate which 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.
In addition, the storage stability improver (dehydrating agent) is used in an amount necessary to remove moisture in the system and improve the storage stability, and the colorant is also used in an amount necessary for coloring the desired color tone. do it.

The plasticizer is used to improve the workability by reducing the viscosity of the moisture curable composition, or to adjust the rubber elastic properties after curing. Examples of the plasticizer include dibutyl phthalate, Phthalic acid esters such as diheptyl phthalate, dioctyl phthalate, di (2-ethylhexyl) phthalate, diisononyl phthalate (DINP), butyl benzyl phthalate, butyl phthalyl butyl glycolate; non-aromatic 2 such as dioctyl adipate, dioctyl sebacate Basic acid esters; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Low molecular weight plasticizers having a molecular weight of less than 500 such as halogenated aliphatic compounds such as chlorinated paraffins, and high molecular weight types having a molecular weight of 500 or more As a plasticizer, Polyester plasticizers such as polyesters from 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, and ether And polyethers such as saccharide-based polyethers; polystyrenes such as poly-α-methylstyrene; low viscosity (meth) acrylic acid ester copolymers, and the like. 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).

A design-imparting agent can be added to moisture-curing compositions to assist in delustering the surface of the cured product, or to give the appearance of natural rough rocks by erasing the surface and providing irregularities. In particular, examples of those that impart matte properties include matt waxes, various waxes such as beeswax, carnauba wax, montan wax, paraffin wax, and stearic acid. And higher aliphatic compounds such as amides.
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 its shape is not only spherical, but also various shapes such as a cubic shape, a rectangular shape, and a confetti shape, and the balloon is slightly broken to such an extent that the effect of imparting irregularities to the moisture curable composition is not lost. Although it is mentioned, a spherical shape is preferable from the viewpoint of good workability of the moisture 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, these balloons coated or surface-treated can be used. For example, inorganic balloons surface-treated with a silane coupling agent, etc., organic balloons coated with calcium carbonate, talc, titanium oxide, etc. The thing which was done is also mentioned.
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.

In the present invention, since the secondary amine produced by hydrolysis of the oxazolidine compound (D) reacts with the isocyanate group of the isocyanate group-containing urethane prepolymer (A) and cures quickly, a curing accelerating catalyst is used. However, it can be used in order to increase the rate of hydrolysis and condensation of the alkoxy group of the component (B) and / or (C) and to speed up the expression of antifouling performance.
Specific examples of the curing accelerating catalyst 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 the metal chelate compound include dibutyltin bis (acetylacetonate), zirconium tetrakis (acetylacetonate), titanium tetrakis (acetylacetonate), aluminum tris (acetylacetonate), acetylacetone iron, and acetylacetone copper. 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.
Among these, a metal chelate compound is preferable and dibutyltin bis (acetylacetonate) is more preferable because of the high effect. The usage-amount of a hardening acceleration | stimulation catalyst is 0.001-5 mass parts with respect to 100 mass parts of isocyanate group containing urethane prepolymer (A), Furthermore, 0.01-2 mass parts is preferable.

Since the moisture-curable composition of the present invention has a low viscosity, it is not necessary to use an organic solvent or it can be used in an extremely small amount and does not release an environmental load substance, so that it is highly safe.
Any organic solvent may be used as long as it does not react with the isocyanate group of the isocyanate group-containing urethane prepolymer (A). For example, aliphatic solvents such as n-hexane, aromatics such as toluene and xylene, and the like. Examples thereof include group solvents, mineral spirits, naphthenes, petroleum fraction solvents such as kerosene and industrial gasoline, ester solvents such as ethyl acetate, ketone solvents such as methyl ethyl ketone, and carbonate solvents such as dimethyl carbonate.
From the viewpoint of safety, the organic solvent is preferably used in the moisture-curable composition so that it is less than 10% by mass, further less than 5% by mass, and further less than 1% by mass, and most preferably 0% by mass. And not to use.

Although it does not specifically limit as a manufacturing method of the moisture hardening type composition of this invention, Each component of said (A), (B) and / or (C), (D), and an additive as needed The one selected from the above is charged into a stirrer / mixer that can block moisture with stainless steel or iron, etc., patched or continuously under various conditions such as normal pressure, reduced pressure, pressurized pressure or nitrogen flow It can be produced by stirring and mixing. Examples of the stirring and mixing apparatus include planetary mixers, kneaders, agitators, nauta mixers, line mixers, and the like.
Since the produced moisture curable composition is thickened and cured by moisture, it is preferably packed and sealed in a container that can block moisture 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 moisture-curable composition is opened, and the object to be constructed is filled and applied using a manual or electric extrusion gun or a coating device.

  The moisture curable composition of the present invention can be used as a two-component type in which water or the like is mixed as a curing agent at the time of construction use. Therefore, it is suitable for use as a one-component moisture-curing type. The one-component moisture-curing type is preferable in that it does not cause inconvenience of curing failure due to measurement error or mixing failure like the two-component type.

Next, the use of the moisture curable composition of the present invention will be described.
The moisture curable composition of the present invention can be widely used as a sealing material, an adhesive, a waterproof coating film, etc. for buildings and civil engineering structures, but the moisture curable composition can be used during curing and for a long time after curing. The moisture-curing composition should be installed in a place where the surface after curing is easily exposed to dust and exposed to sunlight and rainwater, in order to maximize the characteristics of having excellent anti-contamination performance. It is preferable to use it.
In addition, the moisture-curable composition of the present invention exhibits excellent anti-contamination performance on the surface of the cured product even if the physical property after curing is designed to have a low elastic modulus and a high elastic rubber elasticity. Therefore, it is more preferable to use it as a sealing material for buildings and civil engineering structures.
It should be noted that, in the exterior wall joints of buildings formed with siding or metal curtain walls, etc., which this sealing material is the object of construction, after the applied sealing material is cured, the sealing material is cured without overcoating the surface. It is particularly preferable to use the moisture-curable composition of the present invention as a sealing material for exposed joints because joints where the surface of the object is directly exposed to the outdoor environment are collectively referred to as exposed joints.
In the sealing material, the physical properties after curing are low modulus and high elongation is JIS
A 1439 (1997, revised 2002) “Testing method of sealing material for building materials”, 4.21 Tensile adhesion test b) According to tensile test after curing, 50% tensile stress (M ₅₀ ) is 50 N / cm ² or less, It is preferably 30 N / cm ² or less, and the elongation at break (Eb) is 300% or more, preferably 500% or more.

Hereinafter, the present invention will be described in more detail with reference to examples.
Here, the one-component moisture-curing sealing material has been shown as an example of the moisture-curing composition, but is not limited thereto.

Synthesis Example 1 Synthesis of Isocyanate Group-Containing Urethane Prepolymer PU-1 Polyoxypropylenediol (Asahi Glass Co., Ltd.) was introduced into a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet tube and heating / cooling device while flowing nitrogen gas. 163 g of Exenol 3021, number average molecular weight 3,300) and 162 g of polyoxypropylene triol (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., Triol-MN-4000, number average molecular weight 4,000) are charged and stirred with isophorone diisocyanate ( Degussa Japan, VESTANAT IPDI, molecular weight 222) and 135 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd., Neostan U-100) as a reaction catalyst are added and heated to 70-80 ° C. for 4 hours. Reaction, the isocyanate group content is the theoretical value (2.81 The reaction was terminated at the time point when the amount%) or less, was synthesized an isocyanate group-containing urethane prepolymer PU-1.
The obtained isocyanate group-containing urethane prepolymer PU-1 was a viscous liquid transparent at room temperature with a measured isocyanate group content of 2.69% by mass and a viscosity of 8,000 mPa · s / 25 ° C. by titration.

[Synthesis Example 2] Synthesis of partial hydrolysis condensate (average pentamer) of tetraethoxysilane with ethylene glycol monomethyl ether substitution reaction product OES-1 Stirrer, thermometer, nitrogen seal tube, condenser and heating / cooling device 74.5 g of tetraethoxysilane partially hydrolyzed condensate (average pentamer) (manufactured by Colcoat, ethyl silicate 40, molecular weight (average value) 745.2) while flowing nitrogen gas into the attached reaction vessel , 30.4 g of ethylene glycol monomethyl ether (molecular weight 76.1) and 0.01 g of tert-butyl titanate as a reaction catalyst were added and heated while stirring to distill off the by-produced ethanol out of the system. Continued. The distillation start temperature of by-product ethanol was 100 ° C., and the reaction was terminated when ethanol distillation stopped at 160 ° C. after 2 hours. Cooling and partial hydrolysis condensate of tetraethoxysilane (average pentamer) ) Of ethylene glycol monomethyl ether substitution reaction product OES-1. At this time, the amount of byproduct ethanol distilled off was 18 g. The obtained reaction product OES-1 was a translucent liquid.

[Synthesis Example 3] Synthesis of partial hydrolysis-condensation product of tetraethoxysilane (average about 10-mer) diethylene glycol monomethyl ether substitution reaction product OES-2 In a reaction vessel similar to Synthesis Example 2, while flowing nitrogen gas, tetra 140 g of partially hydrolyzed condensate of ethoxysilane (average about 10-mer) (manufactured by Colcoat, ethyl silicate 48, molecular weight 1400), 60 g of diethylene glycol monomethyl ether (molecular weight 120), and tert-butyl titanate as a reaction catalyst The alcohol substitution reaction was continued while adding 0.01 g and heating with stirring to distill off the by-product ethanol out of the system. The distillation start temperature of by-product ethanol is 100 ° C., and the reaction is terminated when ethanol distillation stops at 160 ° C. after 3 hours, and the product is cooled and partially hydrolyzed condensate of tetraethoxysilane (average about 10 volumes) Body) diethylene glycol monomethyl ether (23 mol%) substitution reaction product OES-2 was synthesized. At this time, the amount of byproduct ethanol distilled off was 22 g. The obtained reaction product OES-2 was a translucent liquid.

[Synthesis Example 4] Synthesis of Urethane Bond-Containing Oxazolidine Compound O-1 Diethanolamine (molecular weight 105) was placed in a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube, ester tube and heating / cooling device under a nitrogen stream. 435g and 183g of toluene were added, and 328g of isobutyraldehyde (molecular weight 72.1) was added while stirring, followed by heating and continuing the reflux dehydration reaction at 110-150 ° C for 3 hours, and by-produced water (74.5g) Was removed from the system. After completion of the reaction, the mixture was further heated under reduced pressure (50 to 70 hPa) to remove toluene and unreacted isobutyraldehyde to obtain N-hydroxyethyl-2-isopropyloxazolidine as an intermediate reaction product.
Next, 341 g of hexamethylene diisocyanate (molecular weight 168) was added to 659 g of the obtained N-hydroxyethyl-2-isopropyloxazolidine, and the mixture was heated at 80 ° C. for 8 hours. The time when the measured isocyanate group content by titration was 0.0% by mass was taken as the reaction end point, and Compound O-1 having two oxazolidine rings by urethane bonds in the molecule was obtained. The obtained urethane bond-containing oxazolidine compound O-1 was a translucent 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 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. 20 g of heavy calcium carbonate dried in a drier to a moisture content of 0.05% by mass or less, 100 g of fatty acid surface-treated calcium carbonate (Shiraishi Kogyo Co., Ltd., Shiruka Hana CCR), 10 g of titanium oxide, and diisononyl phthalate (DINP) 40 g was sequentially charged and mixed until the contents were uniform. Next, 1 g of hindered phenol-based antioxidant (Ciba Specialty Chemicals, IRGANOX 1010, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]), p -0.3 g of toluenesulfonyl monoisocyanate, 0.3 g of tetraethoxysilane (manufactured by Colcoat, ethyl silicate 28, monomer), 12 g of the urethane bond-containing oxazolidine compound O-1 obtained in Synthesis Example 4, 0.03 g of dibutyltin bis (acetylacetonate) (manufactured by Nitto Kasei Co., Ltd., Neostan U-220) was charged and further mixed until the contents were uniform. Subsequently, degassed under reduced pressure at 50 to 100 hPa, filled in a container, and sealed to prepare a one-component moisture-curing sealing material S-1.
The obtained one-component moisture-curing sealing material S-1 was a white pasty liquid at room temperature.

Example 2
In the same manner as in Example 1, except that 2 g of tetraethoxysilane (monomer) was used, a one-paste moisture-curing sealing material S-2 as a white pasty liquid was prepared at room temperature.

Example 3
In Example 1, instead of tetraethoxysilane (monomer), the same procedure except that 2 g of tetraethoxysilane partially hydrolyzed condensate (average pentamer) (manufactured by Colcoat, ethyl silicate 40) was used. A one-component moisture-curing sealing material S-3, which is a white pasty liquid at room temperature, was prepared.

Examples 4 and 5
In Example 1, instead of tetraethoxysilane (monomer), partially hydrolyzed condensate of tetraethoxysilane (average about 10-mer) (produced by Colcoat Co., ethyl silicate 48) was 0.5 g and 3 g, respectively. In the same manner except that it was used, one-component moisture-curing sealing materials S-4 and S-5, each of which was a white pasty liquid at room temperature, were prepared.

Example 6
In Example 1, 1 g of tetraethoxysilane was used, and 1 g of tetraethoxysilane partially hydrolyzed condensate (average about 10-mer) (Colcoat Co., ethyl silicate 48) was used. A white paste liquid 1-component moisture curable sealing material S-6 was prepared.

Examples 7 and 8
In Example 1, instead of tetraethoxysilane (monomer), an ethylene glycol monomethyl ether substitution reaction product OES-1 of a partial hydrolysis condensate (average pentamer) of tetraethoxysilane obtained in Synthesis Example 2 was used. In the same manner except that 5 g and 8 g were used, respectively, white paste liquid 1-component moisture curable sealing materials S-7 and S-8 were prepared at room temperature.

Examples 9, 10
In Example 1, instead of tetraethoxysilane (monomer), diethylene glycol monomethyl ether substitution reaction product OES-2 of the partial hydrolysis condensate (average about 10-mer) of tetraethoxysilane obtained in Synthesis Example 3 was used. In the same manner except that 5 g and 8 g were used, respectively, white paste-like liquid one-component moisture-curable sealing materials S-9 and S-10 were prepared at room temperature.

Example 11
In Example 1, instead of tetraethoxysilane, 3 g of ethylene glycol monomethyl ether-substituted reaction product OES-1 of the partial hydrolysis-condensation product (average pentamer) of tetraethoxysilane obtained in Synthesis Example 2 was used as a synthesis example. 1 liquid moisture of white paste liquid at room temperature in the same manner except that 3 g of diethylene glycol monomethyl ether substitution reaction product OES-2 of the partial hydrolysis-condensation condensate (average about 10-mer) of tetraethoxysilane obtained in 3 was used A curable sealing material S-11 was prepared.

Example 12
In Example 1, 1 g of tetraethoxysilane was used, and 3 g of diethylene glycol monomethyl ether substitution reaction product OES-2 of the partial hydrolysis-condensation condensate (average about 10-mer) of tetraethoxysilane obtained in Synthesis Example 3 was used. In the same manner, a one-part moisture-curing sealing material S-12, which is a white pasty liquid at room temperature, was prepared.

Comparative Example 1
In Example 1, except that tetraethoxysilane and urethane bond-containing oxazolidine compound O-1 were not used, a one-paste moisture-curing sealing material comparison S-1 as a white paste liquid was prepared at room temperature.

Comparative Example 2
In Example 1, 2 g of tetraethoxysilane was used and a one-part moisture-curing sealing material comparison S-2 of a white pasty liquid was prepared in the same manner except that the urethane bond-containing oxazolidine compound O-1 was not used. did.

Comparative Example 3
In Example 1, 2 g of a partially hydrolyzed condensate of tetraethoxysilane (average pentamer) (manufactured by Colcoat, ethyl silicate 40) was used instead of tetraethoxysilane, and urethane bond-containing oxazolidine compound O-1 was used. A one-part moisture-curing sealing material comparison S-3 as a white pasty liquid at room temperature was prepared in the same manner except that it was not used.

Comparative Example 4
In Example 1, 3 g of a partially hydrolyzed condensate of tetraethoxysilane (average about 10-mer) was used in place of tetraethoxysilane, and the urethane bond-containing oxazolidine compound O-1 was not used. A one-part moisture-curing sealant comparison S-4 as a white pasty liquid was prepared at room temperature.

Comparative Example 5
In Example 1, instead of tetraethoxysilane, 8 g of ethylene glycol monomethyl ether substitution reaction product OES-1 of the partial hydrolysis condensate (average pentamer) of tetraethoxysilane obtained in Synthesis Example 2 was used, and urethane was used. In the same manner except that the bond-containing oxazolidine compound O-1 was not used, a one-part moisture-curing sealing material comparison S-5 as a white pasty liquid was prepared at room temperature.

Comparative Example 6
In Example 1, 8 g of diethylene glycol monomethyl ether substitution reaction product OES-2 of the partial hydrolysis-condensation product of tetraethoxysilane (average about 10-mer) obtained in Synthesis Example 3 was used instead of tetraethoxysilane, and urethane was used. In the same manner except that the bond-containing oxazolidine compound O-1 was not used, a one-part moisture-curing sealing material comparison S-6 as a white pasty liquid was prepared at room temperature.

Comparative Example 7
In Example 1, 1 g of tetraethoxysilane was used, and 3 g of diethylene glycol monomethyl ether substitution reaction product OES-2 of the partial hydrolysis-condensation condensate (average about 10-mer) of tetraethoxysilane obtained in Synthesis Example 3 was used. In the same manner except that the urethane bond-containing oxazolidine compound O-1 was not used, a one-part moisture-curing sealing material comparison S-7 as a white pasty liquid was prepared at room temperature.

Comparative Example 8
In Example 1, except that tetraethoxysilane was not used, a one-part moisture-curing sealing material comparison S-8, which was a white pasty liquid at room temperature, was prepared in the same manner.

〔Test method〕
Using the 1 liquid moisture hardening type sealing materials S-1 to S-12 obtained in Examples 1 to 12 and the 1 liquid moisture hardening type sealing materials comparison S-1 to Comparative S-8 obtained in Comparative Examples 1 to 8 The test was conducted by the following test method. The result is shown to Tables 1-3 with a compounding composition.
1. Slump JIS A 1439 (1997, revised 2002) The slump (longitudinal) at 23 ° C. was measured by the 4.1 slump test in “Testing method of sealing material for building”.
2. Anti-foaming Lauan plywood is used as a base, and a square rod of Lauan is bonded in parallel on it to produce a joint of width 10mm x depth 10mm x length 150mm. One-part moisture-curing sealing material is foamed on this joint The specimen was filled so that there was no entanglement, and the excess sealing material was scraped off with a spatula to make the surface flat. The specimen was placed in a constant temperature and humidity chamber at 50 ° C. and 80% relative humidity for 2 days for accelerated curing, and then taken out. The cured sealing material was separated from the joint with a cutter, and the presence or absence of bubbles inside the cured product was visually observed. .
A case where cracks or bubbles due to foaming were not recognized or extremely small in the cured product was evaluated as ○, and a case where many foams were observed was evaluated as ×.
3. Contamination (a) Contamination during curing (after 1 day of indoor curing) On the surface of a slate plate having a thickness of 5 mm, a slate plate cut into a strip shape having a thickness of 5 mm and a width of 20 mm is arranged in a square frame shape, and an adhesive is used. Use this to make a joint of depth 5mm x width 20mm x length 150mm, fill this joint with a one-component moisture-curing sealant, scrape off any excess with a spatula, and flatten the surface. A test body was obtained.
The required number of specimens were prepared and immediately placed horizontally in a room at 23 ° C. and 50% relative humidity. After 1 day, black quartz sand (particle size: 70 to 110 μm) was sprinkled on the surface of the test specimen, and then the specimen was immediately turned over and the bottom was 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.
At this time, when the surface of the test specimen was lightly touched with a finger, the sealing material did not adhere to the finger and the surface was cured, but the interior was not cured.
Judgment criteria ○: Black silica sand is hardly adhered to the surface and the surface is clean.
X: A state in which a large amount of black silica sand adheres to the surface and is stained black.
(B) Contamination after curing (7 days after indoor curing) In the contamination test during curing, except that the test specimen was placed in a room at 23 ° C. and 50% relative humidity and then sprinkled with black silica sand after 7 days. Were similarly tested for soiling after curing.
Judgment criteria ○: Black silica sand is hardly adhered to the surface and the surface is clean.
X: A state in which a large amount of black silica sand adheres to the surface and is stained black.
(C) Contamination after outdoor exposure (after one month) After preparing the required number of specimens similar to those prepared in the contamination test during curing, and placing them in a room at 23 ° C. and 50% relative humidity for one day In the vicinity of an intersection with a lot of outdoor traffic, the surface of the joint was placed in the direction facing the road, and the length was set vertically to expose it. After 1 month, the test body was removed, the state of contamination due to dust adhesion on the surface of the test body was visually observed, and the contamination after 1 month of outdoor exposure 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 the surface is black and dirty.
4). Presence or absence of cracks on the surface of the cured product A necessary number of test specimens similar to those prepared in the contamination test during the curing were prepared and placed in a room at 23 ° C. and 50% relative humidity for 7 days, and with this Separately, after being placed in a room at 23 ° C and 50% relative humidity for one day, it is installed near the intersection where there is a lot of outdoor traffic, with the surface of the joint facing the road, with its length direction vertical. The surface of each cured sealant after exposure for 1 month was visually observed, and the case where cracks were not observed on the surface was evaluated as ◯, and the surface where cracks were observed was evaluated as x.

Claims (14)

Of the isocyanate group-containing urethane prepolymer (A) and the silane compound (B) represented by the following general formula (1) and having at least one alkoxy group other than a methoxy group in the molecule and / or the silane compound (B) A moisture-curable composition comprising a partially hydrolyzed condensate (C) and an oxazolidine compound (D).
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, at least one of which is an alkoxy group other than a methoxy group, and when X is plural, they may be the same or different. n is an integer of 1-4. ] Moisture according to claim 1, wherein the silane compound (B) is a silane compound (B-1) represented by the following general formula (2) and having at least one alkoxy group having 2 or more carbon atoms in the molecule. A curable composition.
R _4-m Si- (OR ¹ ) _m (2)
[In the formula (2), R represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and when R is plural, they may be the same or different. R ¹ is a monovalent hydrocarbon group having 1 or more carbon atoms, but at least one of (OR ¹ ) is an alkoxy group having 2 or more carbon atoms. When there are a plurality of (OR ¹ ), they may be the same or different. m is an integer of 1-4. ] The moisture curing according to claim 1, wherein the silane compound (B) is a silane compound (B-2) having at least one oxyalkylene group-containing alkoxy group in the molecule, represented by the following general formula (3). Mold composition.

[In the formula (3), R represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and when R is plural, they may be the same or different. R ² represents a monovalent hydrocarbon group having 1 or more carbon atoms, R ³ represents a divalent aliphatic hydrocarbon group having 2 to ⁴ carbon atoms, and R ⁴ represents a monovalent carbon group having 1 to 6 carbon atoms. Represents a hydrogen group. [O— (R ³ O) _h —R ² ] is an oxyalkylene group-containing alkoxy group, and when there are a plurality of them, they may be the same or different. h is an integer of 1 or more. (OR ⁴ ) may be the same or different when plural. j is an integer of 1 to 4, and k is an integer satisfying k ≦ j of 1 to 4. ]   The silane compound (B) is represented by the general formula (2), and the silane compound (B-1) having at least one alkoxy group having 2 or more carbon atoms in the molecule is represented by the general formula (3). The moisture-curable composition according to claim 1, which is a mixture with a silane compound (B-2) having at least one oxyalkylene group-containing alkoxy group in the molecule.   The moisture-curable composition according to claim 2 or 4, wherein the alkoxy group having 2 or more carbon atoms is an ethoxy group.   The moisture-curable composition according to claim 2 or 4, wherein the silane compound (B-1) is tetraethoxysilane. Reaction product of an alkoxysilane compound (a) represented by the following general formula (4) and an oxyalkylene group-containing monol (b) represented by the following general formula (5), wherein the silane compound (B-2) is represented by the following general formula (4): The moisture-curable composition according to claim 3 or 4, wherein
R _4-j Si (OR ⁴ ) _j (4)
[In the formula (4), R represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and when R is plural, they may be the same or different. R ⁴ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and when (OR ⁴ ) is plural, they may be the same or different. j is an integer of 1-4. ]
HO— (R ³ O) _h —R ² (5)
[In the formula (5), R ² represents a monovalent hydrocarbon group having 1 or more carbon atoms, and R ³ represents a divalent aliphatic hydrocarbon group having 2 to 4 carbon atoms. h is an integer of 1 or more. ]   The moisture-curable composition according to claim 3, 4 or 7, wherein the oxyalkylene group is an oxyethylene group.   The moisture-curable composition according to claim 7, wherein the alkoxysilane compound (a) is tetraethoxysilane.   The moisture-curable composition according to claim 7, wherein the oxyalkylene group-containing monool (b) is ethylene glycol monomethyl ether.   The moisture-curable composition according to claim 7, wherein the oxyalkylene group-containing monool (b) is diethylene glycol monomethyl ether.   The moisture curable composition according to any one of claims 1 to 11, wherein the oxazolidine compound (D) is a urethane bond-containing oxazolidine compound.   Furthermore, the moisture hardening type composition as described in any one of Claims 1-12 which mix | blends an additive (E). Of the isocyanate group-containing urethane prepolymer (A) and the silane compound (B) represented by the following general formula (1) and having at least one alkoxy group other than a methoxy group in the molecule and / or the silane compound (B) A moisture-curing sealant comprising a partially hydrolyzed condensate (C) and an oxazolidine compound (D).
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, at least one of which is an alkoxy group other than a methoxy group, and when X is plural, they may be the same or different. n is an integer of 1-4. ]