JP5365002B2 - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition which is excellent in storage stability and good in the appearance of a cured product, has reduced toxicity, and is improved in the adverse effect on the environment. <P>SOLUTION: The curable composition consists of an isocyanate group-containing urethane prepolymer and a weatherability improving agent, wherein a specific organic solvent having an ether bond and an ester bond in the molecule is used as a solvent, and thereby, a curable composition having extremely reduced adverse effect on the environment and excellent storage stability, causing no deterioration in appearance even if a weatherability improving agent such as an antioxidant is used, and accordingly preventing deterioration in weatherability can be obtained. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a curable composition containing an isocyanate group-containing urethane prepolymer with low toxicity and improved adverse environmental effects.

  The curable composition containing an isocyanate group-containing urethane prepolymer has good properties such as adhesiveness after curing and rubber elasticity. Adhesives for construction, civil engineering, automobiles, sealing materials, paints, etc. Although it is used in many fields, the urethane group of the isocyanate group-containing urethane prepolymer forms hydrogen bonds and has strong agglomeration power. Therefore, it has excellent adhesion and rubber elasticity, but it has excellent cohesive strength. The polymer has a high viscosity, and the curable composition containing the polymer also has a disadvantage that the viscosity becomes high and the workability is poor. Therefore, it is necessary to use an organic solvent to lower the viscosity of the curable composition and improve workability such as coating and filling. Conventionally, it has the advantage of being excellent in solubility and inexpensive with respect to the urethane prepolymer. Aromatic organic solvents such as toluene and xylene are widely used.

  In addition, for the purpose of improving the weather resistance of a curable composition containing an isocyanate group-containing urethane prepolymer, an antioxidant or a light stabilizer is generally added. Has been widely used as a convenient solvent because of its good solubility in antioxidants and light stabilizers.

  However, toluene, xylene, etc. are listed in the organic solvent poisoning prevention regulations (Organic rules) as the second type organic solvent and are highly toxic, directly harming the health of workers and indirectly being released into the atmosphere. If it is released into the living space, it is considered as a causative substance that causes sick house syndrome, and will protect the global environment in recent years. Accordingly, products that do not use the above aromatic organic solvents as solvents are strongly desired.

  In the past, the present applicant has proposed blending a carbonate organic solvent and a water-reactive compound with an isocyanate group-containing urethane prepolymer as a technique for preventing the environmental pollution (see Patent Document 1). However, although carbonate ester organic solvents can improve environmental pollution, they are not sufficiently soluble in light stabilizers and are dissolved when heated, but light stabilizers precipitate when cooled to room temperature. And it turned out that the external appearance of the surface when constructing a curable composition will deteriorate.

  In addition, for the purpose of reducing danger / harmfulness, a two-component urethane having a urethane prepolymer, a specific sorbitol compound, an organic solvent inert to an isocyanate group as an A agent, and an active hydrogen-containing compound as a B agent. In an organic bonding material, an esterified product of an ethylene glycol ether or an esterified product of a propylene glycol ether is disclosed as an organic solvent inert to an isocyanate group (see Patent Document 2), and an isocyanate group-containing urethane prepolymer and , A two-part curable polyurethane composition containing an active hydrogen-containing compound, a specific solubility parameter and an organic solvent having a substrate endotherm, and dimethyl carbonate as an organic solvent is disclosed (see Patent Document 3). However, no mention is made of light stabilizers or antioxidants.

JP 2006-36881 A JP-A-8-295866 JP 2005-272767 A

  The present invention solves the above-mentioned problems, improves the adverse effects on the environment with low toxicity, has a good appearance of the cured product even when a weathering agent is used, and has excellent storage stability The purpose is to provide.

  As a result of studies conducted in view of the above problems, the present inventors have found that in a curable composition comprising an isocyanate group-containing urethane prepolymer and a weather resistance imparting agent, a specific organic compound having an ether bond and an ester bond in the molecule as a solvent. By using a solvent, in addition to having very little adverse effects on the environment, it has excellent storage stability and does not deteriorate the appearance even when an weather resistance-imparting additive such as an antioxidant is used, thus reducing the weather resistance. The present invention has been completed by finding that a curable composition can be obtained.

That is, the present invention
(A) An isocyanate group-containing urethane prepolymer (A), an isocyanate group-inert organic solvent (B) having an ether bond and an ester bond in a molecule other than the cellosolve organic solvent, and a weather resistance imparting agent (C). It is a curable composition characterized by containing.

［但し、式（１）中、Ｒ^１およびＲ^２は、それぞれ独立に炭素数１〜６の１価の脂肪族炭化水素基を表す］

［但し、式（２）中、Ｒ^３は炭素数１〜６の１価の脂肪族炭化水素基を表し、Ｒ^４は炭素数３または４の２価の脂肪族炭化水素基を表し、Ｒ^５は炭素数１または２の１価の炭化水素基を表す。］ And
(B) In the above (a), the isocyanate group-inert organic solvent (B) is preferably a compound represented by the following general formula (1) and / or the following general formula (2).

[In the formula (1), R ¹ and R ² each independently represents a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms]

[In the formula (2), R ³ represents a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms; R ⁴ represents a divalent aliphatic hydrocarbon group having 3 or 4 carbon atoms; ⁵ represents a monovalent hydrocarbon group having 1 or 2 carbon atoms. ]

And
(C) In the above (b), the compound represented by the general formula (1) is methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -It is preferably one or more selected from the group consisting of ethyl ethoxypropionate, propyl 3-ethoxypropionate and ethyl 3-propoxypropionate,
(D) In the above (b), the compound represented by the general formula (2) is propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol monomethyl ether propionate, It is preferably one or more selected from the group consisting of propylene glycol monoethyl ether propionate, butylene glycol monomethyl ether acetate, butylene glycol monoethyl ether acetate.

Also,
(E) In (b), the compound represented by the general formula (1) is particularly preferably ethyl 3-ethoxypropionate,
(F) In the above (b), it is particularly preferable that the compound represented by the general formula (2) is propylene glycol monomethyl ether acetate and / or butylene glycol monomethyl ether acetate.

Furthermore, the present invention provides
(G) In any one of the above (a) to (f), a carbonate organic solvent (D) can be further used.

And
(H) In any one of the above (a) to (g), the weather resistance imparting agent (C) is preferably a hindered amine light stabilizer and / or a hindered phenol antioxidant.

Furthermore, the present invention provides
(Li) In any one of the above (a) to (h), an additive (E) other than the weather resistance imparting agent (C) is further blended.

  Below, the component used by this invention is demonstrated. First, the isocyanate group-containing urethane prepolymer (A) component will be described.

  The isocyanate group-containing urethane prepolymer (A) is obtained by reacting an organic isocyanate and an active hydrogen-containing compound with active hydrogen (group) under an isocyanate group excess condition. From this urethane prepolymer (A), When the resulting curable composition comes into contact with moisture such as moisture, the isocyanate group reacts with moisture and forms a urea bond to crosslink and cure, so that it functions as a curing component in the curable composition of the present invention. is there.

Examples of the organic isocyanate include organic polyisocyanate and organic monoisocyanate optionally used for modifying an isocyanate group-containing urethane prepolymer.
Specific examples of the organic polyisocyanate include toluene diisocyanates (TDI) such as 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, and 2,4′-diphenyl. Diphenylmethane diisocyanate (MDI) such as methane diisocyanate, aromatic diisocyanates such as phenylene diisocyanate, diphenyl diisocyanate, naphthalene diisocyanate, diphenyl ether diisocyanate; araliphatic diisocyanates such as xylylene diisocyanate; hexamethylene diisocyanate, pentamethylene diisocyanate, propylene Aliphatic diisocyanates such as diisocyanate and butylene diisocyanate; cyclohexane diisocyanate, Alicyclic diisocyanates such as lenbis (cyclohexyl isocyanate) and isophorone diisocyanate; and carbodiimide-modified, biuret-modified, allophanate-modified, dimer, trimer or polymethylene polyphenyl polyisocyanate (crude MDI) of these diisocyanates , Polymeric MDI) and the like, and these can be used alone or in combination of two or more.
Of these, aromatic diisocyanates and araliphatic diisocyanates are preferred, MDIs are more preferred, and 4,4′-diphenylmethane diisocyanate is particularly preferred because of excellent tensile adhesiveness and water resistance after curing. .
Examples of the organic monoisocyanate include aliphatic monoisocyanates such as butyl monoisocyanate, hexyl monoisocyanate, tetradecyl monoisocyanate, and octadecyl monoisocyanate.

  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. Examples thereof include a high molecular weight polymer and a low molecular weight monool.

Examples of the polymer polyol include polyester polyols, polycarbonate polyols, polyoxyalkylene polyols, hydrocarbon polyols, poly (meth) acrylate polyols, animal and plant polyols, these copolyols, or a mixture of two or more thereof. Can be mentioned.
The number average molecular weight of the polymer polyol is preferably 1,000 to 100,000, more preferably 1,000 to 30,000, and particularly preferably 1,000 to 20,000. If the number average molecular weight is less than 1,000, rubber elastic properties such as elongation after curing of the resulting curable composition deteriorate, and if it exceeds 100,000, the viscosity of the resulting isocyanate group-containing urethane prepolymer increases. This is not preferable because workability deteriorates.

Polyester polyols include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid, naphthalenedicarboxylic acid, trimellitic acid And one or more of these polycarboxylic acids, acid esters such as methyl esters and ethyl esters of these polycarboxylic acids, or anhydrides of these polycarboxylic acids, 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, neo Pentyl glycol, 1,8-octanediol, , 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 Low molecular weight polyamines such as hexamethylenediamine, xylylenediamine and isophoronediamine; polyester polyol or polyester obtained by dehydration or dealcoholization condensation reaction with one or more low molecular amino alcohols such as monoethanolamine or diethanolamine Amide polyols are mentioned.
Also, lactone polyester polyols 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. Can be mentioned.

  As polycarbonate polyol, dehydrochlorination reaction of low molecular polyols and phosgene used for the synthesis of the above-mentioned polyester polyol, or transesterification reaction of low molecular polyols with diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, etc. Can be obtained.

Polyoxyalkylene polyols include low molecular polyols, low molecular polyamines, low molecular amino alcohols, polycarboxylic acids, sorbitol, mannitol, sucrose, glucose, which are used for the synthesis of the aforementioned polyester polyols. One or more cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, etc., using as an initiator one or more of low molecular weight polyphenols such as saccharide low molecular weight polyhydric alcohols such as bisphenol A and bisphenol F Ring-opening addition polymerization or copolymerization (hereinafter, “polymerization or copolymerization” is referred to as (co) polymerization), polyoxyethylene polyol, polyoxypropylene polyol, polyoxybutylene polyol, polyoxytetramethyl Down 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 number of average alcoholic hydroxyl groups per molecule of the polyoxyalkylene polyol is preferably 2 or more, more preferably 2 to 4, and particularly preferably 2 to 3.

  Furthermore, the polyoxyalkylene-based polyol is produced at the time of its production by a cesium hydride such as cesium hydride, cesium methoxide and cesium ethoxide, a cesium compound 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 mass 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, particularly 1.0 to Narrow the .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.

In addition, for modification of an isocyanate group-containing urethane prepolymer, polyoxyl obtained by ring-opening addition polymerization of a cyclic ether compound such as propylene oxide using a low-molecular monoalcohol such as methyl alcohol, ethyl alcohol or propyl alcohol as an initiator. In some cases, polyoxyalkylene monools such as propylene monools may be used.
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 polyalkylene polyols such as chlorinated polypropylene polyol and chlorinated polyethylene polyol Etc.

  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 above polyoxyalkylene polyol has a low average molecular weight of less than 1,000. Or a mixture of two or more of these.
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.

  The isocyanate group-containing urethane prepolymer in the present invention can be synthesized by either a batch charge reaction method or a multistage charge reaction method, but it is necessary to leave an isocyanate group in the molecule of the prepolymer. The isocyanate group / active hydrogen (group) molar ratio of the isocyanate group of the organic isocyanate and the polymer polyol, and optionally the active hydrogen (group) of the active hydrogen-containing compound such as a chain extender, is 1.1 to 5.0. /1.0 is preferable, and 1.3 to 3.0 / 1.0 is more preferable. The isocyanate group-containing urethane prepolymer thus obtained preferably has an isocyanate group content of 0.1 to 15.0% by mass, particularly preferably 0.3 to 10.0% by mass, and most preferably 0.4 to 5.0% by mass. When the molar ratio is less than 1.1 / 1.0, or the isocyanate group content is less than 0.1% by mass, the molecular weight becomes too large, the viscosity increases, and the workability decreases. Moreover, since there are few crosslinking points in a prepolymer, sufficient adhesiveness cannot be obtained. When the molar ratio exceeds 5.0 / 1.0 or the isocyanate group content exceeds 15.0% by mass, it is difficult to prevent foaming due to carbon dioxide gas generated by the reaction of the isocyanate groups with moisture. And the cured product becomes brittle, which is not preferable.

  For the synthesis of the isocyanate group-containing urethane prepolymer (A), a known reaction catalyst can be used in the urethanization reaction. Moreover, the organic solvent mentioned later can also be used as an organic solvent at the time of a synthesis reaction. In addition, the isocyanate group-containing urethane prepolymer (A) is a one-component moisture-curing type in which the isocyanate group contained is reactively cured with moisture (humidity) in the atmosphere, so that the curable composition comprising this as a curing component is Preferably used.

  Next, the isocyanate group inactive organic solvent (B) component having an ether bond and an ester bond in the molecule other than the cellosolve organic solvent used in the present invention will be described. This isocyanate group-inert organic solvent (B) is obtained by blending into a curable composition comprising the isocyanate group-containing urethane prepolymer (A) and a weather resistance imparting agent (C) described later. The composition has the effect of improving the workability such as extrusion and coating without lowering the viscosity without causing poor appearance of the insoluble matter of the weather resistance-imparting agent (C), and hence without reducing the weather resistance. Is to give. This is because the isocyanate group-inert organic solvent (B) has extremely high solubility in both the isocyanate group-containing urethane prepolymer (A) and the weather resistance imparting agent (C).

［但し、式（１）中、Ｒ^１およびＲ^２は、それぞれ独立に炭素数１〜６の１価の脂肪族炭化水素基を表す］

［但し、式（２）中、Ｒ^３は炭素数１〜６の１価の脂肪族炭化水素基を表し、Ｒ^４は炭素数３または４の２価の脂肪族炭化水素基を表し、Ｒ^５は炭素数１または２の１価の炭化水素基を表す］。 The isocyanate group inactive organic solvent (B) having an ether bond and an ester bond in the molecule other than the cellosolve organic solvent has at least one ether bond and preferably one ester bond in the molecule, preferably at room temperature. And is a compound having a boiling point of 200 ° C. or lower and other than the cellosolve organic solvent. Cellosolve organic solvents such as ethylene glycol monoethyl ether acetate (cellosolve acetate) have an ether bond and an ester bond in the molecule, but they are listed as organic solvents of the second kind and are highly toxic. Since it is not preferable in achieving, it is not used.
The term “isocyanate group inactive” means that the molecule of the organic solvent (B) does not have an active hydrogen-containing functional group such as a hydroxyl group, amino group or carboxyl group that reacts with the isocyanate group.
The isocyanate group-inert organic solvent (B) is preferably a compound represented by the following general formula (1) and / or (2). In the present invention, the compound represented by the general formula (1) alone may be used, the compound represented by the general formula (2) alone may be used, or the compound represented by the general formula (1) may be used. And a compound represented by the general formula (2) may be used in combination.

[In the formula (1), R ¹ and R ² each independently represents a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms]

[In the formula (2), R ³ represents a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms; R ⁴ represents a divalent aliphatic hydrocarbon group having 3 or 4 carbon atoms; ⁵ represents a monovalent hydrocarbon group having 1 or 2 carbon atoms].

In the general formula (1), as R ¹ is a methyl group, an ethyl group, a propyl group, an isopropyl group, and a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms such as hexyl, as R ² is Examples thereof include the same monovalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms as mentioned for R ¹ . Specific examples of the compound represented by the general formula (1) include methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, methyl 3-ethoxypropionate, and 3-ethoxypropion. Examples include ethyl acid, propyl 3-ethoxypropionate, and ethyl 3-propoxypropionate, and these can be used alone or in combination of two or more.

In the general formula (2), a methyl group as R ^3, an ethyl group, a propyl group, an isopropyl group, and a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms such as hexyl, as R ⁴ is , A propylene group, an isopropylene group, a butylene group, and a divalent aliphatic hydrocarbon group having 3 or 4 carbon atoms, such as an isobutylene group. R ³ is a monovalent group having 1 or 2 carbon atoms in a methyl group or an ethyl group. And an aliphatic hydrocarbon group. Specific examples of the compound represented by the general formula (2) include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl. Examples include ether propionate, butylene glycol monomethyl ether acetate, butylene glycol monoethyl ether acetate, and these may be used alone or in combination of two or more.

Among these, 3-ethoxypropion is a compound represented by the general formula (1) because it is easily available and has excellent solubility in both the component (A) and the component (C) described later. Ethyl acid is preferable, and among the compounds represented by the general formula (2), propylene glycol monomethyl ether acetate and butylene glycol monomethyl ether acetate (methoxybutyl acetate) are preferable.
It is preferable to use it so that the usage-amount of an isocyanate group inactive organic solvent (B) may be 1-50 mass% in the whole curable composition, 1-10 mass%, especially 1-5 mass%. If the amount is less than 1% by mass, the effect of lowering the viscosity of the curable composition is small.

  Further, in the present invention, the carbonate organic solvent (D) is used alone to dissolve the weather resistance imparting agent (C) to be described later upon heating, but the weather resistance imparting agent when cooled to room temperature. The curable composition obtained by precipitation of (C) is not preferable because the appearance is deteriorated and the appearance is deteriorated, but is used in combination with the isocyanate group-inert organic solvent (B) to such an extent that the appearance is not deteriorated. be able to.

  Specific examples of the carbonate organic solvent (D) include dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate. Among these, dimethyl carbonate is easy to obtain and easy to handle. Is preferred.

  In addition, in this invention, the organic solvent inactive with respect to an isocyanate group other than the said organic solvents (B) and (D) can also be used in the range which does not impair the objective of this invention.

  Next, the weather resistance imparting agent (C) used in the present invention will be described. The weatherability-imparting agent (C) is a kind of additive, and is blended into the curable composition comprising the isocyanate group-containing urethane prepolymer (A), whereby oxidation and photodegradation after curing of the curable composition. It is used to prevent thermal deterioration and improve weather resistance. Specific examples of the weather resistance-imparting agent (C) include a hindered amine light stabilizer, a hindered phenol antioxidant, and an ultraviolet absorber.

  Examples of hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 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-tetramethylpi Low molecular weight less than 1,000, such as lysine, LA-52, LA-57, LA-62, LA-67, LA-77, LA-82, LA-87 of trade name ADK STAB series manufactured by Asahi Denka Kogyo Co., Ltd. Molecular weight hindered amine antioxidant; LA-63P, LA-68D of the ADK STAB series, or trade name CHIMASSORB series of 119FL, 2020FDL, 944FD, 944LD, etc. manufactured by Ciba Specialty Chemicals Examples thereof include a high molecular weight hindered amine light stabilizer.

  As the hindered phenol-based antioxidant, 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- Examples thereof include 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 thereof include benzoate-based ultraviolet absorbers such as 3,5-di-tert-butyl-4-hydroxybenzoate.

These weatherability-imparting agents (C) can be used alone or in combination of two or more. However, the hindered amine light stabilizer alone or hindered is effective in improving the weather resistance of the curable composition. A phenolic antioxidant alone or a combination of a hindered amine light stabilizer and a hindered phenol antioxidant, that is, a hindered amine light stabilizer and / or a hindered phenol antioxidant is preferable.
The use amount of the weather resistance imparting agent (C) is preferably 0.01 to 20 parts by mass, particularly preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the isocyanate group-containing urethane prepolymer (A).

Next, the additive (E) other than the weather resistance imparting agent (C) that can be further blended in the present invention will be described. Examples of the additive (E) include a moisture-reactive compound, a thixotropic agent, a filler, an adhesion-imparting agent, a colorant, a plasticizer, and a curing acceleration catalyst. These may be used alone or in combination of two or more. Can be used.
Moisture-reactive compounds can enter from the moisture content of the isocyanate group-inert organic solvent (B), weather resistance-imparting agent (C), other additives (E) described later, or from the outside during reaction or storage. By reacting with moisture, the curable composition during production or storage is dehydrated, and the isocyanate group of the isocyanate group-containing urethane prepolymer (A) is prevented from reacting with moisture and thickening, and the curable composition It is used to increase the storage stability of things.

  Examples of the moisture-reactive compound include organic compounds and inorganic compounds having a property of reacting with moisture. Examples of the moisture-reactive organic compound include silicic acid esters such as tetramethoxysilane and tetraethoxysilane; methyltrimethoxysilane, Low molecular weight hydrocarbon group-bonded alkoxysilanes such as methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane; n-butyl monoisocyanate, n-hexyl monoisocyanate, n -Organic monoisocyanate compounds such as octadecyl monoisocyanate, phenyl monoisocyanate, p-toluenesulfonyl monoisocyanate and the like, and moisture-reactive inorganic compounds include magnesium oxide, calcium oxide and the like. Oxides of potassium earth metals.

These can be used singly or in combination of two or more, but organic monoisocyanate compounds require a large amount of use because they have a high reaction rate with moisture and are effective when used in small amounts. Are preferably alkaline earth metal oxides, and p-toluenesulfonyl monoisocyanate is preferable among organic monoisocyanate compounds, and calcium oxide is preferable among alkaline earth metal oxides.
In addition, the alkaline earth metal oxide, which is generated by reacting with moisture, becomes alkaline earth metal hydroxide, has alkalinity, and when the isocyanate group-containing urethane prepolymer is cured by reacting with moisture. Since the generated carbon dioxide gas is reacted and absorbed, it also has the effect of preventing foaming of the cured product due to the generation of carbon dioxide gas.
In the present invention, the moisture-reactive compound may be used in an amount necessary for dehydrating the moisture contained in the system of the curable composition. It is preferable to use 1 to 50 parts by mass. If it is less than 0.1 part by mass, it is insufficient for improving storage stability, and if it exceeds 50 parts by mass, the rubber elastic properties of the cured product are lowered, which is not preferable.

  The thixotropic agent is used to impart thixotropic properties to the curable composition of the present invention so as not to cause sagging (slump) when the composition is filled or applied to a vertical surface such as a building outer wall. Furthermore, this is an extremely important requirement when the curable composition is used as a sealant, but it is an inorganic thixotropic agent such as fine silica, organic surface treated calcium carbonate, organic Examples thereof include organic thixotropic agents such as bentonite and fatty acid amide, and one or more of these can be appropriately selected and added. Of these, finely divided silica is preferable because it can impart thixotropy with a small amount of blending, but if a curing accelerating catalyst described later is used to increase the curing rate of the curable composition, the thixotropic structure is destroyed and the vertical plane is However, organic surface-treated calcium carbonate does not have these disadvantages and gives stable thixotropic properties to the curable composition. This is particularly preferable.

  In this invention, the usage-amount of the said thixotropic agent is 1-200 mass parts with respect to 100 mass parts of isocyanate group containing urethane prepolymer (A), Furthermore, 5-50 mass parts is preferable. If the amount is less than 1 part by mass, the thixotropic effect is lost, and if it exceeds 200 parts by mass, the viscosity of the resulting curable composition increases and the workability deteriorates.

Examples of the fine powder silica include natural silica obtained by pulverizing quartz, silica sand, diatomaceous earth, and the like, wet silica such as precipitated silica, and synthetic silica such as dry silica such as fumed silica. Can be mentioned. Further, the properties of the silica particle surface include a hydrophilic property that is not treated with an organic substance and a hydrophobic property obtained by treating the particle surface with an organic silane compound such as dimethyldichlorosilane. The size of the particles is preferably a so-called colloidal colloid having an average (primary) particle diameter of 1 to 1,000 nm, more preferably 1 to 100 nm, and particularly 5 to 50 nm, from the viewpoint of great thixotropic effect. The BET specific surface area (m ² / g) is 0.1 or more, more preferably 20 to 500, and particularly preferably 40 to 500.
Of these, synthetic colloidal silica and hydrophilic colloidal silica are preferred because of their great thixotropic effect.

  As the organic surface-treated calcium carbonate, finely powdered synthetic calcium carbonate called precipitated calcium carbonate or light calcium carbonate, or heavy calcium carbonate ground by pulverizing natural calcium carbonate, is thixotropic. Fatty acid compounds such as fatty acids, fatty acid alkyl esters, fatty acid metal salts, etc .; for the purpose of imparting imparting ability and preventing secondary aggregation; metal salts of resin acids such as rosin acid, reaction of organic polyisocyanate with stearyl alcohol Examples of the product include calcium carbonate treated with an organic compound such as coupling agents similar to the silane coupling agent described below. The fatty acid metal salt is preferably a sodium, potassium, calcium or aluminum salt of a fatty acid having 10 to 25 carbon atoms such as stearic acid. Examples of these commercially available products include Shiroishi Kogyo Co., Ltd., White Gloss Flower CC, White Gloss Flower CCR, White Gloss Flower R06, VIGOT-10, VIGOT-15, STAVIGOT-15A, NCC # 3010, NCC # 1010 manufactured by Nitto Flour Chemical Co., Ltd. It is done. These can be used alone or in combination of two or more. Of these, fatty acid-based compound surface-treated calcium carbonate is particularly preferred because of its high thixotropic effect.

The average particle diameter of the organic surface-treated calcium carbonate is preferably 0.01 to 1.0 μm, more preferably 0.03 to 0.15 μm, and the BET specific surface area is 5 to 200 m ² / g, and further 10 to 60 m ² / g. preferable. If the average particle size is less than 0.01 μm, or if the BET specific surface area exceeds 200 m ² / g, the viscosity of the resulting curable composition will increase and the workability will deteriorate, and will the average particle size exceed 1.0 μm? If the BET specific surface area is less than 5 m ² / g, the thixotropic effect is lost, which is not preferable.

  The filler is used for increasing and reinforcing, but synthetic silica such as mica, kaolin, zeolite, graphite, diatomaceous earth, clay, clay, talc, silicic anhydride, quartz, aluminum powder, zinc powder, precipitated silica, Inorganic powder fillers such as calcium carbonate, calcium hydroxide, magnesium carbonate and alumina, fiber fillers such as glass fibers and carbon fibers, inorganic balloon fillers such as glass balloons, shirasu balloons, silica balloons and ceramic balloons Inorganic fillers such as wood powder, walnut flour, rice husk flour, pulp powder, cotton chips, rubber powder and other plant fillers; synthetic resin powder filling such as polyethylene, polyvinyl chloride, poly (meth) acrylate, etc. Agents: Organic fillers such as organic balloon fillers such as Saran microballoons, and magnesium hydroxide And flame retardant fillers such as um and aluminum hydroxide also mentioned, the particle size 0.01~1,000μm is preferred. These can be used alone or in combination of two or more.

  The adhesiveness-imparting agent is used for improving the adhesiveness of the curable composition. In addition to the coupling agent, an epoxy resin, a phenol resin, an alkyl titanate, an organic polyisocyanate, and the like can be given.

Examples of the coupling agent include various coupling agents such as silane-based, aluminum-based, and zircoaluminate-based and / or partial hydrolysis condensates thereof. Of these, the silane-based coupling agent and / or the portion thereof. A hydrolyzate is preferable because of its excellent adhesiveness.
Specific examples of the silane coupling agent include vinyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, vinylmethyldimethoxy. Silane, 3- (meth) acryloxypropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3- Low molecular weight compounds containing alkoxysilyl groups such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, etc., having a molecular weight of 500 or less, preferably 400 or less, and / or one of these silane coupling agents Or two or more parts It may include compounds having a molecular weight of 200 to 3,000 in the hydrolysis-condensation product. These can be used alone or in combination of two or more.

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 combination of two or more.

  The total amount of the filler, the adhesion-imparting agent, and the colorant is preferably 0 to 500 parts by mass, particularly preferably 5 to 300 parts by mass with respect to 100 parts by mass of the isocyanate group-containing urethane prepolymer.

  The plasticizer is used to lower the viscosity of the curable composition to improve workability, or to adjust the physical properties after curing, and includes dioctyl phthalate (DOP), dibutyl phthalate, phthalate Phthalate esters such as butyl benzyl acid, dioctyl adipate, diisodecyl succinate, dibutyl sebacate, butyl oleate, etc., phosphate esters such as trioctyl phosphate, tricresyl phosphate, chlorinated paraffin, etc. A low molecular weight plasticizer having a molecular weight of less than 1,000, such as a halogenated aliphatic compound; the same polyoxyalkylene polyol or polyoxyalkylene monool as mentioned in the synthesis of the isocyanate group-containing urethane prepolymer (A); Alkyl etherified or alkyl esterified polymers Hydroxyl group obtained by reacting an ether plasticizer or similar polyoxyalkylene polyol or polyoxyalkylene monool with the same organic monoisocyanate or organic polyisocyanate as mentioned in the synthesis of the urethane prepolymer (A). And polyether urethane plasticizers that do not contain isocyanate groups, saccharide polyethers obtained by addition polymerization of ethylene oxide or propylene oxide to saccharide polyhydric alcohols such as sucrose, alkyl etherification or esterification, polybutadiene, poly High molecular weight plasticizers having a molecular weight of 1,000 or more, such as olefin polymers such as chloroprene, polyisoprene, and hydrogenated polyptene.

  However, since low molecular weight plasticizers such as DOP are likely to migrate (bleed) to the surface of the cured product, there is a drawback that dust in the atmosphere adheres to the surface due to viscosity, and surface contamination occurs. If it leaks into the environment such as rivers and oceans, it is an endocrine disrupting substance, so-called environmental hormones, and it is suspected of disturbing the ecosystem, and it is not preferred to use it. A high molecular weight plasticizer having a molecular weight of 1,000 or more and further having a molecular weight of 1,000 to 20,000 is preferable, and among the high molecular weight plasticizers, polyether urethane plasticizers are preferable.

  For the above reasons, it is desirable to keep the amount of the plasticizer used in a small amount, preferably 50 parts by mass or less, more preferably 20 parts by mass or less, and 0 parts by mass with respect to 100 parts by mass of the isocyanate group-containing urethane prepolymer (A). Most preferably not used with parts.

  Examples of the curing accelerating 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 acids such as octylic acid, octenoic acid, naphthenic acid; metal chelate compounds such as dibutyltin bis (acetylacetonate), zirconium tetrakis (acetylacetonate), titanium tetrakis (acetylacetonate); dibutyltin dilaurate, Salts of organic metals and organic acids such as dioctyltin dilaurate; triethylenediamine, triethylamine, tri-n-butylamine, hexamethylenetetramine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 1, 4-diazabicyclo [2,2,2] octane (DA BCO), tertiary amines such as N-methylmorpholine and N-ethylmorpholine; or salts of these amines with organic acids. These can be used alone or in combination of two or more. Of these, a metal chelate compound or a salt of an organic metal and an organic acid is preferable, and dibutyltin dilaurate is more preferable because it has a high effect of promoting curing.

  The method for producing the curable composition of the present invention is not particularly limited. For example, an organic isocyanate and an active hydrogen-containing compound are charged into a reaction vessel made of stainless steel, and the presence or absence of a urethanization reaction catalyst. In the presence or absence of an organic solvent in the presence or absence of moisture such as in a nitrogen gas stream, the reaction is carried out by heating at 50 to 120 ° C. for 0.5 to 10 hours, and the urethane containing isocyanate groups is previously obtained. A prepolymer (A) is synthesized. In a separately prepared kneading container such as made of stainless steel, the obtained isocyanate group-containing urethane prepolymer (A), an isocyanate group-inert organic solvent (B), a weather resistance imparting agent (C), and a carbonic acid ester-based organic material When using an additive (E) other than the solvent (D) and the weather resistance imparting agent (C), these are charged and kneaded, and then the inside of the kneading vessel is degassed by depressurization, and then made of paper, resin or Examples thereof include a method of producing a curable composition product by packing in a suitably selected container such as a metal cartridge, a pail can, or a bag and sealing it. At this time, after reacting the isocyanate group-containing urethane prepolymer (A), other raw materials may be charged without transferring to another container, or the reaction of the isocyanate group-containing urethane prepolymer (A) You may carry out in presence of other raw materials, such as an inert organic solvent (B) and an additive (E).

  The curable composition of the present invention may be used as a one-component type according to the application, or as a two-component type using the curable composition of the present invention as a main agent and water or an amine compound as a curing agent. However, it is preferable to use it as a one-component moisture-curable curable composition because there is no trouble of mixing the main agent and the curing agent, and there is no inconvenience such as poor mixing and the workability is excellent.

  In addition, examples of the use of the curable composition of the present invention include adhesives, paints, sealing materials, and the like for construction, civil engineering, and automobiles. It is preferably used as an adhesive or a sealing material.

  In addition, the materials to which the curable composition of the present invention is applied include cement-based materials such as mortar and concrete, natural stone materials such as marble, ceramic materials such as siding and tiles, and various materials such as polyethylene and vinyl chloride. A sheet-like or plate-like material made of a synthetic resin, a wood-based material such as wood or plywood, and the like are preferable because of good adhesiveness.

  The curable composition of the present invention has the above-described constitution, and has a low toxicity and an improved adverse effect on the environment. Even when a weathering agent is used, the appearance of the cured product is good and the storage stability is improved. It has the effect of being excellent.

  Although the Example of this invention is shown below, this invention is not limited to this Example.

Synthesis Example 1 Synthesis of Isocyanate Group-Containing Urethane Prepolymer PU-1 Polyoxypropylene diol (manufactured by Asahi Glass Co., Ltd.) while flowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, nitrogen introduction tube and heating / cooling device , EXCENOL 3021, number average molecular weight 3,300) 666 g and polyoxypropylene triol (Mitsui Chemicals Polyurethane, Triol-MN-4000, number average molecular weight 4,000) were charged in 195 g, while stirring, 4,4′- 138 g of diphenylmethane diisocyanate (MDI) (manufactured by Nippon Polyurethane Industry Co., Ltd., Millionate MT, molecular weight 250) and 0.1 g of tin octylate (manufactured by Nitto Kasei Co., Ltd., Neostan U-28) as a reaction catalyst were added and heated to 70. It reacts at -80 ° C for 2 hours, and the isocyanate group content is a theoretical value ( The reaction was terminated at the time point when .33 wt%) or less, was synthesized an isocyanate group-containing urethane prepolymer PU-1.
The obtained urethane prepolymer PU-1 was a viscous liquid transparent at room temperature having an isocyanate group content of 2.16% by mass and a viscosity of 34,000 mPa · s at 25 ° C. by titration.

Example 1
While flowing nitrogen gas into a kneading vessel equipped with a stirrer, a decompression device and a nitrogen introduction tube, 100 g of the isocyanate group-containing urethane prepolymer PU-1 obtained in Synthesis Example 1 was charged, and while stirring, 100 g of heavy calcium carbonate, 30 g of fatty acid surface-treated calcium carbonate (manufactured by Shiroishi Kogyo Co., Ltd., Shiruka Hana CCR-B) was charged and sufficiently kneaded until the contents became uniform. Next, using another beaker, 2 g of ethyl 3-ethoxypropionate (manufactured by Sankyo Chemical Co., Ltd., trade name: EEP) and 2 g of the following hindered amine light stabilizer (made by ADEKA, trade name: ADK STAB LA-63P) In addition, 7 g of a solution prepared by heating and dissolving at 50 to 60 ° C., 1 g of p-toluenesulfonyl monoisocyanate and 0.05 g of dibutyltin dilaurate were sequentially added, and further kneaded until the contents were uniform. . Subsequently, degassed under reduced pressure at 20 to 50 hPa, filled in a paper cartridge container and sealed to prepare a one-component moisture-curing type sealing material S-1. The obtained one-component moisture-curable sealing material S-1 was a paste-like liquid at room temperature.

  Hindered amine light stabilizer: 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol, β, β, β ′, β′-tetramethyl- Condensate with 3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) diethanol (trade name: ADK STAB LA-63P, manufactured by ADEKA)

Examples 2 and 3
In Example 1, 13 g of a solution prepared by heating and dissolving 3 g of a hindered amine light stabilizer at 50 to 60 ° C. in 10 g of ethyl 3-ethoxypropionate in Example 2 using a beaker, and For Example 3, 50 g of 2 g of hindered amine light stabilizer and 2 g of the following hindered phenol antioxidant (trade name: IRGANOX 1010) manufactured by Ciba Specialty Chemicals Co. to 10 g of ethyl 3-ethoxypropionate. In the same manner, except that 14 g of the solution prepared by heating and dissolving at 0 ° C. was blended, one-component moisture-curing sealing materials S-2 and S-3 as paste-like liquids were prepared at room temperature, respectively.
Hindered phenol antioxidant: pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 1010, manufactured by Ciba Specialty Chemicals)

Example 4
In Example 1, 13 g of a solution prepared by adding 3 g of hindered amine light stabilizer to 5 g of ethyl 3-ethoxypropionate and 5 g of dimethyl carbonate using a beaker and heating to 50 to 60 ° C. to dissolve. In the same manner as described above, a one-part moisture-curing sealing material S-4 as a paste-like liquid was prepared at room temperature.

Example 5
In Example 1, 20 g of methyl 3-methoxypropionate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used in place of ethyl 3-ethoxypropionate using a beaker, and 3 g of hindered amine light stabilizer was added thereto. A one-part moisture-curing sealing material S-5 as a paste-like liquid was prepared at room temperature in the same manner except that 23 g of a solution prepared by heating to -60 ° C and dissolving was blended.

Example 6
In Example 1, 5 g of ethyl 3-ethoxypropionate and 5 g of methyl 3-methoxypropionate were used in a beaker, and 2 g of hindered amine light stabilizer and hindered phenolic antioxidant used in Example 3 were used. In the same manner, except that 2 g of the agent was added and 14 g of a solution prepared by heating to 50 to 60 ° C. and dissolving was blended, a one-part moisture-curing sealing material S-6 as a paste-like liquid was prepared at room temperature.

Example 7
In Example 1, 5 g of ethyl 3-ethoxypropionate and 5 g of propylene glycol monomethyl ether acetate (manufactured by Sankyo Chemical Co., Ltd., trade name: PMA) were used in a beaker, and this was carried out with 2 g of a hindered amine light stabilizer. In the same manner as in Example 3, except that 2 g of the hindered phenol antioxidant used in Example 3 was added and 14 g of a solution prepared by heating and dissolving at 50 to 60 ° C. was blended. A curable sealing material S-7 was prepared.

Examples 8-10
In Example 1, using a beaker, instead of ethyl 3-ethoxypropionate, 10 g of propylene glycol monomethyl ether acetate for Example 8, 10 g of propylene glycol monoethyl ether acetate for Example 9, and about Example 10 10 g of methoxybutyl acetate (manufactured by Sankyo Chemical Co., Ltd., trade name: methoxybutyl acetate), 3 g of a hindered amine light stabilizer was added to each, and the solution was prepared by heating to 50 to 60 ° C. and dissolving. In the same manner except that 13 g of each was blended, one-part moisture-curing sealing materials S-8, S-9, and S-10 as paste liquids were prepared at room temperature.

Examples 11-13
In Example 1, instead of using ethyl 3-ethoxypropionate in a beaker, Example 11 contains 5 g of propylene glycol monomethyl ether acetate, 5 g of propylene glycol monoethyl ether acetate and 2 g of a hindered amine light stabilizer and Example 3. 2 g of the hindered phenolic antioxidant used in Example 1, 5 g of propylene glycol monoethyl ether acetate and 5 g of methoxybutyl acetate for Example 12, 3 g of hindered amine light stabilizer, and propylene glycol monoethyl ether for Example 13 2 g of hindered amine light stabilizer and 2 g of hindered phenol antioxidant used in Example 3 were added to 5 g of acetate and 5 g of dimethyl carbonate, respectively, and heated to 50-60 ° C. In the same manner, except that 14 g, 13 g, and 14 g of the dissolved solution prepared respectively were blended, the one-part moisture-curing sealing materials S-11, S-12, and S-13 that were paste-like liquids at room temperature were prepared. .

Comparative Examples 1-3
In Example 1, using a beaker, instead of ethyl 3-ethoxypropionate, 3 g of hindered amine light stabilizer was added to 10 g of dimethyl carbonate for Comparative Example 1 and 10 g of toluene was used for Comparative Example 2 to be hindered amine light stable. In the same manner as in Comparative Example 3, except that 3 g of hindered amine light stabilizer was added to 10 g of xylene for Comparative Example 3 and 13 g of each of the solutions prepared by heating and dissolving at 50 to 60 ° C. was added. A one-part moisture-curing sealing material comparison S-1, a comparison S-2, and a comparison S-3 were prepared.

  The results of the following tests using the one-component moisture-curing sealants S-1 to S-13 and Comparative S-1 to S-3 obtained in Examples 1 to 13 and Comparative Examples 1 to 3 are blended compositions. In addition, Examples 1 to 6 and Comparative Examples 1 to 3 are shown in Table 1, and Examples 7 to 13 are shown in Table 2.

[Test method]
(1) Toxicity of organic solvents Regarding the organic solvents used, those that fall under the category 2 organic solvents listed in the organic solvent poisoning regulations of the Industrial Safety and Health Law are marked with “X”, and those that are not applicable are marked with “◯”.

(2) Slump The slump (longitudinal) at 23 ° C. was measured according to “4.1 slump test method” of “Testing method of sealing material for building” in JIS A 1439 (1997, revised 2002).

(3) Appearance A container filled with a one-component moisture-curing sealing material is placed at 23 ° C. and 50% relative humidity for 1 day, and then flattened to a thickness of 2 to 3 mm on the surface of a 100 × 100 × 3 mm flexible board. The surface was visually observed, and the appearance was evaluated according to the following criteria.
[Criteria]
○: No surface roughness or very little and smooth surface.
X: The surface has many bumps.

(4) Weather resistance A one-component moisture-curing type sealing material is applied to a release paper in the form of a sheet with a thickness of 2 to 3 mm, taking care not to engulf bubbles, and at 23 ° C. and 50% relative humidity. After curing for 14 days, a specimen cut into a strip was used. A sunshine weather meter was used on the surface of the test body according to “5. Open frame carbon arc lamp type weather resistance test” of “Weather resistance test method of vulcanized rubber and thermoplastic rubber” in JIS K 6266 (1996, confirmation 2001). In the SA method, light was irradiated under conditions of water spraying for 18 minutes after irradiation for 102 minutes at a black panel temperature of 63 ° C. After 1000 hours of irradiation, the test specimen was taken out and the surface was visually observed, and the weather resistance was evaluated according to the following criteria.
[Criteria]
○: Clear cracks are not observed on the surface or very few.
X: Many clear cracks are observed on the surface.

Claims (5)

A one-component moisture curable sealing material containing an isocyanate group-containing urethane prepolymer (A), an isocyanate group-inert organic solvent (B), and a weather resistance imparting agent (C),
The isocyanate group-inert organic solvent (B) is methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxy Propyl propionate, ethyl 3-propoxypropionate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, butylene glycol One kind selected from the group consisting of monomethyl ether acetate and butylene glycol monoethyl ether acetate Or two or more compounds,
A one-component moisture-curing sealant, wherein the weather resistance imparting agent (C) is a hindered amine light stabilizer and / or a hindered phenol antioxidant. The one-component moisture-curable sealing material according to claim 1 , wherein the isocyanate group-inert organic solvent (B) is ethyl 3-ethoxypropionate. The one-component moisture-curable sealing material according to claim 1 , wherein the isocyanate group-inert organic solvent (B) is propylene glycol monomethyl ether acetate and / or butylene glycol monomethyl ether acetate. Furthermore, the 1 liquid moisture hardening type sealing material of any one of Claims 1-3 which mix | blends a carbonate ester organic solvent (D). Furthermore, 1 liquid moisture hardening type sealing materials of any one of Claims 1-4 which mix | blend additives (E) other than a weather-resistance imparting agent (C).