JP4959374B2 - Curable composition - Google Patents

Description

  The present invention relates to a curable composition containing an isocyanate group-containing urethane prepolymer.

  Conventionally, it contains an isocyanate group-containing urethane prepolymer as a curing component as a waterproofing sealant for exterior wall joints of buildings, resin sheets such as vinyl chloride sheets, adhesives or coating floors for building members such as tiles and wooden boards, etc. Excellent properties such as ease of work, high adhesiveness after curing, and wide range of rubber elastic properties after curing from low modulus to high modulus (high elongation to low elongation) Widely used.

As a recent trend, buildings and houses are required not only to maintain long-term structural durability, but also to improve stain resistance so that the roof and outer walls of the building maintain an aesthetic appearance without being stained for many years. Is also growing. Here, when a curable composition containing an isocyanate group-containing urethane prepolymer as a curing component is applied outdoors for applications such as an elastic sealing material for architectural use or a waterproof coating material, the surface after curing will be exposed to the outdoor environment. It will be exposed directly, and dust such as dust floating in the atmosphere and soot such as automobile exhaust gas will adhere to the surface of the cured product and become black, and the appearance of the building will deteriorate. There is a problem that causes the problem of end.
As a method for improving the stain resistance, a method of blending an isocyanate-terminated prepolymer derived from an aliphatic and / or alicyclic diisocyanate monomer with a photocurable substance or an unsaturated compound capable of reacting with oxygen (for example, a patent) Document 1 and Patent Document 2) have been proposed, but these methods have certain effects, but are still insufficient in terms of preventing pollution.

Japanese Patent Laid-Open No. 2002-37832 Japanese Patent Laid-Open No. 2002-37846

  In view of the above-mentioned conventional problems, the present invention relates to a curable composition containing an isocyanate group-containing urethane prepolymer, even if it is exposed to the outdoor environment for a long time after curing. It is an object of the present invention to provide a curable composition that has no stickiness) and is therefore not significantly contaminated by adhesion of dust or the like to the surface of the cured product, and is extremely excellent in antifouling properties.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained an isocyanate group obtained by reacting a first organic isocyanate compound comprising an aliphatic isocyanate compound with an active hydrogen-containing compound in a curable composition. The present invention was completed by finding that the presence of the second organic isocyanate compound in the containing urethane prepolymer allows the curable composition to exhibit remarkably excellent antifouling performance after curing.

  That is, this invention is a curable composition which has the characteristics of following (1)-(12).

(1) An isocyanate group-containing urethane prepolymer (A) obtained by reacting a first organic isocyanate compound (a-1) composed of an aliphatic isocyanate compound with an active hydrogen-containing compound (b); A curable composition comprising an organic isocyanate compound (a-2).

(2) The first organic isocyanate compound (a-1) and the second organic isocyanate compound (a-2) made of an aliphatic isocyanate compound are compounds having the same structure, Curable composition.

(3) The first organic isocyanate compound (a-1) composed of an aliphatic isocyanate compound and the second organic isocyanate compound (a-2) are compounds having different structures, according to the item (1). Curable composition.

(4) The 1st organic isocyanate compound (a-1) in which the said 2nd organic isocyanate compound (a-2) consists of an unreacted aliphatic isocyanate compound in the synthesis | combination of an isocyanate group containing urethane prepolymer (A). The curable composition according to item (1) or item (2).

(5) The curing according to any one of items (1) to (3), which is added when the second organic isocyanate compound (a-2) is used to produce a curable composition. Sex composition.

(6) The curable composition according to any one of items (1) to (5), wherein the second organic isocyanate compound (a-2) is an aliphatic isocyanate.

(7) The curable composition according to item (6), wherein the aliphatic isocyanate compound is hexamethylene diisocyanate.

(8) The curable composition according to (1), (3), or (5), wherein the second organic isocyanate compound (a-2) is octadecyl monoisocyanate.

(9) Any one of the items (1) to (8), wherein the amount of the second organic isocyanate compound (a-2) is 0.1 parts by mass or more in 100 parts by mass of the curable composition. The curable composition according to item.

(10) The curable composition according to any one of (1) to (9), further comprising an additive (B).

(11) The additive (B) is selected from the group consisting of a curing accelerator, a plasticizer, a weathering stabilizer, a filler, a thixotropic agent, an adhesion improver, a storage stability improver, and a colorant. The curable composition according to item (10), which is a seed or two or more kinds.

(12) The curable composition is used in a place where the cured surface of the curable composition is directly exposed to an outdoor environment. (1) Items 1 to 11 The curable composition as described in any one of the items).

  By setting it as said structure, the curable composition of this invention does not have the adhesiveness on the surface after hardening, and there exists an effect which exhibits the outstanding antifouling performance. And this curable composition is applied to a place where the curable composition is applied in a building or the like where the surface after curing of the curable composition is directly exposed to the outdoor environment and dust is likely to adhere. When used for a certain purpose, it is possible to maximize the effect of the excellent anti-contamination performance and maintain the aesthetic appearance of the building for many years.

  Each component used in the curable composition of the present invention will be described in detail below.

  First, the isocyanate group-containing urethane prepolymer (A) component will be described. The urethane prepolymer (A) component reacts the first organic isocyanate compound (a-1) composed of an aliphatic isocyanate compound and the active hydrogen-containing compound (b) under the condition of excess isocyanate groups with respect to active hydrogen. In the curable composition of the present invention, the isocyanate group contained reacts with moisture such as moisture in the atmosphere to form urea bonds and crosslinks and cures, thereby acting as a curing component. is there. In addition, by using an aliphatic isocyanate compound, the resulting curable composition exhibits non-yellowing or non-yellowing even when exposed to sunlight after curing, and has excellent weather resistance. Become.

  Specifically, the isocyanate group-containing urethane prepolymer (A) is a first organic isocyanate compound (a-) in a state of blocking moisture such as under a nitrogen gas stream in a reaction vessel made of glass or stainless steel. The molar ratio (isocyanate group / active hydrogen) of the isocyanate group of 1) to the active hydrogen (group) of the active hydrogen-containing compound (b) is preferably 1.5 to 5.0 / 1.0, more preferably 1. It can be obtained by reacting at a temperature of 50 to 100 ° C., in an amount of 5 to 3.0 / 1.0, in a batch charge or multistage charge, in the presence or absence of a reaction catalyst, preferably at a temperature of 50 to 100 ° C. . The isocyanate group content of the isocyanate group-containing urethane prepolymer (A) thus obtained is preferably 0.2 to 10.0% by mass, more preferably 0.4 to 5.0% by mass, and the number average molecular weight. Is preferably 1,000 to 100,000, more preferably 1,000 to 30,000. If the isocyanate group content is less than 0.2% by mass or the number average molecular weight exceeds 100,000, the crosslinking point in the prepolymer decreases and the adhesiveness decreases, the molecular weight increases too much, and the viscosity increases. Since workability deteriorates, it is not preferable. Further, when the isocyanate group content exceeds 10.0% by mass or the number average molecular weight is less than 1,000, it becomes difficult to prevent foaming due to the generation of carbon dioxide gas, or the cured product becomes brittle. It is not preferable.

  In addition, examples of the reaction catalyst include compounds similar to those exemplified as the metal catalyst among the curing accelerators described later.

  In the present specification, the number average molecular weight is a numerical value in terms of polystyrene measured by gel permeation chromatography (GPC).

  The first organic isocyanate compound (a-1) comprising an aliphatic isocyanate compound is an isocyanate compound in which an isocyanate group is bonded to an aliphatic hydrocarbon. Specifically, an aliphatic polyisocyanate and And aliphatic monoisocyanate optionally used for modifying the isocyanate group-containing urethane prepolymer (A).

  Examples of the aliphatic polyisocyanate include araliphatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate, and examples of the araliphatic polyisocyanate include xylylene diisocyanate. Includes hexamethylene diisocyanate, pentamethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, and examples of the alicyclic polyisocyanate include cyclohexane diisocyanate, methylene bis (cyclohexyl isocyanate), and isophorone diisocyanate.

  Moreover, the carbodiimide modified body, biuret modified body, allophanate modified body, dimer, trimer, etc. of these diisocyanates are also mentioned, These can be used individually or in combination of 2 or more types. Of these, aliphatic polyisocyanates are preferable in terms of excellent weather resistance and antifouling properties after curing, and xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate are more preferable. Diisocyanate is preferred.

  Moreover, n-butyl monoisocyanate, n-hexyl monoisocyanate, n-octadecyl monoisocyanate etc. are mentioned as an aliphatic monoisocyanate used by the case for modification | denaturation of an isocyanate group containing urethane prepolymer.

  As the active hydrogen-containing compound, in addition to a polymer polyol or polymer polyamine, a low molecular polyol, a low molecular amino alcohol, a low molecular polyamine, or a modification of an isocyanate group-containing urethane prepolymer as a chain extender used in some cases. For example, a polymer or a low molecular weight monool used depending on circumstances is used.

  Examples of the polymer polyol include polyester polyol, polycarbonate polyol, polyoxyalkylene polyol, hydrocarbon polyol, poly (meth) acrylate polyol, animal and plant polyol, these copolyols, or a mixture of two or more of these. Etc.

  The number average molecular weight of the polymer polyol is 500 or more, preferably 1,000 to 100,000, more preferably 1,000 to 30,000, and particularly preferably 1,000 to 20,000. When the number average molecular weight is less than 500, rubber elastic properties such as elongation after curing of the resulting curable composition deteriorate, and when it exceeds 100,000, the viscosity of the resulting isocyanate group-containing urethane prepolymer (A) is high. Since it becomes too much and workability | operativity deteriorates, it is unpreferable.

  Examples of the polyester polyol include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid, naphthalenedicarboxylic acid, triphthalic acid, and the like. One or more of polycarboxylic acids such as merit acid, or esters and acid anhydrides thereof, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3 -Butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9 -Nonanediol, diethylene glycol, dipropylene glycol , 1,4-cyclohexanedimethanol, ethylene oxide or propylene oxide adduct of bisphenol A, low molecular polyols such as trimethylolpropane, glycerin, pentaerythritol; butylenediamine, hexamethylenediamine, xylylenediamine, Low molecular polyamines such as isophorone diamine; polyester polyol or polyester amide polyol obtained by esterification reaction or transesterification reaction with one or more low molecular amino alcohols such as monoethanolamine and diethanolamine.

  Also, for example, lactone polyesters obtained by ring-opening polymerization of cyclic ester (lactone) monomers such as ε-caprolactone and γ-valerolactone using low molecular polyols, low molecular polyamines, and low molecular amino alcohols as initiators. A polyol is mentioned.

  Examples of the polycarbonate polyol include dehydrochlorination reaction of low molecular polyols and phosgene used for the synthesis of the above-described polyester polyol, or esters of the low molecular polyols with diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and the like. What is obtained by an exchange reaction is mentioned.

  Examples of the polyoxyalkylene polyol include low molecular polyols, low molecular polyamines, low molecular amino alcohols, polycarboxylic acids, sorbitol, mannitol, sucrose used for the synthesis of the above-described polyester polyols. 1 or more of cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using one or more of low molecular weight polyhydric alcohols such as saccharides such as glucose and low molecular weight polyphenols such as bisphenol A and bisphenol F as initiators A polyoxyethylene-based polyol, a polyoxypropylene-based polyol, a polyoxybutylene-based polyol, a polyoxyethylene, which is obtained by ring-opening addition polymerization or copolymerization (hereinafter, “polymerization or copolymerization” is referred to as (co) polymerization). Ramechiren polyols, poly - (oxyethylene) - (oxypropylene) - random or block copolymer polyols, further polyester polyether polyol initiator polyester polyols and polycarbonate polyols described above, such as polycarbonate polyether polyols. Moreover, the polyol which made these various polyols and organic isocyanate react by hydroxyl group excess with respect to an isocyanate group, and made the molecular terminal a hydroxyl group is also mentioned.

  The average number of alcoholic hydroxyl groups per molecule of the polyoxyalkylene polyol is preferably 2 or more, more preferably 2 to 4, particularly 2 to 3.

  Furthermore, the polyoxyalkylene-based polyol is produced at the time of production thereof by cesium hydride, cesium methoxide, cesium alkoxide such as cesium ethoxide, cesium-based compounds such as cesium hydroxide, diethyl zinc, iron chloride, metalloporphyrin, phosphazenium compound, The total unsaturation obtained by using a double metal cyanide complex such as a double metal cyanide complex such as a zinc hexacyanocobaltate glyme complex or diglyme complex as a catalyst is 0.1 meq / g or less. 07 meq / g or less, particularly 0.04 meq / g or less is preferable, and molecular weight distribution [ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene by gel permeation chromatography (GPC) = Mw / Mn] is 1.6 or less, especially 1.0 Having a narrow 1.3, viscosity of the resulting diisocyanate sulfonate group-containing urethane prepolymer can reduce, and rubber elasticity properties after curing of the resulting cured composition is preferable in that is good.

  For the modification of the isocyanate group-containing urethane prepolymer (A), a cyclic ether compound such as propylene oxide is subjected to ring-opening addition polymerization using a low-molecular monoalcohol such as methyl alcohol, ethyl alcohol or propyl alcohol as an initiator. In addition, polyoxyalkylene monools such as polyoxypropylene monools may be used in some cases.

  The “system” such as the polyoxyalkylene polyol or polyoxyalkylene monool is 50% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass of the portion excluding the hydroxyl group in 1 mol of the molecule. % Or more is composed of polyoxyalkylene, which means that the remaining part may be modified with ester, urethane, polycarbonate, polyamide, poly (meth) acrylate, polyolefin, etc., except for hydroxyl groups. Most preferably, 95% by mass or more of the molecules consist of polyoxyalkylene.

  Examples of hydrocarbon polyols include polyolefin polyols such as polybutadiene polyol and polyisoprene polyol; polyalkylene polyols such as hydrogenated polybutadiene polyol and hydrogenated polyisoprene polyol; halogenated poly such as chlorinated polypropylene polyol and chlorinated polyethylene polyol. Examples include alkylene polyols.

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

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

  As the chain extender, in addition to the low molecular weight polyols, polyamines and amino alcohols used in the synthesis of the polyester polyol, the polyoxyalkylene polyol described above has a low molecular weight with a number average molecular weight of less than 500, Or the mixture of these 2 or more types is illustrated.

  The compounds mentioned as the active hydrogen-containing compound can be used alone or in combination of two or more, but among these, the rubber elastic properties and adhesiveness of the resulting curable composition are good, High molecular polyols are preferred, polyoxyalkylene polyols are more preferred, and polyoxypropylene polyols are most preferred.

  Next, the 2nd organic isocyanate compound (a-2) component in this invention is demonstrated. After the second organic isocyanate compound (a-2) coexists with the isocyanate group-containing urethane prepolymer (A) component in the curable composition, the curable composition is cured by moisture such as moisture, The surface has no tackiness and exhibits an effect of imparting remarkably excellent antifouling performance. This is because when the curable composition is cured, a part of the second organic isocyanate compound (a-2) is transferred to the surface of the cured product, and an intermolecular isocyanate group and a hydrocarbon group (preferably a methylene group) are formed. This is presumed to prevent adhesion of dust by forming a film by forming a urea bond and curing the isocyanate group in the state of being aligned.

As a method for causing the second organic isocyanate compound (a-2) to be present in the curable composition,
(1) A method of allowing the isocyanate group-containing urethane prepolymer (A) to exist in the form of an unreacted first organic isocyanate compound (a-1) produced during synthesis
(2) A method of adding the second organic isocyanate compound (a-2) when producing the curable composition,
(3) It is made to exist in the form of the 1st organic isocyanate compound (a-1) which consists of an unreacted aliphatic isocyanate compound produced in the case of the synthesis | combination of an isocyanate group containing urethane prepolymer (A), and also a curable composition. A method of adding the second organic isocyanate compound (a-2) when producing
Etc. In the case of the method (1), the second organic isocyanate compound (a-2) is a compound having the same structure as the first organic isocyanate compound (a-1). In the case of the method (2), the second organic isocyanate compound (a-2) may be a compound having the same structure as the first organic isocyanate compound (a-1) or a compound having a different structure. There may be. In the case of the method (3), the second organic isocyanate compound (a-2) may be a compound having the same structure as that of the first organic isocyanate compound (a-1). A combination of a compound having the same structure as the organic isocyanate compound (a-1) and a compound having a different structure from the first organic isocyanate compound (a-1) may be used.

  In the methods (2) and (3), the second organic isocyanate compound (a-2) is added before and after charging the urethane prepolymer (A) when producing the curable composition. Or what was previously added to the urethane prepolymer (A) may be blended in the curable composition.

  The amount of the second organic isocyanate compound (a-2) to be present in the curable composition is preferably 0.1 parts by mass or more, more preferably 0.1 to 10 parts by mass in 100 parts by mass of the curable composition. In particular, 0.2 to 5 parts by mass is preferable. Moreover, 0.2 mass part or more is preferable with respect to 100 mass parts of isocyanate group containing urethane prepolymer (A), Furthermore, 0.2-20 mass parts, Especially 0.5-10 mass parts are preferable. Less than 0.1 parts by mass in 100 parts by mass of the curable composition and less than 0.2 parts by mass with respect to 100 parts by mass of the urethane prepolymer (A) are not preferable because there is no effect of preventing contamination.

  As the second organic isocyanate compound (a-2), a low molecular weight compound having a molecular weight of 1,000 or less, more preferably 500 or less is preferable because it easily migrates to the surface of the cured product as described above.

  The second organic isocyanate compound (a-2) includes 2,4-toluene diisocyanate in addition to the same compounds as the aliphatic isocyanate compounds mentioned in the synthesis of the isocyanate group-containing urethane prepolymer (A). Toluene diisocyanates (TDI) such as 2,6-toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, diphenylmethane diisocyanate (MDI) such as 2,4′-diphenylmethane diisocyanate, aromatic polyisocyanates such as naphthalene diisocyanate, Alternatively, these dimers, trimers and the like can also be mentioned, and these can be used alone or in combination of two or more thereof. Among these, the effect of imparting anti-staining to the curable composition is high, and hardly yellowing or no Yellowing An aliphatic isocyanate compound is preferred, and an aliphatic polyisocyanate and an aliphatic monoisocyanate are preferred. In particular, an aliphatic polyisocyanate is hexamethylene diisocyanate (HDI), and an aliphatic monoisocyanate is n-octadecyl monoisocyanate (ODI). Is preferred.

Next, the additive (B) that can be further blended in the curable composition of the present invention will be described.
Examples of the additive (B) include a curing accelerator, a plasticizer, a weather resistance stabilizer, a filler, a thixotropic agent, an adhesion improver, a storage stability improver (dehydrating agent), and a colorant.

  The curing accelerator is added to accelerate the reaction between the isocyanate group of the isocyanate group-containing urethane prepolymer (A) and moisture such as moisture to improve the curing rate of the curable composition of the present invention. For example, a metal catalyst, an amine catalyst, etc. are mentioned.

  Examples of the metal catalyst include metal alkoxides such as tetra-n-butyl titanate; metals such as zinc, tin, lead, zirconium, bismuth, cobalt, manganese, and iron, such as stannous octylate and tin octenoate. Salts with organic carboxylic acid compounds described later such as octyl acid and octenoic acid; metal chelate compounds such as dibutyltin bis (acetylacetonate), zirconium tetrakis (acetylacetonate), titanium tetrakis (acetylacetonate); dibutyltin Examples thereof include salts of organic metals such as dilaurate and dioctyltin dilaurate with organic carboxylic acid compounds described later.

  Examples of amine catalysts include triethylenediamine, triethylamine, tri-n-butylamine, hexamethylenetetramine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 1,4-diazabicyclo [2,2, 2] Tertiary amines such as octane (DABCO), N-methylmorpholine, N-ethylmorpholine, salts of these amines with organic carboxylic acid compounds described later, and the like.

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

  These can be used singly or in combination of two or more. Among these, a metal catalyst is preferred because of its excellent curing acceleration effect, and further, a metal chelate compound, an organic metal and an organic carboxylic acid compound. Salts are preferred, and dibutyltin acetylacetonate and dibutyltin dilaurate are particularly preferred.

  0.001-10 mass parts is preferable with respect to 100 mass parts of isocyanate group containing urethane prepolymer (A), and, as for the compounding quantity of the said hardening accelerator, 0.1-5 mass parts is more preferable. If the amount is less than 0.001 part by mass, the effect of accelerating the curing is small, and if it exceeds 10 parts by mass, the storage stability of the curable composition and the water resistance and heat resistance of the cured product are deteriorated.

  The plasticizer is used to lower the viscosity of the resulting curable composition to improve workability, and to adjust rubber elastic properties such as modulus and elongation after curing.

  Examples of the plasticizer include a low molecular weight plasticizer and a high molecular weight plasticizer. Specific examples of the low molecular weight plasticizer include dioctyl phthalate, dibutyl phthalate, diisononyl phthalate (DINP), and phthalic acid. Phthalates such as butylbenzyl; Aliphatic carboxylates such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate and butyl oleate; Phosphate esters such as trioctyl phosphate and tricresyl phosphate; chlorinated paraffins The thing of low molecular weight whose molecular weight is less than 500 is mentioned. Examples of the high molecular weight plasticizer include compounds having a number average molecular weight of 500 or more and having a polar group in the molecule and a liquid and relatively low viscosity at room temperature, and the polar group includes an ester group and an ether group. (Oxyalkylene group), urethane group and the like may be mentioned, and the number of these groups may be one or more in the molecule. Moreover, when it has two or more groups, the kind may be the same and may differ.

  The high molecular weight plasticizer will be described in more detail. The number average molecular weight is 500 to 50,000, more preferably 1,000 to 30,000, particularly preferably 1,000 to 20,000, and 1,000 to 10,000. Is most preferred. When the number average molecular weight exceeds 50,000, the viscosity of the plasticizer increases and the workability of the resulting curable composition is deteriorated.

  Moreover, it is preferable that a high molecular weight plasticizer is a compound which does not have the reactive functional group which exerts a bad influence on cured compositions, such as a hydroxyl group or isocyanate, in a molecule | numerator. This “substantially free” means that when a high molecular weight plasticizer is synthesized, a small amount of hydroxyl groups or isocyanate groups may remain in the obtained plasticizer depending on the molar ratio of the raw materials. The urethane prepolymer (A) reacts with the isocyanate group of the component to cause an increase in viscosity, or the content of the isocyanate group is increased, and the cured product is not adversely affected such as foaming. In order to achieve the object of the invention, it means that there is no inconvenience even if it is regarded as having no reactive functional group. Specifically, the amount of the reactive functional group present in the plasticizer molecule is preferably 0.2% by mass or less, more preferably 0.1% by mass or less, and particularly preferably 0.05% by mass or less.

  Specific examples of the high molecular weight plasticizer include, for example, a compound having a polar group, a polyether derivative of a saccharide-based polyhydric alcohol, and a terminal alkyl ether of a polyoxyalkylene glycol such as polyoxyethylene glycol or polyoxypropylene glycol. Derivatives and alkyl ester derivatives; Liquid polyether (polyoxyalkylene) derivatives such as liquid urethane bond-containing polyether derivatives; Liquid (meth) acrylate (co) polymer resins; Polyesters of dicarboxylic acids and glycols Examples include terminal alkyl etherification and alkyl esterification derivatives. Examples of the compound having no polar group include liquid polyolefin resins such as polybutadiene and polyisoprene; and liquid polyalkylene resins such as hydrogenated polybutadiene and hydrogenated polyisoprene.

  The low molecular weight plasticizer and the high molecular weight plasticizer can be used alone or in combination of two or more, but they have good compatibility with the isocyanate group-containing urethane prepolymer (A) and migrate from the curable composition (bleed. DINP is preferable among low molecular weight plasticizers in that it is excellent in antifouling properties when combined with the second organic isocyanate compound (a-2) described above, and high molecular weight plasticizers. Of these, liquid polyether derivatives and liquid (meth) acrylate (co) polymer resins are preferred, and liquid urethane bond-containing polyether derivatives and liquid (meth) acrylate (co) polymer resins are more preferred.

  As the polyether derivative of the saccharide polyhydric alcohol, an alkylene oxide such as ethylene oxide or propylene oxide is added (co-) to the hydroxyl group of the saccharide polyhydric alcohol such as sucrose (glucose), glucose, mannitol, sorbitol. General commercially available products of polyether derivatives of sucrose polyhydric alcohols, such as resins that are polymerized, alkyl etherified or alkyl esterified, and end-capped with alkyl groups, and that have substantially no hydroxyl groups in the molecule As SPX-80 manufactured by Sanyo Chemical Industries.

  The liquid urethane bond-containing polyether derivative contains a polyoxyalkylene group (polyether group) and a urethane group in the molecule obtained by reacting a polyoxyalkylene alcohol and an organic isocyanate, and is substantially a hydroxyl group. Alternatively, a high molecular weight resin having no isocyanate group is preferable. The most molecular distribution of the liquid urethane bond-containing polyether derivative [ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene by gel permeation chromatography (GPC) = Mw / Mn] is 1. By making the width 6 or less, particularly preferably as narrow as 1.0 to 1.3, even when the liquid urethane bond-containing polyether derivative has a high molecular weight, the viscosity can be kept low, and the resulting curable composition Workability can be improved.

  Specifically, the polyoxyalkylene alcohol and the organic isocyanate are within the range where the molar ratio of isocyanate group / hydroxyl group is 0.9 to 1.1 / 1.0, most preferably 1.00 to 1.05. It can be suitably produced by reacting in the range of /1.00. When the molar ratio is less than 0.9 / 1.0, the maximum hydroxyl group content increases, so that it reacts with the isocyanate group of the isocyanate group-containing urethane prepolymer (A) to increase the viscosity and deteriorate the workability. If it exceeds /1.0, the content of isocyanate groups increases, which is not preferable in that the influence of the cured product on the rubber elastic properties cannot be ignored.

  Examples of the polyoxyalkylene alcohol include polyoxyalkylene monools, polyoxyalkylene polyols, and mixtures thereof. Examples of organic isocyanates include organic monoisocyanates, organic polyisocyanates, and mixtures thereof. The combination of the polyoxyalkylene alcohol and the organic isocyanate is a combination of a polyoxyalkylene monool and an organic monoisocyanate, a combination of a polyoxyalkylene monool and an organic polyisocyanate, or a polyoxyalkylene polyol. The combination of polyoxyalkylene monool and organic monoisocyanate is a polyoxyalkylene type in that the viscosity of the resulting urethane bond-containing polymer plasticizer can be kept low. A combination of a polyol and an organic monoisocyanate is preferred.

  Examples of the polyoxyalkylene monool include low-molecular alkyl monoalcohols such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, tert-butanol, and cyclohexanol; phenol, cresol and the like Phenols of the above; those obtained by ring-opening addition (co) polymerization of cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide, and mixtures of two or more thereof to an initiator such as a mixture of two or more of these It is done. The initiator is preferably a low-molecular alkyl monoalcohol having 5 or less carbon atoms such as methanol or ethanol.

  Further, the polyoxyalkylene monool is produced using the same catalyst as that used as the catalyst used for producing the polyoxyalkylene polyol used for the synthesis of the isocyanate group-containing urethane prepolymer (A). The total degree of unsaturation is preferably 0.1 meq / g or less, more preferably 0.07 meq / g or less, particularly preferably 0.04 meq / g or less, and the molecular weight distribution (Mw / Mn) is 1.6 or less, particularly 1 A narrow one of 0.0 to 1.3 is preferable in that the viscosity of the obtained liquid polyoxyalkylene urethane resin can be reduced, and the workability of the resulting curable composition is improved.

  The “system” of the polyoxyalkylene monool has the same meaning as the “system” of the polyoxyalkylene polyol used for the synthesis of the isocyanate group-containing urethane prepolymer (A) described above. .

  Examples of the polyoxyalkylene-based polyol include the same compounds as those used in the synthesis of the isocyanate group-containing urethane prepolymer.

  Among the polyoxyalkylene alcohols, polyoxyalkylene monools are preferred in that the viscosity of the resulting liquid urethane bond-containing polyether derivative can be reduced, and the workability of the resulting curable composition is improved. Polyoxypropylene monool is particularly preferable.

  As said organic isocyanate compound, the compound similar to what was mentioned as said 2nd organic isocyanate compound (a-2) is mentioned, These can be used individually or in combination of 2 or more types. Of these, aliphatic polyisocyanates and aliphatic monoisocyanates are preferred in that the viscosity of the liquid urethane bond-containing polyether derivative can be reduced, and the workability of the resulting curable composition is good. Of these, aliphatic polyisocyanates are preferable, hexamethylene diisocyanate (HDI) is more preferable, and n-octadecyl monoisocyanate (ODI) is preferable among the aliphatic monoisocyanates.

  In the synthesis of the liquid urethane bond-containing polyether derivative, the same compounds as those exemplified as the metal catalyst among the curing accelerators described later can be used as the reaction catalyst, and an isocyanate group can be used in a known organic solvent. Alternatively, those that do not react with hydroxyl groups can be used.

  As the liquid (meth) acrylic acid alkyl ester-based (co) polymer resin, specifically, a (meth) acrylic acid alkyl ester-based monomer and, if necessary, other ethylenically unsaturated compounds and Can be obtained by a known radical polymerization reaction such as batch polymerization or continuous polymerization at 50 to 350 ° C. in the presence or absence of a polymerization initiator and in the presence or absence of an organic solvent (co). Polymer resin, preferably obtained by continuous high temperature polymerization reaction at 100 to 300 ° C., Tg of 0 ° C. or less, more preferably −100 to −20 ° C., viscosity at 25 ° C. of 50,000 mPa · s or less Is a low-viscosity (co) polymer resin having a narrow molecular weight distribution of 100 to 10,000 mPa · s, particularly preferably 200 to 5,000 mPa · s. Others include those having no isocyanate group. If the Tg exceeds 0 ° C. and the viscosity exceeds 50,000 mPa · s, the workability of the curable composition is deteriorated.

  The (meth) acrylic acid alkyl ester-based (co) polymer resin may be obtained by polymerizing a (meth) acrylic acid alkyl ester-based monomer alone, or a (meth) acrylic acid alkyl ester-based monomer. Two or more of these may be copolymerized, or may be a copolymer of a (meth) acrylic acid alkyl ester monomer and another ethylenically unsaturated compound. Of these, (meth) acrylic acid alkyl ester copolymer resins are preferred because the resulting resin has low crystallinity and low viscosity.

  Examples of the (meth) acrylic acid alkyl ester monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid. Isobutyl, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic Cyclohexyl acid, cetyl (meth) acrylate, behenyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, ethoxylated phenol (meth) acrylate, ethoxylated paracumylphenol (meth) acrylate, ethoxylated Nonylphenol (meth) a Mono (meth) acrylic acid esters such as relate, propoxylated nonylphenol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-phenoxy (meth) acrylate, etc. Ethoxylated bisphenol F di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, caprolactone di (meth) acrylate , Neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, ethylene glycol Cold di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Poly (meth) acrylic acid ester monomers such as polypropylene glycol di (meth) acrylate, etc. can be used, and these can be used singly or in combination of two or more, but among these are liquid and relatively low viscosity (Meth) acrylic acid alkyl ester-based (co) polymer resins are preferred, and low molecular weight mono (meth) acrylic acid alkyl ester monomers having a molecular weight of less than 500, more preferably less than 300, are preferred, and (meth) acrylic. Methyl acid, ( More preferred are ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

  Examples of the ethylenically unsaturated monomer other than the (meth) acrylic acid ester monomer that can be used as needed include, for example, ethylene, propylene, isobutylene, butadiene, chloroprene, vinyl chloride, and vinylidene chloride. , Vinyl acetate, acrylonitrile, styrene, chlorostyrene, 2-methylstyrene, divinylbenzene, (meth) acrylamide, N-vinyl-pyrrolidone, etc., and these can be used alone or in combination of two or more. Of these, styrene is preferred in the same manner as described above.

  The plasticizer is preferably blended in an amount of 1 to 200 parts by weight, particularly 5 to 50 parts by weight, per 100 parts by weight of the isocyanate group-containing urethane prepolymer (A). If it is less than 1 part by mass, the effect of reducing the viscosity of the cured composition is lost, and if it exceeds 200 parts by mass, the durability of the cured product, such as heat resistance and water resistance, is decreased.

  The weather resistance stabilizer is used to prevent oxidation and light deterioration, heat deterioration, and the like of the cured product and further improve not only the weather resistance but also the heat resistance, for example, a hindered amine light stabilizer, Examples include hindered phenol antioxidants and ultraviolet absorbers.

  Examples of hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (2,2,6,6-tetramethyl-1 (octyloxy) -decanoate. 4-piperidyl) ester, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate Methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- [3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, dimethyl succinate 1- (2-hydroxyethyl) -4-hydroxy-2,2 , 6,6-tetramethylpiperidine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2, 2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], N, N′-bis (3-aminopropyl) And ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate. . Moreover, high molecular weight hindered amine light stabilizers such as those manufactured by ADEKA and trade names Adeka tabs LA-63P and LA-68LD are also included.

  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-hydroxyphenylpropioamide], benzenepropanoic acid 3, 5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5 Di -tert- butyl-4-hydroxyphenyl) propionate] 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- Triazine ultraviolet absorbers such as 1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, benzophenone ultraviolet absorbers such as octabenzone, 2,4-di-tert-butyl Examples thereof include benzoate ultraviolet absorbers such as phenyl-3,5-di-tert-butyl-4-hydroxybenzoate.

  These can be used singly or in combination of two or more. Among these, a hindered amine light stabilizer and a hindered phenol antioxidant are preferable because of high weather resistance.

  The weathering stabilizer is preferably blended in an amount of 0.01 to 30 parts by weight, particularly 0.1 to 10 parts by weight, based on 100 parts by weight of the isocyanate group-containing urethane prepolymer (A).

  Fillers, thixotropic agents, adhesion improvers, storage stability improvers (dehydrating agents), and colorants reinforce and increase physical properties, prevent sagging (slump), improve adhesion, and improve storage stability. For coloring, etc., it can be used by blending with the curable composition of the present invention.

  Fillers include mica, kaolin, zeolite, graphite, diatomaceous earth, white clay, clay, talc, slate powder, anhydrous silicic acid, quartz fine powder, aluminum powder, zinc powder, synthetic silica such as precipitated silica, heavy calcium carbonate Inorganic powder fillers such as precipitated calcium carbonate, magnesium carbonate, alumina, calcium oxide, magnesium oxide, fibrous fillers such as glass fiber and carbon fiber, glass balloons, shirasu balloons, silica balloons, ceramic balloons, etc. Inorganic fillers such as balloon fillers; 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, thermoplastic or thermosetting Resin fine powder, polyethylene powder, hollow body, Saran microballoon, etc. Other organic fillers such as organic balloons fillers, also listed and flame retardant fillers such as magnesium hydroxide and aluminum hydroxide, the particle diameter 0.01~1,000μm is preferred.

  Examples of the thixotropic agent include inorganic thixotropic agents such as hydrophilic or hydrophobic colloidal silica and fatty acid-treated calcium carbonate; organic thixotropic agents such as organic bentonite and fatty acid amide. It can be selected and added.

  Examples of the adhesion improver include a coupling agent, an epoxy resin, and a phenol resin. Examples of the coupling agent include various coupling agents such as silane-based, aluminum-based, and zircoaluminate-based compounds, or partial hydrolysis condensates thereof. Among them, a silane coupling agent or a partially hydrolyzed condensate thereof is preferable because of its excellent adhesiveness.

  Specific examples of the silane coupling agent include vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane. Methoxysilane, vinylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and other alkoxysilyl group-containing molecular weight of 500 or less, Mashiku may be mentioned 400 or lower molecular weight compound or a compound having a molecular weight of 200 to 3,000 with one or more partially hydrolyzed condensate of the silane-based coupling agent. These can be used alone or in combination of two or more.

  Examples of the storage stability improver include vinyltrimethoxysilane and calcium oxide 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.

  These can be used alone or in admixture of two or more.

  The total amount of the filler, thixotropic agent, adhesion improver, storage stability improver, and colorant is 0 to 500 parts by mass with respect to 100 parts by mass of the isocyanate group-containing urethane prepolymer (A). In particular, the amount is preferably 5 to 300 parts by mass.

  In the curable composition of the present invention, each of the additive components can be used alone or in combination of two or more.

  Next, uses of the curable composition of the present invention will be described. The curable composition of the present invention is excellent in surface contamination prevention performance after curing, and also excellent in durability such as adhesion, water resistance, weather resistance, etc. It can be used for various applications such as paints, waterproofing coatings, adhesives, and sealing materials. The target materials for construction include inorganic materials such as mortar and concrete, natural stone materials such as marble, siding and tiles. Ceramic materials such as polypropylene, vinyl and other synthetic resin sheets and plates, and wood materials such as wood and plywood are preferable because of their good adhesion.

  Furthermore, the curable composition of the present invention is a construction that is capable of maximizing the characteristics that the surface has excellent surface contamination prevention performance even when the physical properties after curing are low hardness and high elongation is soft. In civil engineering and civil engineering structures, the surface of the cured product is not overcoated, but is directly exposed to the outdoor environment. Suitable for the application, building sealants for this application are particularly preferred.

  Typical examples of the place subject to the contamination include so-called exposed joints such as exterior wall joints formed by siding that has been colored and pre-designed in a factory, and joint exterior wall joints formed of concrete or metal panels. It is mentioned as a thing. Therefore, as a use of the curable composition of the present invention, a sealing material for exposed joints in the building field is preferable, and a sealing material for siding outer wall joints and a sealing material for building outer wall joints are more preferable.

The method for producing the curable composition of the present invention is not particularly limited. For example, first, the isocyanate group-containing urethane prepolymer (A) component is synthesized using a reaction apparatus made of glass, stainless steel, or iron. To do. This reaction may be carried out in the presence or absence of an additive component. Next, the isocyanate group-containing urethane prepolymer (A) component is charged into a stirring and mixing apparatus, and if necessary, an additive component is added and kneaded. At this time, the first organic isocyanate compound (a-1) composed of an unreacted aliphatic isocyanate compound remains in the isocyanate group-containing urethane prepolymer (A) component, and this remains as the second organic isocyanate compound (a- 2) If it is possible, the second organic isocyanate compound (a-2) is not contained in the urethane prepolymer (A) component or if it is insufficient, the second organic isocyanate compound ( The method of adding and mixing a-2) and manufacturing is mentioned. After mixing, it is preferable to perform degassing under reduced pressure at a vacuum degree of 50 to 100 hPa.
The component (A), the component (a-1), and the component (a-2) react when exposed to moisture, increase in viscosity and deteriorate workability. Therefore, synthesis reaction, stirring, and mixing do not contact moisture. Thus, it is preferable to carry out in a sealed state and in a state where moisture is shut off such as in a nitrogen gas atmosphere. Examples of the agitation and mixing apparatus include a stainless steel and iron planetary mixer, a kneader, an agitator, a nauta mixer, a line mixer, and the like. Since the produced curable composition also reacts when exposed to moisture and thickens and hardens, it is preferably stored in a container that can block moisture, and sealed and stored. The container is not particularly limited. For example, a metal drum can made of stainless steel or iron, a pail can or bag container made of metal or synthetic resin, a laminated paper cartridge or container made of synthetic resin, etc. There are various types.

  In use, the container filled with the curable composition is opened, and the filling and coating device such as a manual or electric extrusion gun is used to fill and construct the construction site such as the exposed joint. .

  Although the Example of this invention is shown below, it cannot be overemphasized that it is not limited to this.

Synthesis Example 1 (Synthesis of HDI-derived isocyanate group-containing urethane prepolymer P-1)
Polyoxypropylene diol (manufactured by Mitsui Chemicals Polyurethanes, PPG-Diol-3000, number average molecular weight 3,000) while flowing nitrogen gas through a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet tube and heating / cooling device 560 g and 100 g of polyoxypropylene triol (manufactured by Mitsui Chemicals Polyurethane, PPG-MN-4000, number average molecular weight 4,000) while stirring and stirring, hexamethylene diisocyanate (HDI) (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: 75 g of HDI, molecular weight 168.2) was charged. The number of moles of isocyanate groups / number of moles of hydroxyl groups is 2.0. Next, 1.0 g of dibutyltin dilaurate 10 mass% DMC solution prepared by dissolving 1.0 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd., Neostan U-100) in 9.0 g of dimethyl carbonate (DMC) was added as a reaction catalyst. And heated for 4 hours at 75 to 85 ° C., and when the isocyanate group content by titration is less than the theoretical value (2.54% by mass), the reaction is terminated, and the isocyanate group-containing urethane derived from HDI Prepolymer P-1 was synthesized.
The obtained urethane prepolymer P-1 was a viscous liquid transparent at normal temperature with an isocyanate group content of 2.46% by mass measured by titration.

Synthesis Example 2 (Synthesis of HDI-derived isocyanate group-containing urethane prepolymer P-2)
560 g of polyoxypropylene diol (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., PPG-Diol-3000, number average molecular weight 3,000) and polyoxypropylene triol (Mitsui) were passed through the same reaction vessel as in Synthesis Example 1. 100 g of Chemical Polyurethane, PPG-MN-4000, number average molecular weight 4,000) was charged, and 80 g of hexamethylene diisocyanate (HDI) (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: HDI, molecular weight 168.2) with stirring. Prepared. The number of moles of isocyanate groups / number of moles of hydroxyl groups at this time is 2.1. Next, 1.0 g of a 10% by mass DMC solution of dibutyltin dilaurate as in Synthesis Example 1 was added as a reaction catalyst, heated and reacted at 75 to 85 ° C. for 4 hours. The isocyanate group content by titration was a theoretical value (2 .85% by mass) or less, the reaction was terminated, and an isocyanate group-containing urethane prepolymer P-2 derived from HDI was synthesized.
The obtained urethane prepolymer P-2 was a viscous liquid transparent at room temperature with an isocyanate group content of 2.78% by mass measured by titration.

Synthesis Example 3 (Synthesis of IPDI-derived isocyanate group-containing urethane prepolymer P-3)
560 g of polyoxypropylene diol (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., PPG-Diol-3000, number average molecular weight 3,000) and polyoxypropylene triol (Mitsui) were passed through the same reaction vessel as in Synthesis Example 1. 100 g of Chemical Polyurethane, PPG-MN-4000, number average molecular weight 4,000) was charged, and 100 g of isophorone diisocyanate (IPDI) (manufactured by Degussa Japan, trade name: IPDI, molecular weight 222.3) was charged while stirring. . The number of moles of isocyanate groups / number of moles of hydroxyl groups is 2.0. Next, 1.5 g of a 10% by weight DMC solution of dibutyltin dilaurate as in Synthesis Example 1 was added as a reaction catalyst, heated and reacted at 75 to 85 ° C. for 6 hours. The isocyanate group content by titration was a theoretical value (2 .50 mass%) or less, the reaction was terminated and an IPDI-derived isocyanate group-containing urethane prepolymer P-3 was synthesized.
The obtained urethane prepolymer P-3 was a viscous liquid transparent at room temperature with an isocyanate group content of 2.40% by mass measured by titration.

Synthesis Example 4 (Synthesis of XDI-derived isocyanate group-containing urethane prepolymer P-4)
560 g of polyoxypropylene diol (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., PPG-Diol-3000, number average molecular weight 3,000) and polyoxypropylene triol (Mitsui) were passed through the same reaction vessel as in Synthesis Example 1. 88.5 g of xylylene diisocyanate (XDI) (manufactured by Mitsui Chemicals Polyurethanes, Takenate 500, molecular weight 188.2) with stirring while stirring and 100 g of Chemical Polyurethane, PPG-MN-4000, number average molecular weight 4,000. Prepared. The number of moles of isocyanate groups / number of moles of hydroxyl groups at this time is 2.1. Next, 1.0 g of a 10% by mass DMC solution of dibutyltin dilaurate as in Synthesis Example 1 was added as a reaction catalyst, heated and reacted at 75 to 85 ° C. for 4 hours. The isocyanate group content by titration was a theoretical value (2 The reaction was terminated at the time when it was less than or equal to .77% by mass), and an isocyanate group-containing urethane prepolymer P-4 derived from XDI was synthesized.
The obtained urethane prepolymer P-4 was a viscous liquid transparent at room temperature with a measured isocyanate group content of 2.70% by mass by titration.

Synthesis Example 5 (Synthesis of MDI-derived isocyanate group-containing urethane prepolymer P-5)
560 g of polyoxypropylene diol (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., PPG-Diol-3000, number average molecular weight 3,000) and polyoxypropylene triol (Mitsui) were passed through the same reaction vessel as in Synthesis Example 1. Chemical Polyurethane, PPG-MN-4000, number average molecular weight 4,000) charged with 100 g and toluene 120 g, while stirring, 4,4′-diphenylmethane diisocyanate (MDI) (manufactured by Nippon Polyurethane Industry, Millionate MT, molecular weight 250) was charged. The number of moles of isocyanate groups / number of moles of hydroxyl groups is 2.0. Next, 0.1 g of a 10% by mass DMC solution of dibutyltin dilaurate similar to Synthesis Example 1 was added as a reaction catalyst, heated and reacted at 75 to 85 ° C. for 4 hours. The isocyanate group content by titration was a theoretical value (2 .11% by mass) or less, the reaction was terminated and an MDI-derived isocyanate group-containing urethane prepolymer P-5 was synthesized.
The obtained urethane prepolymer P-5 was a viscous liquid transparent at normal temperature with an isocyanate group content of 2.00% by mass measured by titration.

Synthesis Example 6 (Synthesis of urethane bond-containing polyether polymer plasticizer U-1)
While flowing nitrogen gas through the same reaction vessel as in Synthesis Example 1, polyoxypropylene diol (manufactured by Asahi Glass Co., Ltd., PML-4010, number average molecular weight 10,000, molecular weight distribution (Mw / Mn) 1.0 to 1.1 ) 800 g was charged, and 50 g of n-octadecyl monoisocyanate (manufactured by Hodogaya Chemical Co., Ltd., Millionate O, molecular weight 295.5) was charged with stirring. The number of moles of isocyanate groups / number of moles of hydroxyl groups is 1.06. Next, 1.0 g of a 10% by mass DMC solution of dibutyltin dilaurate as in Synthesis Example 1 was added as a reaction catalyst, and the mixture was heated and reacted at 70 to 80 ° C. for 4 hours. The isocyanate group content was the theoretical value (0 .04 mass%) or less, the reaction was terminated, and a liquid urethane bond-containing polyether polymer plasticizer U-1 was synthesized.
The obtained urethane bond-containing polyether polymer plasticizer U-1 has a measured isocyanate group content of 0.02% by mass by titration, a viscosity of 7,000 mPa / 25 ° C., and a molecular weight distribution (Mw / Mn) of 1.0 to 1.1. It was a translucent viscous liquid at room temperature.

Example 1
While flowing nitrogen gas into a kneading vessel with a heating / cooling device and a nitrogen seal tube, 100 g of the HDI-derived isocyanate group-containing urethane prepolymer P-1 obtained in Synthesis Example 1 and 40 g of diisononyl phthalate (DINP) were charged and stirred. However, 50 g of fatty acid surface-treated calcium carbonate (Shiraishi Kogyo Co., Ltd., white gloss flower CCR) each dried in advance with a dryer at 100 to 110 ° C. and having a moisture content of 0.05% by mass or less, titanium oxide 15 g, 70 g of heavy calcium carbonate was charged and mixed for 1 hour until the contents were uniform. Next, 1.7 g of a 30% by weight DMC solution of a hindered amine light stabilizer in which 6 g of a hindered amine light stabilizer (manufactured by ADEKA, ADK STAB LA-6P, molecular weight 2,000) was dissolved in 14 g of dimethyl carbonate (DMC) 6 g of hindered phenol-based antioxidant (pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]) (manufactured by Ciba Specialty Chemicals, Irganox 1010) 3.3 g of a 30% by weight DMC solution of a hindered phenolic antioxidant dissolved in 14 g of dimethyl carbonate (DMC) and 3.0 g of a 10% by weight DMC solution of dibutyltin dilaurate similar to those of Synthesis Example 1 were sequentially added. After mixing for 1 hour until the contents become more uniform Vacuum defoamed 50～100HPa, poured into a container, then sealed to prepare a one-part moisture-curable sealant S1.
About the obtained 1 liquid moisture hardening type sealing material S1, content of the free HDI monomer measured by the determination method of the free organic isocyanate compound by the following gas chromatography was 0.7 mass%.
This free HDI monomer is unreacted HDI contained in the urethane prepolymer P-1 obtained in Synthesis Example 1, and this is the second organic isocyanate as it is.

Example 2
In the same manner as Example 1, except that DINP was not used and 40 g of the urethane bond-containing polyether polymer plasticizer U-1 obtained in Synthesis Example 6 was used instead, the one-component moisture-curing sealant S2 was used. Was prepared.
The free HDI monomer content of the obtained one-component moisture-curing sealing material S2 was 0.8% by mass.
The free HDI monomer is unreacted HDI contained in the urethane prepolymer P-1 obtained in Synthesis Example 1 as in Example 1, and this is the second organic isocyanate as it is.

Example 3
In Example 1, after the urethane prepolymer P-1 was charged, 1.0 g of octadecyl monoisocyanate (ODI) was charged, and without using DINP, the urethane bond-containing polyether-based polymer obtained in Synthesis Example 6 was used instead. A one-component moisture-curing sealing material S3 was prepared in the same manner except that 40 g of the molecular plasticizer U-1 was used.
The total free organic isocyanate monomer content of the obtained one-component moisture-curing sealing material S3 was 1.1% by mass.
This free organic isocyanate monomer is the total of unreacted HDI contained in the urethane prepolymer P-1 obtained in Synthesis Example 1 and ODI added later, and this becomes the second organic isocyanate. ing.

Example 4
In Example 1, without using the HDI-derived isocyanate group-containing urethane prepolymer P-1 obtained in Synthesis Example 1, 100 g of the HDI-derived isocyanate group-containing urethane prepolymer P-2 obtained in Synthesis Example 2 was used instead. After preparing this urethane prepolymer P-2, a one-component moisture-curing sealing material S4 was prepared in the same manner except that 0.5 g of HDI was added.
The content of free organic isocyanate monomer in the obtained one-component moisture-curable sealing material S4 was 1.3% by mass.
This free organic isocyanate monomer is the total of unreacted HDI contained in the urethane prepolymer P-2 obtained in Synthesis Example 2 and HDI added later, and this becomes the second organic isocyanate. ing.

Example 5
In Example 4, 1.0 g of HDI added later is used, and further, DINP is not used, and 40 g of the urethane bond-containing polyether polymer plasticizer U-1 obtained in Synthesis Example 6 is used instead. In the same manner, a one-component moisture-curing sealing material S5 was prepared.
The content of free organic isocyanate monomer in the obtained one-component moisture-curable sealing material S5 was 1.4% by mass.
This free organic isocyanate monomer is the total of unreacted HDI contained in the urethane prepolymer P-2 obtained in Synthesis Example 2 and HDI added later, and this becomes the second organic isocyanate. ing.

Example 6
In Example 4, a one-component moisture-curing type sealing material S6 was prepared in the same manner except that 1.0 g of octadecyl monoisocyanate (ODI) was added instead of using HDI added later.
The total content of free organic isocyanate monomers in the obtained one-component moisture-curable sealing material S6 was 1.3% by mass.
The free organic isocyanate monomer is the total of unreacted HDI contained in the urethane prepolymer P-2 obtained in Synthesis Example 2 and ODI added later, and this becomes the second organic isocyanate. ing.

Example 7
In Example 1, without using the HDI-derived isocyanate group-containing urethane prepolymer P-1 obtained in Synthesis Example 1, 100 g of the IPDI-derived isocyanate group-containing urethane prepolymer P-3 obtained in Synthesis Example 3 was used instead. After preparing this urethane prepolymer P-3, a one-component moisture-curing sealing material S7 was prepared in the same manner except that 2.0 g of HDI was added.
The total free organic isocyanate monomer content of the obtained one-component moisture-curing sealing material S7 was 1.4% by mass.
This free organic isocyanate monomer is the total of unreacted IPDI contained in the urethane prepolymer P-3 obtained in Synthesis Example 3 and HDI added later, and this becomes the second organic isocyanate. ing.

Example 8
In Example 1, without using the HDI-derived isocyanate group-containing urethane prepolymer P-1 obtained in Synthesis Example 1, 100 g of the XDI-derived isocyanate group-containing urethane prepolymer P-4 obtained in Synthesis Example 4 was used instead. After preparing this urethane prepolymer P-4, a one-component moisture-curing sealing material S8 was prepared in the same manner except that 2.0 g of HDI was added.
The total free organic isocyanate monomer content of the obtained one-component moisture-curable sealing material S8 was 1.2% by mass.
This free organic isocyanate monomer is the total of unreacted XDI contained in the urethane prepolymer P-4 obtained in Synthesis Example 4 and HDI added later, and this becomes the second organic isocyanate. ing.

Comparative Example 1
In Example 1, without using the HDI-derived isocyanate group-containing urethane prepolymer P-1 obtained in Synthesis Example 1, 100 g of the MDI-derived isocyanate group-containing urethane prepolymer P-5 obtained in Synthesis Example 5 was used instead. In the same manner, a one-component moisture-curing sealant-Comparative S1 was prepared.
The content of free organic isocyanate monomer in the obtained one-component moisture-curing sealant-Comparative S1 was 0.6% by mass.
This free organic isocyanate monomer is unreacted MDI contained in the MDI-derived isocyanate group-containing urethane prepolymer P-5 obtained in Synthesis Example 5, and this is the second organic isocyanate.

Comparative Example 2
In Comparative Example 1, a one-component moisture-curing sealing material-Comparison S2 was prepared in the same manner except that 2.0 g of IPDI was further added after the urethane prepolymer P-5 was charged.
The content of free organic isocyanate monomer in the obtained one-component moisture-curing sealant-Comparison S2 was 1.3% by mass.
This free organic isocyanate monomer is the total of unreacted MDI contained in the MDI-derived isocyanate group-containing urethane prepolymer P-5 obtained in Synthesis Example 5 and IPDI added later. It is an organic isocyanate.

  Using each of the one-component moisture curable sealing material compositions obtained in Examples 1 to 8 and Comparative Examples 1 and 2, the content of the second organic isocyanate compound in the following composition, adhesiveness, Tables 1 and 2 show the results of testing for contamination A and contamination B together with the composition.

[Test method]
(1) Content of Second Organic Isocyanate Compound in Composition Using each of the one-component moisture curable sealing materials obtained in Examples 1 to 8 and Comparative Examples 1 and 2 as samples, the following (1-1 ) To (1-5) are sequentially performed, and the results of measuring the content of the free organic isocyanate compound are shown in Table 1 and Table 2 together with the type of the organic isocyanate compound.

(1-1) Preparation of internal standard solution About 0.25 g of anthracene was precisely weighed in a 100 ml beaker, and an appropriate amount of ethyl acetate was added and dissolved. This was transferred to a 250 ml volumetric flask and added while washing the beaker with ethyl acetate to make exactly 250 ml.

(1-2) Preparation of HDI standard stock solution, ODI standard stock solution, IPDI standard stock solution, XDI standard stock solution and MDI standard stock solution About 1.0 g of HDI was precisely weighed into a 100 ml beaker, and ethyl acetate was added to dissolve. This was transferred to a 100 ml volumetric flask and further added while washing the beaker with ethyl acetate to make exactly 100 ml to prepare an HDI standard stock solution.
Similarly, an ODI standard stock solution, an IPDI standard stock solution, an XDI standard stock solution, and an MDI standard stock solution were prepared using each of ODI, IPDI, XDI, and MDI.

(1-3) Preparation of HDI standard injection solution, ODI standard injection solution, IPDI standard injection solution, XDI standard injection solution and MDI standard injection solution The HDI standard stock solution prepared in (1-2) is adjusted to a 20 ml sample bottle. Pipette 0.5 ml, 1.0 ml, 2.0 ml, 3.0 ml and 5.0 ml, add the internal standard solution prepared in (1-1) with a 10 ml whole pipette, mix, The injection solution was adjusted.
Similarly, an ODI standard injection solution, an IPDI standard injection solution, an XDI standard injection solution, and an MDI standard injection solution were prepared.

(1-4) Preparation of HDI calibration curve, ODI calibration curve, IPDI calibration curve, XDI calibration curve and MDI calibration curve Using the HDI standard injection solution prepared in (1-3), it was subjected to gas chromatography under the following conditions. An HDI calibration curve was created from the peak height.
Similarly, an ODI calibration curve, an IPDI calibration curve, an XDI calibration curve, and an MDI calibration curve were prepared.

(1-5) Preparation of sample solution and measurement of free organic isocyanate content Approximately 20 g of sample is accurately weighed into a 20 ml sample bottle, and 10 ml of the internal standard solution obtained in (1-1) is added to this with a whole pipette. The sample solution was prepared by dissolution. This sample solution is subjected to gas chromatography under the following conditions, and from the peak height, the amount of organic isocyanate is determined by the calibration curve of the corresponding organic isocyanate, divided by the sample amount, and the content of the second organic isocyanate in the sample is determined. Asked.
In addition, about Example 3, 6, 7, 8 and the comparative example 2, two types of organic isocyanate content was calculated | required, respectively, and it calculated by adding together.

[Conditions for gas chromatography]
Measuring instrument: Gas chromatograph GC-14B (manufactured by Shimadzu Corporation)
Column: HR-1701 (diameter 0.32 mm x 25 m)
Column temperature: Temperature rise from 170 ° C. to 270 ° C. at a rate of temperature rise of 10 ° C./min Post run: 270 ° C., 10 min
Set temperature: Inj. 200 ° C., Det. 280 ° C
Carrier gas: He
Detector: FID
Injection volume: 0.50 μl

(2) Adhesiveness One-part moisture-curing sealing material was applied to the surface of the slate plate with a thickness of about 5 mm, and cured and cured for 14 days at 23 ° C. and 50% relative humidity to obtain a test specimen. The surface of the test specimen after curing was lightly touched with a finger wiped with ethanol, and no or little adhesion (stickiness) was evaluated as “good”, and one that felt strong adhesion was evaluated as “poor”.

(3) Pollution (A)
Two pieces of a commercially available siding board having a thickness of 18 mm cut into a size of 100 mm width × 300 mm length were arranged on a plywood, and a gap having a width of 17 mm was arranged and adhered with an adhesive. Next, a square backup material made of polyethylene having a thickness of 10 mm, a width of 18 mm, and a length of 300 mm was inserted into the groove to form a joint formed by siding having a depth of 8 mm, a width of 17 mm, and a length of 300 mm. Next, a masking tape was attached to both sides of the joint, and a primer (manufactured by Auto Chemical Industry Co., Ltd., OP-2531) was applied to the adherend surface in the joint using a brush, followed by primer treatment. 30 minutes after applying the primer, fill the joint with the one-component moisture-curing sealing material obtained on this joint using a manual gun, scrape off the excess sealing material with a spatula, smooth the surface, and then apply the masking tape. A joint was prepared by peeling, filling the sealing material, and constructing it.

This specimen was cured in a room at 23 ° C and 50% relative humidity. After one month, black quartz sand (particle size 70 to 110 µm) was sprinkled on the surface of the specimen. Tap to remove excess black silica sand. The state of the black silica sand (dirt) remaining on the surface was visually observed, and the surface contamination of the specimen was evaluated according to the following criteria.
Judgment criteria:
○: Black silica sand is hardly adhered to the surface of the hardened sealant, and the surface is clean.
X: A state in which a large amount of black silica sand adheres to the surface of the cured sealing material and is blackened.

(4) Pollution (B)
After preparing a test body similar to that prepared with the above-mentioned contamination (A), the joint was immediately placed near the intersection with a high traffic volume with the joint length direction vertical. After 1 month, the surface of the cured sealing material was visually observed, and the contamination state due to dust adhering to the surface was evaluated according to the following criteria.
Judgment criteria:
○: The surface of the cured sealant is clean with almost no dust adhering.
X: A state in which a large amount of dust adheres to the surface of the cured sealing material and is blackened.

Claims (8)

An isocyanate group-containing urethane prepolymer (A) obtained by reacting a first organic isocyanate compound (a-1) comprising an aliphatic isocyanate compound with an active hydrogen-containing compound (b), and a second organic isocyanate compound a (a-2) that Do from the hardening composition, the second organic isocyanate compound (a-2), a curable composition characterized in that an aliphatic mono Ishia sulfonates.   The curable composition according to claim 1, wherein the first organic isocyanate compound (a-1) and the second organic isocyanate compound (a-2) comprising an aliphatic isocyanate compound are compounds having different structures. .   The curable composition according to claim 1 or 2, wherein the second organic isocyanate compound (a-2) is added when the curable composition is produced.   The curable composition according to any one of claims 1 to 3, wherein the second organic isocyanate compound (a-2) is octadecyl monoisocyanate. The curable composition according to any one of claims 1 to 4 , wherein the amount of the second organic isocyanate compound (a-2) is 0.1 parts by mass or more in 100 parts by mass of the curable composition. object. Furthermore, an additive (B) is mix | blended, The curable composition as described in any one of Claims 1-5 characterized by the above-mentioned. The additive (B) is one or two selected from the group consisting of a curing accelerator, a plasticizer, a weathering stabilizer, a filler, a thixotropic agent, an adhesion improver, a storage stability improver, and a colorant. The curable composition of Claim 6 which is a seed | species or more. The curable composition, wherein a surface after curing of the curable composition are those used in a location that is directly exposed to outdoor environment, in any one of claims 1-7 The curable composition as described.