JP2016145321A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition that has excellent workability and can quicken the curing of a depth portion at the time of curing to shorten a period for the work.SOLUTION: A curable composition comprises a composition (A) comprising curable resin and a composition (B) that comprises water comprising metal ions.SELECTED DRAWING: None

Description

  The present invention relates to a curable composition excellent in deep part curability.

  A curable composition containing a polyurethane resin, a silicone resin, a modified silicone resin, or a polysulfide resin as a curing component is a sealing material composition for architectural, civil engineering, automobile, etc., waterproof material composition, adhesive composition, coating It is used as a material composition. Among them, curable compositions containing polyurethane resins and modified silicone resins as curing components are widely used for construction and civil engineering because of their good workability and excellent rubber properties after curing and adhesion to various components. ing. As a curable composition containing a polyurethane resin or a modified silicone resin as a curing component, a one-component curable composition that is mainly cured by reacting with moisture in the air, and a main component and a curing agent are mixed and reacted to be cured. There are two-component curable compositions.

  The one-component curable composition is superior in workability because there is no trouble of mixing the main agent and the curing agent and there is no curing failure due to a measurement error of the main agent and the curing agent. It may take a long time to proceed. In addition, the two-component curable composition is more curable than the one-component curable composition, but the construction period may be longer if a curing period is provided until the curing is slow in winter when the temperature is low. .

  As an attempt to speed up the curing of the curable composition, for example, a two-component sealant composition containing an isocyanate group-containing prepolymer has been proposed (see, for example, Patent Document 1). Although the composition disclosed in Patent Document 1 is more curable than the one-component sealant composition, in order to shorten the work period (for example, shorten the work period in winter) with the construction of the sealant composition Further, it is necessary to further accelerate the curability of the composition, particularly the deep curability. As a means for this, a curing accelerating catalyst can be blended in the composition to accelerate the curability, but when a curing accelerating catalyst is blended, not only the deep curability at the time of curing but also the surface curability is accelerated. A new problem arises that the pot life after mixing the agent is shortened and workability is deteriorated.

  Moreover, when placing a curable composition, a curing tape and a curing sheet are often affixed so that a curable composition may not adhere to the periphery of a member. If the curability of the curable composition is fast, when the curing tape or the curing sheet is peeled off, the curable composition remaining on the curing tape or the curing sheet is also pulled at the same time, which may cause a design defect.

JP 2014-047268 A

  In view of the above problems, an object of the present invention is to provide a curable composition capable of accelerating the deep curability during curing and shortening the construction period. Moreover, it is providing the curable composition which prevents the malfunction in the design at the time of peeling a curing tape or a curing sheet, even if hardening property is accelerated.

As a result of intensive studies to solve the above-mentioned requirements, the present inventor contains a composition (A) containing a curable resin and a composition (B) containing water containing metal ions. The present inventors have found that the composition is excellent in deep part curability and can shorten the work period of construction, and has completed the present invention. That is, this invention is shown to following (1)-(10).
(1) A curable composition comprising a composition (A) containing a curable resin and a composition (B) containing water containing metal ions.
(2) The curable composition according to (1), wherein the curable resin is an isocyanate group-containing resin or a crosslinkable silyl group-containing resin.
(3) The curable composition according to (1) or (2), wherein the composition (A) contains a block amine compound.
(4) The curable composition according to any one of (1) to (3), wherein the block amine compound is at least one compound selected from an oxazolidine compound, an aluminidine compound, and a ketimine compound.
(5) The curable composition according to any one of (1) to (4), wherein the composition (A) contains a carboxylic anhydride compound and / or a carboxylic acid silyl ester compound.
(6) The curable composition according to any one of (1) to (5), wherein the metal ion is an alkali metal ion and / or an alkaline earth metal ion.
(7) The curable composition according to any one of (1) to (6), further comprising an additive.
(8) The amount of water containing the metal ions is 0.1 to 5 parts by mass with respect to 100 parts by mass of the curable resin, according to any one of (1) to (7) Curable composition.
(9) The curable composition according to any one of (1) to (8), wherein the curable composition is a curable composition for construction or civil engineering.
(10) The curable composition according to any one of (1) to (9), wherein the curable composition is a sealing material composition, a waterproof material composition, an adhesive composition, or a coating material composition. Composition.

  The curable composition of the present invention is excellent in deep part curability and can shorten the construction period. Moreover, even if sclerosis | hardenability is accelerated | stimulated, the curable composition which prevents the malfunction on the design at the time of peeling a curing tape or a curing sheet can be provided.

  Hereinafter, the present invention will be described in detail according to embodiments.

  The present invention is a curable composition comprising a composition (A) containing a curable resin and a composition (B) containing water containing metal ions. Hereinafter, each component will be described in detail.

Composition (A)
The composition (A) in the present invention is a composition containing a curable resin, and the curable resin reacts with the active hydrogen-containing compound to be cross-linked and cured to obtain a cured product. The curable resin is not particularly limited as long as it is cured by reacting with the active hydrogen-containing compound. Specific examples include isocyanate group-containing resins and crosslinkable (hydrolyzable) silyl group-containing resins.

  The isocyanate group-containing resin is a resin having one or more isocyanate groups in the resin, and the isocyanate groups react with active hydrogen (groups) to form urethane bonds, urea bonds, and the like, and are cured by crosslinking. As the isocyanate group-containing resin, an isocyanate group-containing urethane prepolymer (hereinafter referred to as an isocyanate group-containing urethane prepolymer and an isocyanate group-containing urethane prepolymer into which a photoreactive unsaturated bond described later is introduced is simply referred to as “urethane prepolymer”) May also be mentioned.

  In the isocyanate group-containing urethane prepolymer, the organic isocyanate compound and the active hydrogen-containing compound have an isocyanate group / active hydrogen molar ratio of preferably 1.2 to 10/1, more preferably 1.2 to 5/1. The reaction can be performed collectively or sequentially within the range so that the isocyanate group remains in the urethane prepolymer. When the molar ratio is less than 1.2 / 1, the viscosity of the urethane prepolymer increases, and the workability of the curable composition deteriorates. On the other hand, if the molar ratio exceeds 10/1, the amount of carbon dioxide generated when the isocyanate group reacts with water increases, which causes foaming during curing.

  The isocyanate group content in the isocyanate group-containing urethane prepolymer is preferably 0.3 to 15% by mass, particularly preferably 0.5 to 5% by mass. When isocyanate group content is less than 0.3 mass%, the viscosity of a urethane prepolymer will become high and the workability | operativity of a curable composition will worsen. Moreover, when isocyanate group content exceeds 15 mass%, the quantity of the carbon dioxide gas generate | occur | produced when an isocyanate group reacts with water increases, and causes foaming at the time of hardening.

  The number average molecular weight of the isocyanate group-containing urethane prepolymer is preferably 1,500 or more, more preferably 1,500 to 20,000, still more preferably 1,500 to 15,000, and particularly preferably 1,500 to 10,000. preferable. In addition, the number average molecular weight in this invention is a numerical value of polystyrene conversion measured by gel permeation chromatography (GPC).

  As a method for producing an isocyanate group-containing urethane prepolymer, specifically, an organic isocyanate compound and an active hydrogen-containing compound are charged into a reaction vessel made of glass or stainless steel, and in the presence or absence of a reaction catalyst or an organic solvent. Below, the method of making it react at 50-120 degreeC stirring is mentioned. At this time, when the isocyanate group reacts with water such as moisture in the air, the urethane prepolymer thickens. Therefore, it is preferable to replace the inside of the container with nitrogen gas in advance or perform the reaction under a nitrogen gas stream.

  An organic polyisocyanate can be mentioned as an organic isocyanate compound. The organic polyisocyanate is a compound having two or more isocyanate groups in the compound. Specifically, toluene polyisocyanate such as 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, 4,4′- Diphenylmethane polyisocyanate such as diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4,6 -Phenylene polyisocyanate such as trimethylphenyl-1,3-diisocyanate, 2,4,6-triisopropylphenyl-1,3-diisocyanate, 1,4-naphthalene diisocyanate, , 5-naphthalene diisocyanate naphthalene polyisocyanate, chlorophenylene-2,4-diisocyanate, 4,4'-diphenyl ether diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenyl And aromatic polyisocyanates such as -4,4'-diisocyanate. 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, Aliphatic polyisocyanates such as decamethylene diisocyanate and lysine diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, aromatic aliphatic polyisocyanates such as p-xylylene diisocyanate, 1,4-cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenation Examples thereof include alicyclic polyisocyanates such as toluene diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Furthermore, polymeric isocyanates, such as polymethylene polyphenyl polyisocyanate and crude toluene diisocyanate, are mentioned. Furthermore, modified isocyanates having one or more uretdione bonds, isocyanurate bonds, allophanate bonds, burette bonds, uretonimine bonds, carbodiimide bonds, urethane bonds or urea bonds, obtained by modifying these organic polyisocyanates. Any of these may be used alone or in combination of two or more.

  Of these, aliphatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, and modified isocyanates obtained by modifying these organic polyisocyanates are preferred because of the excellent weather resistance of the curable composition.

  Moreover, organic monoisocyanate can be used with organic polyisocyanate. That is, a mixture of organic polyisocyanate and organic monoisocyanate can be used as the above-mentioned organic isocyanate compound. The organic monoisocyanate is a compound having one isocyanate group in the compound, specifically, n-butyl monoisocyanate, n-hexyl monoisocyanate, n-hexadecyl monoisocyanate, n-octadecyl monoisocyanate, Examples thereof include p-isopropylphenyl monoisocyanate and p-benzyloxyphenyl monoisocyanate.

  An active hydrogen-containing compound is a compound having one or more active hydrogens (groups) in the compound. Specifically, in addition to polymer polyols and polymer polyamines, low molecular polyols, low molecular amino alcohols, low molecular polyamines used as chain extenders in some cases, polymers and low molecular materials used for modification of urethane prepolymers Monool is mentioned.

  Examples of the polymer polyol include polyester polyol, polycarbonate polyol, polyoxyalkylene polyol, hydrocarbon polyol, poly (meth) acrylate polyol, animal and plant polyol, and copolyols thereof. In the present invention, “(meth) acrylate” means “acrylate and / or methacrylate”.

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

  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, etc. Polycarboxylic acids of these; anhydrides of these acids or one or more of alkyl esters such as methyl ester and ethyl ester; and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene Polyester obtained by reaction with one or more of low molecular polyols such as glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, ethylene oxide or propylene oxide adduct of bisphenol A, trimethylolpropane, glycerin, pentaerythritol, etc. A polyol is mentioned. In addition to these polycarboxylic acids and acid anhydrides, low-molecular polyols, low-molecular polyamines such as butylene diamine, hexamethylene diamine, xylylene diamine, and isophorone diamine, and low-molecular molecules such as monoethanol amine and diethanol amine Also included are polyester amide polyols obtained by reaction with one or more amino alcohols.

  Furthermore, 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 in the synthesis of the above-mentioned polyester polyol, or transesterification reaction of low molecular polyols with diethylene carbonate, dimethyl carbonate, diethyl carbonate, and diphenyl carbonate. Can be obtained.

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

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

  Furthermore, the polyoxyalkylene-based polyol is produced at the time of its production, cesium hydride, cesium methoxide, cesium alkoxides such as cesium ethoxide, cesium compounds such as cesium hydroxide, diethyl zinc, iron chloride, metalloporphyrin, phosphazenium compounds, Double metal cyanide complexes can be used as catalysts.

  Above all, it can catalyze double metal cyanide complexes such as zinc hexacyanocobaltate glyme complex and diglyme complex in that the viscosity of the resulting urethane prepolymer can be lowered and the rubber properties after curing of the curable composition will be good. As a total unsaturation of 0.1 meq / g or less, further 0.07 meq / g or less, particularly 0.04 meq / g or less, molecular weight distribution [polystyrene conversion by gel permeation chromatography (GPC) The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) = Mw / Mn] is 1.6 or less, particularly 1.0 to 1.3.

  For modification of urethane prepolymers, polyoxypropylene-based monopolymers obtained by ring-opening addition polymerization of cyclic ether compounds such as propylene oxide using low molecular monoalcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol as initiators. Polyoxyalkylene monools such as all can also 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. % 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 molecule is composed of polyoxyalkylene.

  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 copolymerized in the presence or absence of.

  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 Is mentioned.

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

  Any of the above polymer polyols can be used alone or in combination of two or more. Of these, polyoxyalkylene-based polyols and poly (meth) acrylate-based polyols are preferable from the viewpoint of good rubber properties and adhesiveness of the resulting curable composition.

  In order to provide weather resistance to the isocyanate group-containing urethane prepolymer, a photoreactive unsaturated bond can also be introduced into the urethane prepolymer. The urethane prepolymer into which a photoreactive unsaturated bond is introduced functions as a curing component in the curable composition of the present invention and has an effect of imparting excellent weather resistance to the cured product. The above-mentioned photoreactive unsaturated bond is an unsaturated bond that undergoes a chemical change such as polymerization in a relatively short time when exposed to light. Specifically, a vinyl group, vinylene group, (meth) An unsaturated bond derived from an acryloyl group can be mentioned. In the present invention, “(meth) acryloyl group” means “acryloyl group and / or methacryloyl group”.

  The isocyanate group of the isocyanate group-containing urethane prepolymer into which the photoreactive unsaturated bond is introduced reacts with the active hydrogen-containing compound to be crosslinked and cured. In addition, the photoreactive unsaturated bond of the isocyanate group-containing urethane prepolymer into which the photoreactive unsaturated bond has been introduced undergoes a polymerization reaction when exposed to light to form a cured film having excellent weather resistance on the surface of the cured product. This cured film is presumed to give excellent weather resistance to the cured product. The photoreactive unsaturated bond is preferably an unsaturated bond derived from a (meth) acryloyl group in that the weather resistance imparting effect is high.

As a method of introducing a photoreactive unsaturated bond into an isocyanate group-containing urethane prepolymer,
(A) an organic isocyanate compound, an active hydrogen-containing compound such as a polymer polyol, and a low molecular weight compound (number average molecular weight less than 1,000) having active hydrogen and a photoreactive unsaturated bond in the molecule, The method obtained by making it react on conditions with excess isocyanate group with respect to the total amount of active hydrogen.
(B) a compound having a high molecular weight (number average molecular weight of 1,000 or more) having an organic isocyanate compound and active hydrogen and a photoreactive unsaturated bond in the molecule (for example, mono (meth) acrylate of polyoxyalkylenetriol, A method obtained by reacting (meth) acrylic acid alkylene oxide adduct, polybutadiene polyol) with an excess of isocyanate groups with respect to the total amount of active hydrogen.
(C) an organic isocyanate compound, a low molecular weight (number average molecular weight less than 1,000) compound having a photoreactive unsaturated bond and an isocyanate group in the molecule (for example, (meth) acryloyl isocyanate), and a polymer polyol A method obtained by reacting an active hydrogen-containing compound such as a compound with an excess of isocyanate groups with respect to the total amount of active hydrogen.
Is mentioned. The method (a) is preferred from the viewpoints of availability of raw materials and ease of reaction. In the present invention, “(meth) acrylic acid” means “acrylic acid and / or methacrylic acid”.

  The reaction for introducing the photoreactive unsaturated bond into the isocyanate group-containing urethane prepolymer may be either a batch charge reaction method or a multistage charge reaction method. The equivalent ratio (isocyanate group / active hydrogen) of the isocyanate group of the organic isocyanate compound to the active hydrogen of the active hydrogen-containing compound (including a compound having an active hydrogen and a photoreactive unsaturated bond) is 1.2 to 10 / 1 is preferable, and 1.2 to 5/1 is more preferable. The isocyanate group content in the isocyanate group-containing urethane prepolymer introduced with a photoreactive unsaturated bond is preferably 0.3 to 15% by mass, and more preferably 0.5 to 5% by mass. When the isocyanate group content is less than 0.3% by mass, the molecular weight becomes too large, the viscosity increases, and the workability decreases. Moreover, since the crosslinking point in a urethane prepolymer decreases, sufficient adhesiveness cannot be obtained. If the isocyanate group content exceeds 15% by mass, the amount of carbon dioxide generated when the isocyanate group reacts with water increases, which causes foaming during curing.

  The concentration of the photoreactive unsaturated bond in the isocyanate group-containing urethane prepolymer introduced with the photoreactive unsaturated bond is preferably 0.01 mmol / g or more, more preferably 0.03 to 1 mmol / g, particularly 0.05-0.5 mmol / g is preferable.

  Compounds having active hydrogen and photoreactive unsaturated bonds (low molecular weight and high molecular weight) are composed of active hydrogen (group) such as hydroxyl group, amino group, carboxyl group and the like, vinyl group, vinylene group, (meta ) A compound having both a photoreactive unsaturated bond such as an acryloyl group, and a compound having a hydroxyl group and a (meth) acryloyl group in the compound from the viewpoint of easy reaction and high weather resistance imparting effect. The molecular weight of the compound having an active hydrogen (group) and a photoreactive unsaturated bond is preferably less than 1,000 in terms of easy reaction.

  Examples of the compound having a hydroxyl group and a (meth) acryloyl group include 2-hydroxyethyl (meth) acrylate, which is a monoester of alkylene glycol such as ethylene glycol, propylene glycol, butylene glycol and (meth) acrylic acid, 2- Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxypentyl (meth) acrylate, hydroxyneopentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate , Hydroxyheptyl (meth) acrylate, monohydroxy mono (meth) acrylates such as hydroxyoctyl (meth) acrylate, glycerin, trimethylolpropane, pentaerythritol A monoester or diester of a tri- or higher-functional alkylene polyol and a polyester such as a triester, glycerol di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate Monohydroxy poly (meth) acrylates such as, glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, polyhydroxymono (meth) acrylates such as pentaerythritol mono (meth) acrylate, pentaerythritol di (meta) And polyhydroxy poly (meth) acrylates such as acrylate. In addition to these, monohydroxy mono (meta) such as diethylene glycol, dipropylene glycol, polyoxyethylene polyol, polyoxypropylene polyol, polyol obtained by adding alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to bisphenol A or bisphenol F. ) Acrylates, polyhydroxy mono (meth) acrylates, polyhydroxy poly (meth) acrylates, hydroxyalkyl (meth) acrylates such as (meth) acrylic acid and hydroxyethyl (meth) acrylate, and the active hydrogen, ethylene oxide, propylene oxide , Compounds to which alkylene oxide such as butylene oxide is added and having a hydroxyl group, modified caprolactone of hydroxyethyl acrylate, etc. Compound having a hydroxyl group may also be mentioned. These can be used alone or in combination of two or more. Of these, monohydroxy poly (meth) acrylates and dihydroxy poly (meth) acrylates are preferred in that the viscosity of the urethane prepolymer can be kept low and the weather resistance imparting effect can be enhanced.

  The crosslinkable silyl group-containing resin is a resin having at least one crosslinkable (hydrolyzable) silyl group in the resin, and the crosslinkable silyl group reacts with an active hydrogen-containing compound (for example, water). A siloxane bond is formed and crosslinked and cured to form a cured product. Examples of the crosslinkable silyl group-containing resin include those generally called silicone resins or modified silicone resins. Particularly preferred are modified silicone resins.

  The silicone resin is a resin having a main chain of organopolysiloxane and a crosslinkable silyl group in the resin. Specifically, a one-part silicone resin containing an organopolysiloxane having a silanol group at the terminal as a main component and a low-molecular compound containing a crosslinkable silyl group as a crosslinking component, and an organopolysiloxane having a silanol group at the terminal as a main component A two-part silicone resin containing siloxane and aminoxyalkylsilane as a curing agent can be mentioned. Examples of the crosslinkable silyl group-containing low molecular weight compound include acyloxyalkylsilanes, aminoxyalkylsilanes, and alkoxyalkylsilanes.

  As the modified silicone resin, for example, JP-A-52-73998, JP-A-55-9669, JP-A-59-122541, JP-A-60-6747, JP-A-61-233043 JP, 63-6003, JP 63-112642, JP 3-79627, JP 4-283259, JP 5-287186, JP 11-80571. And those disclosed in JP-A-11-116763 and JP-A-11-130931. Specifically, the resin has a crosslinkable silyl group and the main chain is an aliphatic hydrocarbon hydrocarbon such as vinyl polymer, polyoxyalkylene polymer, polyisoprene, polyisobutylene or polybutanediene. Examples thereof include a polymer, a polyester polymer, a polysulfide polymer, a copolymer thereof, and a mixture thereof. Any of these may be used alone or in combination of two or more.

  The main chain of the modified silicone resin is composed of a polyoxyalkylene polymer, a (meth) acrylic-modified polyoxyalkylene polymer, (meth) from the viewpoint of rubber properties such as tensile adhesion after curing and modulus. ) Acrylic copolymers are preferred.

  In the present invention, “(meth) acryl-modified” may mean a polyoxypropylene polymer obtained by block or pendant copolymerization of a (meth) acrylic monomer, or a polyoxyalkylene polymer. It means a mixture of (meth) acrylic copolymers, or a polymer of (meth) acrylic monomers in a polyoxyalkylene polymer having a crosslinkable silyl group introduced.

From the viewpoint of curability of the curable composition and physical properties after curing, it is preferable that one or more crosslinkable silyl groups are contained in the molecule, and more preferably 1 to 5, more preferably 1 to 3. Preferably included.
Further, the crosslinkable silyl group is preferably one represented by the following general formula which is easily crosslinked and easy to produce.

（式中、Ｒは炭化水素基であり、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基または炭素数７〜２０のアラルキル基が好ましく、メチル基が最も好ましい。Ｘで示される反応性基はハロゲン原子、水素原子、水酸基、アルコキシ基、アシルオキシ基、ケトキシメート基、アミド基、酸アミド基、メルカプト基、アルケニルオキシ基およびアミノオキシ基より選ばれる加水分解性の基であり、Ｘが複数の場合には、Ｘは同じ基であっても異なった基であってもよい。このうちＸはアルコキシ基が好ましく、メトキシ基またはエトキシ基が最も好ましい。ａは０、１または２の整数であり、０または１が最も好ましい。）

Wherein R is a hydrocarbon group, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and most preferably a methyl group. The reactive group is a hydrolyzable group selected from a halogen atom, hydrogen atom, hydroxyl group, alkoxy group, acyloxy group, ketoximate group, amide group, acid amide group, mercapto group, alkenyloxy group and aminooxy group, When X is plural, X may be the same group or different groups, among which X is preferably an alkoxy group, most preferably a methoxy group or an ethoxy group, and a is 0, 1 or 2 And is most preferably 0 or 1.)

Introduction of the crosslinkable silyl group into the main chain can be performed, for example, by the following known method.
(A) An organic compound (for example, allyl isocyanate) having an active group and an unsaturated group that are reactive with a polyoxyalkylene-based or vinyl-based polymer having a functional group such as a hydroxyl group at the terminal. And then hydrosilylating the resulting reaction product with a hydrosilane having a hydrolyzable group.
(B) A compound having a functional group and a crosslinkable silyl group which are reactive with a polyoxyalkylene-based or vinyl-based polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group at the terminal How to react.
Examples of the compound having a reactive functional group and a crosslinkable silyl group include amino group-containing silanes, mercapto group-containing silanes, epoxy group-containing silanes, vinyl type unsaturated group-containing silanes, chlorine atom-containing silanes, and isocyanates. Examples thereof include group-containing silanes and hydrosilanes.
(C) A compound having a polymerizable unsaturated bond and a crosslinkable silyl group (for example, CH ₂ ═CHSi (OCH ₃ ) ₃ or CH ₂ ═CHCOO (CH ₂ ) ₂ Si (OCH ₃ ) ₃ ) and (meth) acrylic A method of copolymerizing an acid alkyl ester monomer.
(D) a compound having a polymerizable unsaturated bond and a functional group (for example, hydroxyethyl (meth) acrylate or allyl (meth) acrylate) is added to the (meth) acrylic acid alkyl ester monomer and copolymerized; Subsequently, the resulting copolymer is converted into a compound having a reactive functional group and a crosslinkable silyl group (for example, a compound having an isocyanate group and —Si (OCH ₃ ) ₃ group, trimethoxysilane, triethoxysilane or the like). A hydrosilane having a decomposable group).

  In the present invention, the number average molecular weight of the silicone resin and the modified silicone resin is preferably 1,000 or more, and particularly preferably 6,000 to 30,000. A narrow molecular weight distribution is preferred because the viscosity of the curable composition is low, and rubber properties such as strength, elongation and modulus after curing are excellent.

  The blocked amine compound is a compound obtained by blocking the active hydrogen bonded to the nitrogen atom of a compound having a primary and / or secondary amino group by dehydration reaction with a compound having a carbonyl group such as a ketone or aldehyde. The curable composition combining this with an isocyanate group-containing resin, which is a curable resin, does not react while being sealed and stored in a container, but when it is opened and contacted with water, the block amine compound is hydrolyzed. Then, active hydrogen bonded to the nitrogen atom is generated (regenerated). The generated active hydrogen reacts with the isocyanate group of the isocyanate group-containing resin to be crosslinked and cured.

  The rate at which the active hydrogen of the produced amino group reacts with the isocyanate group is faster than the rate at which water reacts with the isocyanate group, so the amount of carbon dioxide generated by the reaction of water and the isocyanate group can be reduced. Foaming due to carbon dioxide gas is difficult to occur.

  Specific examples of the block amine compound include ketimine compounds and enamine compounds that are a reaction product of a polyamine and a carbonyl compound; and oxazolidine compounds that are a reaction product of an amino alcohol and a carbonyl compound. From the viewpoint of shortening the curing time of the curable composition and storage stability, it is preferable to use an oxazolidine compound.

  The oxazolidine compound is a compound having 1 or more, preferably 1 to 6 oxazolidine rings in the molecule, which is a saturated 5-membered heterocyclic ring containing an oxygen atom and a nitrogen atom. The oxazolidine compound reacts with water to undergo hydrolysis, and the oxazolidine ring generates (regenerates) a secondary amino group and an alcoholic hydroxyl group, thereby functioning as a latent curing agent for the isocyanate group-containing resin. When the isocyanate group of the isocyanate group-containing resin reacts with water, it forms a urea bond and cures, but at this time, carbon dioxide gas is also generated, bubbles are generated in the cured product due to carbon dioxide gas, deterioration of the appearance, Problems such as breakage and lowering of adhesiveness may occur. On the other hand, when a mixture of an isocyanate group-containing resin and an oxazolidine compound is reacted with water, first, water and the oxazolidine compound react preferentially, and the oxazolidine ring of the oxazolidine compound becomes a secondary amino group and an alcoholic hydroxyl group ( Active hydrogen group). Next, since the generated active hydrogen groups (especially secondary amino groups) react preferentially with isocyanate groups, the generation of carbon dioxide gas due to the reaction of water and isocyanate groups is suppressed, and foaming during curing of the curable composition is suppressed. Can be prevented.

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

  Examples of the oxazolidine compound include a urethane bond-containing oxazolidine compound, an ester group-containing oxazolidine compound, an oxazolidine silyl ether compound, and a carbonate group-containing oxazolidine compound. These oxazolidine compounds are obtained by reacting a hydroxyl group of a compound having a hydroxyl group and an oxazolidine ring with an isocyanate group of an organic polyisocyanate compound or a carboxyl group of an organic carboxylic acid compound. Of these oxazolidine compounds, urethane bond-containing oxazolidine compounds are preferred from the viewpoint of easy production and low viscosity.

  Specific examples of the compound having a hydroxyl group and an oxazolidine ring include N-hydroxyalkyloxazolidine obtained by a dehydration condensation reaction between a secondary amino group of an alkanolamine and a carbonyl group of a ketone compound or an aldehyde compound. As a method for producing the compound having a hydroxyl group and an oxazolidine ring, 1 mol or more, preferably 1 to 1.5 mol, more preferably 1 to 1.5 mol of a carbonyl group of an aldehyde compound or a ketone compound with respect to 1 mol of a secondary amino group of alkanolamine. Can be used in an amount of 1 to 1.2 moles, heating and refluxing in a solvent such as toluene and xylene, and performing a dehydration condensation reaction while removing by-product water. Excess aldehyde compounds and ketone compounds may be removed by distillation.

  Examples of the alkanolamine include diethanolamine, dipropanolamine, and N- (2-hydroxyethyl) -N- (2-hydroxypropyl) amine. Examples of the ketone compound include acetone, diethyl ketone, isopropyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl tert-butyl ketone, diisobutyl ketone, cyclopentanone, and cyclohexanone. Examples of the aldehyde compound include acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, 2-methylbutyraldehyde, n-hexylaldehyde, 2-methylpentylaldehyde, n-octylaldehyde, 3, 5 Aliphatic aldehyde compounds such as 1,5-trimethylhexylaldehyde; aromatic aldehyde compounds such as benzaldehyde, methylbenzaldehyde, trimethylbenzaldehyde, ethylbenzaldehyde, isopropylbenzaldehyde, isobutylbenzaldehyde, methoxybenzaldehyde, dimethoxybenzaldehyde, and trimethoxybenzaldehyde. Any of these may be used alone or in combination of two or more.

  Of these, diethanolamine is preferred as the alkanolamine because it is easy to produce a compound having a hydroxyl group and an oxazolidine ring and has excellent antifoaming properties when the curable composition is cured. Of these, aldehyde compounds are preferable, and isobutyraldehyde, 2-methylpentylaldehyde, and benzaldehyde are more preferable.

  Specific examples of the compound having a hydroxyl group and an oxazolidine ring include 2-isopropyl-3- (2-hydroxyethyl) oxazolidine, 2- (1-methylbutyl) -3- (2-hydroxyethyl) oxazolidine, 2-phenyl- 3- (2-hydroxyethyl) oxazolidine is mentioned.

  As the urethane bond-containing oxazolidine compound, the molar ratio of isocyanate group / hydroxyl group between the isocyanate group of the organic polyisocyanate compound and the hydroxyl group of the compound having an oxazolidine ring is 0.9 / 1 to 1.2 / 1, preferably 0. Suitable examples include those obtained by reacting at a temperature of 50 to 120 ° C. in the presence or absence of an organic solvent.

  Examples of the organic polyisocyanate compound used for the production of the urethane bond-containing oxazolidine compound include the same as those used for the production of the urethane prepolymer. Of these, araliphatic polyisocyanate and aliphatic polyisocyanate are preferred in that the crystallinity of the urethane bond-containing oxazolidine compound can be lowered and the workability of the curable composition can be improved, and in particular xylylene diisocyanate (XDI), Hexamethylene diisocyanate (HDI) is preferred.

  The ester group-containing oxazolidine compound can be obtained by reacting the above-mentioned compound having a hydroxyl group and an oxazolidine ring with a lower alkyl ester of dicarboxylic acid or polycarboxylic acid.

  The oxazolidine silyl ether compound includes a compound having a hydroxyl group and an oxazolidine ring described above, trimethoxysilane, tetramethoxysilane, triethoxysilane, dimethoxydimethylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethyl. It can be obtained by dealcoholization reaction with alkoxysilane such as methoxysilane and 3-glycidoxypropyltriethoxysilane.

  The carbonate group-containing oxazolidine compound can be obtained by reacting the above-mentioned compound having a hydroxyl group and an oxazolidine ring with a carbonate such as diallyl carbonate using a polyhydric alcohol such as diethylene glycol or glycerin.

  Any of these oxazolidine compounds can be used alone or in combination of two or more.

  The oxazolidine compound preferably does not have an active hydrogen-containing functional group such as an amino group or a hydroxyl group that reacts with the isocyanate group of the isocyanate group-containing resin at room temperature (or normal temperature) of 5 to 35 ° C., or an isocyanate group. . This is to prevent an increase in viscosity of the isocyanate group-containing resin and a decrease in foaming prevention performance of the oxazolidine compound. However, in the production of the above-mentioned urethane bond-containing oxazolidine compound, a small amount of active hydrogen-containing functional group or isocyanate group may remain in the molecule depending on the molar ratio selected. In this case, the purpose of the present invention is achieved. It can be regarded as not having. The “small amount” means that the amount of active hydrogen-containing functional groups or isocyanate groups remaining in the molecule is preferably 0.05 mmol or less, more preferably 0.02 mmol or less per 1 g of the oxazolidine compound.

  When the oxazolidine compound is used as the block amine compound, the active hydrogen of the secondary amino group generated (regenerated) by hydrolysis of the oxazolidine compound with respect to 1 mol of isocyanate group of the isocyanate group-containing resin is 0.00. It is preferable to mix | blend so that it may become 1-1 mol, and it is more preferable to mix | blend so that it may become 0.3-1 mol. If the active hydrogen of the secondary amino group produced (regenerated) by hydrolysis of the oxazolidine compound is less than 0.1 mol, foaming prevention is insufficient, which is not preferable.

  The composition (A) in the present invention can further contain a carboxylic anhydride compound and a carboxylic acid silyl ester compound. Any of these may be used alone or in combination of two or more.

  The carboxylic acid anhydride compound and the carboxylic acid silyl ester compound accelerate the deep curability at the time of curing in a curable composition in which a block amine compound is blended with a curable resin. In particular, in a composition containing an isocyanate group-containing resin as a curable resin and an oxazolidine compound as a block amine compound, deep curability during curing is accelerated.

  Specific examples of the carboxylic anhydride compound include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, malic acid, maleic acid, fumaric acid, itaconic acid, citric acid, tartaric acid, phthalic acid, and tetrahydrophthalic acid. , Hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenone dicarboxylic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, biphenyl And carboxylic acid anhydrides such as dicarboxylic acid and biphenyl ether tetracarboxylic acid.

The carboxylic acid silyl ester compound includes a carboxylic acid silyl ester group represented by the following formulas (5) and (6), the number M of the carboxylic acid silyl ester group represented by the following formula (5), and the following formula ( It is preferable that the number N of the carboxylic acid silyl ester group represented by 6) satisfies the relationship of the following formula (7).
R ¹ COO-Si≡ (5)
R ² COO-Si≡ (6)
0.10 ≦ M / (M + N) ≦ 0.80 (7)
(In the formula, R ¹ represents a monovalent hydrocarbon group having 13 to 21 carbon atoms, preferably 13 to 17 carbon atoms, and R ² represents an alkyl group having 5 to 11 carbon atoms, preferably 7 to 11 carbon atoms.)

  Even if the carboxylic acid silyl ester compound uses a compound having a carboxylic acid silyl ester group represented by the above formulas (5) and (6) in different molecules, these carboxylic acid silyl ester groups The compound itself in the same molecule or a compound containing the compound may be used. Among these, the latter is preferable from the viewpoint of productivity. In the present invention, the latter embodiment includes an embodiment in which the silicon (Si) atoms of the carboxylic acid silyl ester groups represented by the above formulas (5) and (6) are the same atom.

In the above formula (5), the monovalent hydrocarbon group having 13 to 21 carbon atoms of R ¹ is specifically an unsaturated group such as an alkenyl group or a saturated monovalent aliphatic group such as an alkyl group. And hydrocarbon groups; monovalent alicyclic hydrocarbon groups such as cyclohexyl groups; monovalent aromatic-containing hydrocarbon groups such as phenyl groups, tolyl groups, benzyl groups, and styryl groups. Specifically, preferred examples of the alkyl group include n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, and n-octadecyl group.

Specific examples of the alkyl group having 5 to 11 carbon atoms of R ^{2 in} the above formula (6) include, for example, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, tert- Pentyl group, neopentyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2,2-dimethylpentyl group, 3,3-dimethylpentyl group, 2,3-dimethylpentyl group, Examples include 2,4-dimethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl group, n-nonyl group, and n-undecyl group. Of these, a 1-ethylpentyl group and an n-undecyl group are preferable.

  On the other hand, as shown by the above formula (7), the ratio of the number M of the carboxylic acid silyl ester group represented by the above formula (5) and the number N of the carboxylic acid silyl ester group represented by the above formula (6). (M / (M + N)) is in the range of 0.10 to 0.80, preferably in the range of 0.20 to 0.80.

  The carboxylic acid silyl ester compound preferably has a siloxane unit represented by the following formulas (8) and (9) including the carboxylic acid silyl ester group represented by the above formulas (5) and (6).

上記式（８）、上記式（９）中、Ｒ^１は炭素数１３〜２１の１価の炭化水素基を表し、Ｒ^２は炭素数５〜１１のアルキル基を表し、Ｒ^３は水素原子または置換基を有していてもよい炭素数１〜８の１価の炭化水素基を表す。

In the above formula (8) and the above formula (9), R ¹ represents a monovalent hydrocarbon group having 13 to 21 carbon atoms, R ² represents an alkyl group having 5 to 11 carbon atoms, and R ³ represents a hydrogen atom. Alternatively, it represents a monovalent hydrocarbon group having 1 to 8 carbon atoms which may have a substituent.

Here, R ¹ in the above formula (8) and R ² in the above formula (9) are respectively R ¹ explained in the above formula (5) and R ² explained in the above formula (6). It is the same. Further, in the above formula (8) and (9), the monovalent hydrocarbon group having 1 to 8 carbon atoms which may have a substituent group R ^3, for example, an alkyl group, a vinyl group, an allyl group A monovalent aliphatic hydrocarbon group such as cyclohexyl group; a monovalent alicyclic hydrocarbon group such as cyclohexyl group; a monovalent aromatic hydrocarbon group such as phenyl group, tolyl group, benzyl group, styryl group; and And a combination thereof. Specifically, preferred examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-octyl group. Of these, a methyl group and a phenyl group are preferable.

  Specifically as a siloxane unit represented by the said Formula (8), the siloxane unit represented by each formula of following formula (I) is illustrated suitably.

Specifically as a siloxane unit represented by the said Formula (9), the siloxane unit represented by each formula of following formula (II) is illustrated suitably.

  Any of the siloxane units represented by the above formulas (8) and (9) can be used alone or in combination of two or more.

The carboxylic acid silyl ester compound preferably further has an ether-containing silyl group represented by the following formula (10), and the carboxylic acid silyl ester is represented by the above formulas (5) and (6). A compound having an ester group and an ether-containing silyl group represented by the following formula (10) in the same molecule is more preferable.
R ⁶ O— (R ⁵ O) _r —R ⁴ —Si≡ (10)
(In the formula (10), ^{R 4} and ^{R 5} each independently represent an alkylene group having 2 to 6 carbon atoms which may have a substituent, ^{R 6} is a hydrogen atom, C1-30 Or an organic group represented by R ¹³ — (CO) — (R ¹³ represents a hydrocarbon group having 1 to 30 carbon atoms), r represents an integer of 1 or more, and r is 2. In the case of the above integers, the plurality of R ⁵ may be the same or different from each other.)

Specific examples of the alkylene group having 2 to 6 carbon atoms that may have a substituent of R ^{4 in} the above formula (10) include, for example, an ethylene group and a trimethylene group (—CH ₂ CH ₂ CH ₂ -), propylene group _{(-CH (CH 3) -CH 2} -), tetramethylene group, 1,1-dimethylethylene group. Of these, an ethylene group and a trimethylene group are preferable.

R ⁵ in the above formula (10) is the same as R ⁴ in the above formula (10), but when r is 2 or more, the plurality of R ⁵ may be the same or different. Good. In addition, in the above formula (10),-(OR ⁵ ) _r -is not particularly limited with respect to the arrangement thereof, and examples thereof include random, block, and arrangement by mixing random and block. Among these, it is preferable that R ⁵ is an ethylene group or a propylene group. That is, — (OR ⁵ ) _r — is preferably composed of a repeating unit represented by — (OCH ₂ CH ₂ ) — and a repeating unit represented by — (OCH (CH ₃ ) CH ₂ ) —. .

In the above formula (10), R ⁶ is, for example, a monovalent aliphatic hydrocarbon group such as an alkyl group, a vinyl group or an allyl group; a monovalent alicyclic hydrocarbon group such as a cyclohexyl group. A monovalent aromatic hydrocarbon group such as a phenyl group, a tolyl group, a benzyl group, and a styryl group; and a combination thereof. Specifically, preferred examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-octyl group, and a 2-ethylhexyl group. Of these, an n-butyl group, an n-octyl group, and a 2-ethylhexyl group are preferable.

  In said formula (10), as an integer of 1 or more of r, it is preferable that it is an integer of 5 or more, and it is more preferable that it is 10-100.

It is preferable that a carboxylic acid silyl ester compound has a siloxane unit represented by the following formula (11) including an ether-containing silyl group represented by the above formula (10).

In the above formula (11), R ³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, and R ⁴ and R ⁵ are each independently a substituent. Represents an alkylene group having 2 to 6 carbon atoms, and R ⁶ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an organic group represented by R ¹³ — (CO) — (R ¹³ represents Represents a hydrocarbon group having 1 to 30 carbon atoms, and r represents an integer of 1 or more. When r is an integer of 2 or more, the plurality of R ⁵ may be the same or different. Here, ^{R 3} in the formula (11) is the same as ^{R 3} as described in the above formula (8) and (9) in. Further, ^R 4, ^{R 5} and ^{R 6} and r in the formula (11) are respectively the same as ^R 4, ^{R 5} and ^{R 6} and r described in the above formula (10) in.

Specific examples of the siloxane unit represented by the above formula (11) include siloxane units represented by the following formula (III).

  Any of the siloxane units represented by the above formula (11) can be used alone or in combination of two or more.

  As a carboxylic acid silyl ester compound, a polysiloxane containing a siloxane unit represented by the above formulas (8) and (9) and a siloxane unit represented by the above formula (11) in either or both of the inside and the end of the molecule. It is preferable to use siloxane.

  In the present invention, the siloxane units represented by the above formulas (8), (9) and (11) are not particularly limited with respect to the arrangement thereof, and examples thereof include random, block, and arrangement by mixing random and block. It is done.

The polysiloxane may have a siloxane unit other than the siloxane units represented by the above formulas (8), (9) and (11). Examples of such a siloxane unit include the following formula (12): The siloxane unit represented is mentioned.

In the above formula (12), R ⁸ represents a methyl group, an ethyl group or a phenyl group, and R ⁹ represents a hydrogen atom or a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include unsaturated monovalent aliphatic hydrocarbon groups such as alkenyl groups and saturated or alkyl groups; monovalent alicyclic hydrocarbon groups such as cyclohexyl groups; Groups, monovalent aromatic-containing hydrocarbon groups such as a tolyl group, a benzyl group, and a styryl group. Specifically, preferred examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-octyl group. Of these, a methyl group and a phenyl group are preferable.

Specifically as a siloxane unit represented by the said Formula (12), the siloxane unit represented by the following formula (13) or (14) is illustrated suitably.

The molecular terminal of the polysiloxane is not particularly limited, and examples of the terminal group include -SiR ¹⁰ ₃ , -Si (OR ¹⁰ ) ₃ , -Si (R ¹⁰ ) ₂ (OH) (wherein R ¹⁰ represents A hydrocarbon group having 1 to 12 carbon atoms, specifically, a methyl group, an ethyl group or a phenyl group, and a plurality of R ^{10 s} may be the same or different. Particularly preferred are trimethylsilyl group and triethylsilyl group.

  The polymerization degree of the polysiloxane is preferably 2 to 1,000, and more preferably 10 to 100. When the polymerization degree of the polysiloxane is within this range, the handleability is good.

  Among the polysiloxanes, examples of the polysiloxane having a siloxane unit represented by the above formulas (8) and (9) include a polysiloxane represented by the following formula (15).

In the above formula (15), R ¹ represents a monovalent hydrocarbon group having 13 to 21 carbon atoms, R ² represents an alkyl group having 5 to 11 carbon atoms, and R ³ has a hydrogen atom or a substituent. Represents a monovalent hydrocarbon group having 1 to 8 carbon atoms which may be present. R ¹⁰ represents a hydrocarbon group having 1 to 12 carbon atoms, specifically, a methyl group, an ethyl group or a phenyl group, which may be the same or different, and a and b in the above formula (15) are each Independently represents an integer of 1 or more.

Wherein, ^{R 1} and ^{R 2} in the formula (15) are each the same as ^{R 2} described in ^{R 1} and the formula (6) in which described in the above formula (5), the formula ( 15) ^{R 3} in is the same as ^{R 3} as described in the above formula (8) and (9) in.

  A in the formula (15) represents the number of repeating units of the siloxane unit having a carboxylic acid silyl ester group represented by the formula (5), that is, the siloxane unit represented by the formula (8). It is the above-mentioned integer, preferably 1 to 100, more preferably 1 to 50.

  B in the formula (15) represents the number of repeating units of the siloxane unit having a carboxylic acid silyl ester group represented by the formula (6), that is, the siloxane unit represented by the formula (9). It is the above-mentioned integer, preferably 1 to 100, more preferably 1 to 50.

  In the above formula (15), each of the two siloxane units having a carboxylic acid silyl ester group is not particularly limited with respect to the arrangement thereof, and examples thereof include random, block, and arrangement by mixing random and block.

  Specific examples of the polysiloxane represented by the above formula (15) include polysiloxane represented by the following formula (16).

  In the above formula (16), each of the two siloxane units having a carboxylic acid silyl ester group is not particularly limited in terms of arrangement, and examples thereof include random, block, and arrangement by mixing random and block.

  The production method of the polysiloxane having the siloxane unit represented by the above formulas (8) and (9) is not particularly limited. For example, by a method of reacting a Si-H group-containing polysiloxane described later with a predetermined carboxylic acid. Can be manufactured. In this reaction, a Group VIII transition metal complex such as palladium, rhodium, nickel, or platinum can be used as a catalyst.

On the other hand, among the polysiloxanes, specific examples of polysiloxanes having siloxane units represented by the above formulas (8) and (9) and siloxane units represented by the above formula (11) include the following formulas ( The organosiloxane represented by 17) is preferably exemplified.
(R ¹ COO) _a (R ² COO) _b R ³ _c R ⁷ _d SiO ^{(4-abbcd) / 2} (17)
0.10 ≦ a / (a + b) ≦ 0.8 (18)
1 ≦ c <2 (19)
0.001 ≦ d <1 (20)
1.95 ≦ a + b + c + d ≦ 2.60 (21)

In the above formula (17), R ¹ represents a monovalent hydrocarbon group having 13 to 21 carbon atoms, R ² represents an alkyl group having 5 to 11 carbon atoms, and R ³ has a hydrogen atom or a substituent. Represents a monovalent hydrocarbon group having 1 to 8 carbon atoms which may be present. In the formula, R ⁷ represents a polyether-containing group represented by —R ⁴ — (OR ⁵ ) _r —OR ⁶ , and R ⁴ and R ⁵ each independently have a substituent. Or an alkylene group having 2 to 6 carbon atoms, wherein R ⁶ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an organic group represented by R ¹³ — (CO) — (R ¹³ is an alkyl group having 1 to 30 represents a hydrocarbon group), and r represents an integer of 1 or more. When r is an integer of 2 or more, the plurality of R ⁵ in the polyether-containing group may be the same or different. Further, a, b, c and d in the above formulas (17) to (21) represent numbers satisfying the relations of the above formulas (18) to (21).

Wherein, ^{R 1} and ^{R 2} in the formula (17) are respectively the same as ^{R 2} described in ^{R 1} and the formula (6) in which described in the above formula (5). Further, ^{R 3} in the formula (17) is the same as ^{R 3} as described in the above formula (8) and (9) in. R ⁴ , R ^5, R ⁶ and r in the polyether-containing group (—R ⁴ — (OR ⁵ ) _r —OR ⁶ ) represented by R ⁷ in the above formula (17) are each represented by the above formula ( 10) The same as R ⁴ , R ⁵ and R ⁶ and r described in 10).

  A, b, c and d representing the numbers satisfying the relations of the above formulas (18) to (21) are 0.01 ≦ a ≦ 1.0, 0.05 ≦ b ≦ 1.0, 1.0, respectively. It is preferable that ≦ c ≦ 1.3 and 0.005 ≦ d ≦ 0.05.

  In the above formula (17), the ratio of the polyether-containing group to the total number of carboxylic acid silyl ester groups, that is, d / (a + b) is preferably 0.01 to 0.7, preferably 0.01 to 0. .5 is more preferable.

Examples of such an organosiloxane include polysiloxane represented by the following formula (22).

In the formula (22), R ¹ represents a monovalent hydrocarbon group having 13 to 21 carbon atoms, R ² represents an alkyl group having 5 to 11 carbon atoms, and R ³ has a hydrogen atom or a substituent. Represents a monovalent hydrocarbon group having 1 to 8 carbon atoms which may be present. R ⁴ and ^{R 5} each independently represent an alkylene group having 2 to 6 carbon atoms which may have a substituent, ^{R 6} is a hydrogen atom, an alkyl group, or ^{R 13} having 1 to 30 carbon atoms - ( CO) — represents an organic group (R ¹³ represents a hydrocarbon group having 1 to 30 carbon atoms), and r represents an integer of 1 or more. When r is an integer of 2 or more, the plurality of R ⁵ in the polyether-containing group may be the same or different. R ¹⁰ represents a hydrocarbon group having 1 to 12 carbon atoms, specifically, a methyl group, an ethyl group, or a phenyl group, and may be the same or different. In the above formula (22), a, b and d each independently represent an integer of 1 or more.

Wherein, ^{R 1} and ^{R 2} in the formula (22) are each the same as ^{R 2} described in ^{R 1} and the formula (6) in which described in the above formula (5), the formula ( 22) ^{R 3} in is the same as ^{R 3} as described in the above formula (8) and (9) in, ^R 4, ^{R 5} and ^{R 6} and r in the formula (22), respectively, the The same as R ⁴ , R ^5, R ⁶ and r described in the formula (10).

  A and b in the above formula (22) are the same as a and b described in the above formula (15), respectively. Moreover, d in the said Formula (22) represents the number of repeating units of the siloxane unit which has an ether containing silyl group represented by the said Formula (10), ie, the siloxane unit represented by the said Formula (11), It is an integer of 1 or more, preferably 1 to 10, and more preferably 1 to 5.

  In the above formula (22), each of the two siloxane units having a carboxylic acid silyl ester group and the siloxane unit having an ether-containing silyl group are not particularly limited with respect to the arrangement thereof, for example, random, block, random and block, The arrangement | sequence by mixing is mentioned.

  Specific examples of the organosiloxane represented by the above formula (22) include polysiloxane represented by the following formula (23).

  In the above formula (23), a, b and d each independently represent an integer of 1 or more, s and t each independently represents an integer of 0 or more, and s + t is 1 or more.

Here, a and b in the above formula (23) are respectively the same as a and b described in the above formula (15), and d in the above formula (23) is in the above formula (22). It is the same as d explained in. In the above formula (23), s represents the number of repeating units of —OCH ₂ CH ₂ —, and t represents the number of repeating units of —OCH ₂ CH (CH ₃ ) —. In the above formula (23), s and t have a relationship of r = s + t with r in the above formula (10) or (11). s + t is 1 or more, preferably 5 or more, and more preferably 10 to 100. In the formula (23), —OCH ₂ CH ₂ — and —OCH (CH ₃ ) CH ₂ — are not particularly limited with respect to the arrangement thereof. For example, the arrangement is random, block, or a mixture of random and block. Is mentioned.

  In the above formula (23), each of the two siloxane units having a carboxylic acid silyl ester group and the siloxane unit having an ether-containing silyl group are not particularly limited with respect to the arrangement thereof, for example, random, block, random and block, The arrangement | sequence by mixing is mentioned.

  A more specific example of the organosiloxane represented by the above formula (23) includes a polysiloxane represented by the following formula (24).

  The production method of the polysiloxane having the siloxane unit represented by the above formulas (8) and (9) and the siloxane unit represented by the above formula (11) is not particularly limited. Siloxane and alkenyl ether are reacted to form a siloxane unit represented by the above formula (11), and then a predetermined carboxylic acid is reacted to form siloxane units represented by formulas (8) and (9). And a method for producing a polysiloxane; a method for simultaneously reacting a Si-H group-containing polysiloxane, an alkenyl ether and a predetermined carboxylic acid. In these reactions, it is desirable to use a group VIII transition metal catalyst such as platinum, rhodium, palladium, nickel as the catalyst. Specifically, chloroplatinic acid, alcohol-modified chloroplatinic acid, A platinum-vinylsiloxane complex or the like can be preferably used. In addition, the usage-amount of a catalyst is not specifically limited, It is preferable that it is 50 ppm or less with a metal content, and it is more preferable that it is 20 ppm or less.

  Specifically, as the former production method, for example, a Si-H group-containing polysiloxane and an alkenyl ether, which will be described later, are reacted by adding a Group VIII transition metal complex such as platinum as a catalyst, and then reacting. One preferred embodiment is a method of reacting the carboxylic acid.

  In this production method, when the Si—H group-containing polysiloxane and the alkenyl ether are not compatible, a hydrocarbon solvent such as toluene or xylene can be used. As a result, the reaction proceeds promptly. The reaction temperature is preferably 60 to 120 ° C, particularly preferably 80 to 110 ° C.

  In the reaction with the carboxylic acid, the Group VIII transition metal complex can be used as a catalyst as in the reaction with the Si—H group-containing polysiloxane and the alkenyl ether. The reaction temperature with the carboxylic acid is usually 80 to 110 ° C. In particular, it is preferable from the viewpoint of safety and efficiency that the reaction temperature is low in the early stage of the reaction and higher in the late stage of the reaction.

  The Si—H group-containing polysiloxane used for the production of the polysiloxane is not particularly limited, and specific examples thereof include polysiloxane having an alkyl hydrogen siloxane unit represented by the following formula (25).

In the above formula ^{(25), R 11} is a methyl group, an ethyl group, or a phenyl group.

  The polysiloxane having an alkylhydrogensiloxane unit represented by the above formula (25) is not particularly limited, and conventionally known ones can be used. Specific examples include polysiloxanes represented by the following formulas (IV).

  Any of the above Si-H group-containing polysiloxanes can be used alone or in combination of two or more.

The said alkenyl ether used for manufacture of the said polysiloxane is not specifically limited, As the specific example, the alkenyl ether represented by following formula (26) is mentioned.
^{_{CH 2 = CH-R 12 -}} (OR 5) r -OR 6 ··· (26)

In the above formula (26), ^{R 5} represents an alkylene group having 2 to 6 carbon atoms which may have a substituent, ^{R 6} represents a hydrogen atom, an alkyl group, or ^R 13 having 1 to 30 carbon atoms - (CO )-Represents an organic group (R ¹³ represents a hydrocarbon group having 1 to 30 carbon atoms), R ¹² does not exist (is a single bond) or represents a methylene group, and r is 1 It represents the above integer. When r is an integer of 2 or more, the plurality of R ⁵ in the polyether-containing group may be the same or different.

Here, ^R 5, ^{R 6} and r in the formula (26) are the same as ^R 5, ^{R 6} and r described in the above formula (10) in.

  Examples of the alkenyl ether represented by the above formula (26) include polyethylene glycol, polypropylene glycol, and a copolymer of ethylene glycol and propylene glycol represented by the following formulas (V).

In the following formula representing a copolymer of ethylene glycol and propylene glycol, s represents the number of repeating units of —OCH ₂ CH ₂ —, t represents the number of repeating units of —OCH (CH ₃ ) CH ₂ —, s and t are each independently an integer of 0 or more. Further, s + t is 1 or more, preferably 5 or more, and more preferably 10 to 100. Note that r in the above formula (26) and the formulas s and t in the following formula (V) have a relationship of r = s + t. Among these, a copolymer of ethylene glycol and propylene glycol having a molecular weight of 500 or more is preferable. Any of the alkenyl ethers can be used alone or in combination of two or more.

  The predetermined carboxylic acid used in the production of the polysiloxane is, for example, tridecyl acid, tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecanoic acid as a carboxylic acid for forming the siloxane unit represented by the above formula (8). (Palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid) can be used, and as carboxylic acid for forming the siloxane unit represented by the above formula (9), for example, hexanoic acid (caproic acid), heptane Acid, octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), dodecylic acid (lauric acid) can be used. Especially, as carboxylic acid for forming the siloxane unit represented by the said Formula (8), a palmitic acid and a stearic acid are preferable, As carboxylic acid for forming the siloxane unit represented by the said Formula (9) Is preferably capric acid or lauric acid. In addition, these carboxylic acids can be used alone or in combination of two or more.

  The blending amount when the carboxylic anhydride compound or the carboxylic acid silyl ester compound is used alone, and the blending amount when the carboxylic anhydride compound and the carboxylic acid silyl ester compound are used in combination are 100 parts by mass of the curable resin. The amount is preferably 0.001 to 10 parts by mass, and more preferably 0.1 to 10 parts by mass.

  In addition to carboxylic anhydride compounds and carboxylic acid silyl ester compounds, compounds that accelerate the curability of a composition containing a curable resin and a block amine compound include metal catalysts, amine catalysts, organic carboxylic acid catalysts, and phosphoric acid ester compounds. A catalyst, p-toluenesulfonyl monoisocyanate, a reaction product of p-toluenesulfonyl monoisocyanate and water can be used. These compounds can be used alone or in combination of two or more. Moreover, these compounds can be used in combination with a carboxylic anhydride compound or a carboxylic acid silyl ester compound.

  Examples of the metal-based catalyst and amine-based catalyst include the same organic metal compounds, tertiary amines, tertiary amines and carboxylic acid salts that are mentioned as additives for the curing acceleration of the urethane prepolymer described later. It is done.

  Examples of organic carboxylic acid catalysts 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. Examples include α, β-unsaturated carboxylic acids such as aliphatic carboxylic acid, maleic acid, and acrylic acid, and aromatic carboxylic acids such as phthalic acid, benzoic acid, and salicylic acid.

  Examples of the phosphoric acid ester catalyst include regular phosphoric acid ester compounds and phosphorous acid ester compounds. Examples of the orthophosphate compound include acidic phosphate compounds such as ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, oleyl acid phosphate, and the phosphite compound includes triethyl phosphite, Triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monodecyl phosphite and other oxalic acid triester compounds, dilauryl hydrogen phosphite, dioleyl Examples thereof include phosphorous acid diester compounds such as hydrogen phosphite and diphenyl hydrogen phosphite.

  The reaction product of p-toluenesulfonyl monoisocyanate and water may be obtained by reacting p-toluenesulfonyl monoisocyanate and water in advance before blending with the curable composition of the present invention, What was made to react by adding water while mix | blending p-toluenesulfonyl monoisocyanate with a curable composition, or what was made to react with the water which exists in a curable composition may be used.

Composition (B)
The composition (B) in the present invention contains water containing metal ions. The curable resin of the composition (A) reacts with water containing metal ions to be crosslinked and cured. When the water containing a metal ion is blended in the composition (B), the deep curability of the curable composition is excellent. Further, when the curing sheet or the curing tape is peeled off, the composition remaining on the curing sheet or the curing tape is peeled off cleanly, so that no design defects are caused. Furthermore, when the block amine compound is blended with the composition (A), the water containing metal ions reacts with the block amine compound to generate a primary amino group and / or a secondary amino group. In particular, when an isocyanate group-containing resin is used as the curable resin, the primary amino group and / or the secondary amino group generated from the block amine compound react with the isocyanate group of the isocyanate group-containing resin to form a urea bond. Thus, since it is crosslinked and cured, it has excellent anti-foaming properties at the time of curing, and the adjustment of the curing rate becomes easy.

  When the curable composition of the present invention contains a carboxylic acid anhydride compound and / or a carboxylic acid silyl ester compound in addition to the isocyanate group-containing resin and the block amine compound in the composition (A), the deep curable property is remarkably excellent. It will be. Although its mechanism of action is not necessarily clear, water containing metal ions reacts with a carboxylic anhydride compound or a carboxylic acid silyl ester compound to produce an acid compound, and the acid compound accelerates hydrolysis of the block amine compound. This is considered to promote the generation of primary amino groups and / or secondary amino groups. The isocyanate group of the isocyanate group-containing resin reacts preferentially with the primary amino group and / or secondary amino group generated rather than with water. It is considered that the curing of the curable composition is accelerated by promoting the generation of primary amino groups and / or secondary amino groups.

  Specifically, water containing metal ions can be obtained, for example, by mixing a metal salt and water and dissolving the metal salt in water. As a method for producing water containing metal ions, specifically, a method in which a metal salt and water are put in a mixing vessel made of resin, glass, metal or the like equipped with a stirrer and stirred to dissolve the metal salt. There is. If the metal salt is difficult to dissolve in water, it may be heated as necessary.

  As the metal ion, any metal that is ionized in the presence of water can be used without particular limitation. Among metal ions, alkali metal ions and alkaline earth metal ions are preferable because they are easily ionized in the presence of water and are relatively easily available. In particular, alkali metal ions are preferred because they are excellent in deep part curability of the curable composition of the present invention. Any of these may be used alone or in combination of two or more.

  Specific examples of alkali metal ions include lithium ions, sodium ions, potassium ions, and rubidium ions. Of these, sodium ions and potassium ions are preferable from the viewpoint of availability and versatility.

  Specific examples of the alkaline earth metal ions include magnesium ions, calcium ions, and barium ions.

  1-30 mass parts is preferable with respect to 100 mass parts of water, and, as for the compounding quantity of a metal ion, 1-20 mass parts is more preferable. When the compounding amount of the metal ions is less than 1 part by mass, the effect of accelerating the deep curability of the curable composition of the present invention is poor.

  Examples of the metal salt include an alkali metal salt and an alkaline earth metal salt. Any of these may be used alone or in combination of two or more.

  Examples of the alkali metal salt include a halide of an alkali metal, a salt of an alkali metal and an inorganic acid, and a salt of an alkali metal and an organic acid.

  Examples of the alkali metal halide include lithium chloride, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, and potassium iodide.

  Examples of the salt of an alkali metal and an inorganic acid include lithium sulfate, lithium nitrate, lithium carbonate, sodium sulfate, sodium nitrate, sodium carbonate, sodium hydrogen phosphate, potassium sulfate, potassium nitrate, potassium carbonate, and potassium hydrogen phosphate.

  Examples of alkali metal and organic acid salts include sodium formate, sodium acetate, sodium propionate, sodium pentanoate, sodium oxalate, sodium sorbate, sodium benzoate, potassium formate, potassium acetate, potassium propionate, potassium pentanoate, Examples include potassium oxalate, potassium sorbate, and potassium benzoate.

  Examples of the alkaline earth metal salt include a halide of an alkaline earth metal, a salt of an alkaline earth metal and an inorganic acid, and a salt of an alkaline earth metal and an organic acid.

  Examples of the alkaline earth metal halide include magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, barium chloride, barium bromide, and barium iodide.

  Examples of the alkaline earth metal and inorganic acid salt include magnesium sulfate, magnesium nitrate, calcium nitrate, and barium nitrate.

  Examples of the alkaline earth metal and organic acid salt include magnesium formate, magnesium acetate, calcium formate, calcium acetate, barium formate, and barium acetate.

  Water is not particularly limited as long as it reacts with the curable resin of the composition (A), and preferably reacts with a block amine compound, a carboxylic anhydride compound, and a carboxylic acid silyl ester compound. The composition (B) can accelerate the deep curability of the curable composition of the present invention by including water containing metal ions.

  Specific examples of water include tap water, ground water, distilled water, and ion exchange water.

  It is preferable that the compounding quantity of the water containing a metal ion is 0.1-5 mass parts with respect to 100 mass parts of curable resin of a composition (A), Furthermore, it is 0.1-3 mass parts. Particularly preferred is 0.1 to 2 parts by mass. In addition to the curable resin, in addition to the curable resin, the blending amount of water containing metal ions in the case of blending a block amine compound, a carboxylic anhydride compound, and a carboxylic acid silyl ester compound is the curable resin, block 0.1 to 6 parts by mass is preferable with respect to 100 parts by mass of the total amount of the amine compound, carboxylic anhydride compound and carboxylic acid silyl ester compound, more preferably 0.1 to 4 parts by mass, particularly 0.1 to 3 parts by mass. Is preferred.

  The curable composition of the present invention may further contain various additives as necessary in addition to the above-described components within a range not impairing the object of the present invention. Additives are used in the curable composition to improve various performances such as curing acceleration and adhesion of the curable composition. Specific examples include curing accelerators, plasticizers, weathering stabilizers, fillers, thixotropic agents, adhesion improvers, storage stability improvers (dehydrating agents), colorants, and organic solvents. Any of these may be used alone or in combination of two or more.

  An additive may be mix | blended with a composition (A), may be mix | blended with a composition (B), and may be mix | blended when mixing a composition (A) and a composition (B). It is preferable to mix in the composition (A) or when mixing the composition (A) and the composition (B) because of the ease of compounding the additive.

  The curing accelerating catalyst is used to promote the crosslinking and curing of the curable resin by reacting with water. In addition, when a curable resin and a block amine compound are blended in the composition (A), it is used to promote the reaction between the primary and / or secondary amino group generated from the block amine compound and the curable resin. To do. Further, the curing accelerating catalyst can be used as a reaction catalyst during the production of the urethane prepolymer described above. In addition, when it uses as a reaction catalyst at the time of manufacture of a urethane prepolymer, the reaction catalyst which remains in a urethane prepolymer acts also as a hardening acceleration | stimulation catalyst of a curable composition.

  Specific examples of the curing accelerating catalyst include salts of metals and organic acids, salts of organic metals and organic acids, metal chelate compounds, and tertiary amines. Examples of the salt of metal and organic acid include salts of various metals such as tin, bismuth, zirconium, zinc and manganese with organic acids such as octylic acid, neodecanoic acid, stearic acid and naphthenic acid. Specific examples include tin octylate, tin naphthenate, bismuth octylate, and zirconium octylate. As salts of organic metal and organic acid, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimaleate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin diversate, reaction of dibutyltin oxide and phthalate Things. As the metal chelate compound, dibutyltin bis (acetylacetonate), EXCESTAR C-501 made by Asahi Glass Co., which is a tin-based chelate compound, zirconium tetrakis (acetylacetonate), titanium tetrakis (acetylacetonate), aluminum tris (acetylacetate) Natto), aluminum tris (ethyl acetoacetate), acetylacetone cobalt, acetylacetone iron, acetylacetone copper, acetylacetone magnesium, acetylacetone bismuth, acetylacetone nickel, acetylacetone zinc and acetylacetone manganese. Tertiary amines include triethylamine, tributylamine, triethylenediamine, hexamethylenetetramine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 1,4-diazabicyclo [2,2,2]. Examples include octane (DABCO) and salts of these tertiary amines and organic carboxylic acids. Any of these may be used alone or in combination of two or more.

  Among these, since the curability of the curable composition is excellent, a salt of a metal and an organic acid, a salt of an organic metal and an organic acid, and a metal chelate compound are preferable, and a salt of tin and an organic acid, bismuth and Salts of organic acids, salts of organic tin and organic acids, salts of organic bismuth and organic acids, tin chelate compounds, and bismuth chelate compounds are preferred.

  The amount of the curing accelerating catalyst used is preferably 0.005 to 5 parts by mass, particularly preferably 0.005 to 2 parts by mass with respect to 100 parts by mass of the curable resin. When the usage-amount of a hardening acceleration catalyst exceeds 5 mass parts, there exists a tendency for the storage stability of a curable composition to fall.

  The plasticizer is used for the purpose of lowering the viscosity of the curable composition to improve workability and adjusting the rubber physical properties after curing of the curable composition. Specific examples include phthalates such as dioctyl phthalate, diisononyl phthalate, dibutyl phthalate, and butyl benzyl phthalate; aliphatic carboxylic acid esters such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate, and butyl oleate. Low molecular weight plasticizers such as the above; compounds obtained by urethanization, etherification or esterification of the same polyoxyalkylene polyols or polyoxyalkylene monools that can be used for the synthesis of the isocyanate group-containing urethane prepolymers described above; Examples thereof include high molecular weight plasticizers having a number average molecular weight of 1,000 or more that do not react with isocyanate groups such as poly-α-methylstyrene and polystyrenes such as polystyrene. Any of these may be used alone or in combination of two or more.

  The plasticizer is preferably used in an amount of 1 to 200 parts by weight, more preferably 2 to 50 parts by weight, based on 100 parts by weight of the curable resin.

  The weather resistance stabilizer is used for the purpose of further improving the weather resistance and heat resistance by preventing oxidation, light deterioration and heat deterioration of the curable composition. Examples of the weathering stabilizer include a hindered amine light stabilizer, a hindered phenol antioxidant, and an ultraviolet absorber. Any of these weather stabilizers can be used alone or in combination of two or more.

  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) -4 decanoate. -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]- Low molecular weight compounds having a molecular weight of less than 1,000, such as 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) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1 , 3,5-triazine condensate Other, ADEKA Corp. STAB LA-63P, compounds having a molecular weight of 1,000 or more high molecular weight, such as LA-68LD and the like.

  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-hydroxyphenyl) propioamide], 3,5-bisbenzenepropanoate (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) phenol.

  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 ultraviolet absorbers; benzophenone ultraviolet absorbers such as octabenzone; 2,4-di-tert-butylphenyl-3 Benzoate ultraviolet absorbers such as, 5-di-tert-butyl-4-hydroxybenzoate.

  Among these, a hindered amine light stabilizer, a hindered phenol antioxidant, and a mixture thereof are preferable in that the effect of improving weather resistance is high. The weathering stabilizer is preferably used in an amount of 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the curable resin.

  The filler is used for the purpose of reinforcing the physical properties of the hardener or the extender of the curable composition. Specifically, synthetic silica such as mica, kaolin, zeolite, graphite, diatomaceous earth, white clay, clay, talc, slate powder, anhydrous silicic acid, quartz fine powder, aluminum powder, zinc powder, precipitated silica, calcium carbonate, carbonic acid Inorganic powder fillers such as magnesium, alumina, calcium oxide, magnesium oxide; fibrous fillers such as glass fiber and carbon fiber; inorganic balloon fillers such as glass balloon, shirasu balloon, silica balloon, ceramic balloon; wood Powder, walnut shell powder, rice husk powder, pulp powder, cotton chip, rubber powder, fine powder of thermoplastic or thermosetting resin, powder or hollow body of polyethylene, organic balloon filler such as Saran microballoon; Other examples include flame retardant fillers such as magnesium hydroxide and aluminum hydroxide. The filler preferably has a particle size of 0.01 to 1,000 μm.

  The thixotropic agent imparts thixotropic properties to the curable composition, and prevents the occurrence of sagging and slump when the curable composition is used on a vertical surface or an inclined surface. It is used for the purpose of maintaining the shape of the coating when it is applied with a comb or the like. As thixotropic agents, fine silica such as hydrophilic or hydrophobic colloidal silica; inorganic thixotropic agents such as fatty acid surface-treated calcium carbonate; organic thixotropic agents such as organic bentonite and fatty acid amide; Can be mentioned. These can be used alone or in combination of two or more.

  The adhesion improver is used for the purpose of improving the adhesion of the cured product. Specific examples include various coupling agents such as silane, aluminum, and zircoaluminate, and partial hydrolysis condensates thereof. Of these, a silane coupling agent or a partially hydrolyzed condensate thereof is preferable because of its excellent adhesiveness.

  Examples of silane coupling agents include vinyltrimethoxysilane, vinylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) Low molecular weight compounds having a molecular weight of 500 or less, preferably 400 or less, containing alkoxysilyl groups such as -3-aminopropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane Or these sila It may include compounds having a molecular weight of 200 to 3,000 with one or more partially hydrolyzed condensate of the system a coupling agent. Any of these may be used alone or in combination of two or more.

  The storage stability improver (dehydrating agent) is used particularly for the purpose of improving the storage stability of the composition (A). Specific examples include vinyltrimethoxysilane, calcium oxide, and p-toluenesulfonyl isocyanate (PTSI) that react with water present in the composition (A) to act as a dehydrating agent. Any of these may be used alone or in combination of two or more.

  The colorant is used for the purpose of coloring the curable composition and imparting design properties to the cured product. Specific examples include inorganic pigments such as titanium oxide and iron oxide, organic pigments such as copper phthalocyanine, and carbon black. Any of these may be used alone or in combination of two or more.

  The organic solvent is used for the purpose of lowering the viscosity of the curable composition and improving the workability of extrusion and coating. As the organic solvent, any organic solvent that has good compatibility with other components in the curable composition and that does not react can be used without particular limitation. Specifically, carbonate solvents such as dimethyl carbonate, ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate and butyl acetate, aliphatic solvents such as n-hexane, and alicyclic systems such as cyclohexane Examples thereof include organic solvents such as solvents, aromatic solvents such as toluene and xylene, and petroleum distillate solvents such as mineral spirits and industrial gasoline. Any of these may be used alone or in combination of two or more.

  When constructing using the curable composition of the present invention, materials (members) to be constructed include mortar, concrete, ALC (Autoclaved Lightweight Concrete), glass, marble, granite, siding, tile, tile, brick Inorganic materials such as iron, copper, stainless steel, galvanium steel plate, metal materials such as iron, aluminum, titanium, acrylic resin, polyester resin, vinyl chloride, ABS (Acrylonitrile-Butadiene-Styrene copolymer), FRP (Fiber Reinforced Plastic), etc. A material made of synthetic resin, such as wood or plywood.

  Examples of the present invention are shown below, but the present invention is not construed as being limited to the examples.

Synthesis Example 1 (Synthesis of isocyanate group-containing urethane prepolymer PU-1)
While flowing nitrogen gas through a reactor equipped with a stirrer, thermometer, nitrogen seal tube and heating / cooling device, 280 g of polyoxypropylene diol (trade name Diol-3000, number average molecular weight 3,000, manufactured by Mitsui Chemicals, Inc.) , 46 g of polyoxypropylene triol (trade name Triol-MN-4000, number average molecular weight 4,000, manufactured by Mitsui Chemicals, Inc.) and 6 g of pentaerythritol triacrylate (molecular weight 298) were charged and stirred with isophorone diisocyanate (Degussa Japan). 50 g of molecular weight 222.3) and 0.06 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd., trade name Neostan U-100) were charged, heated, and reacted at 75 to 85 ° C. for 4 hours. The reaction was terminated when the isocyanate group content became the theoretical value (2.3% by mass) or less, and an isocyanate group-containing urethane prepolymer PU-1 was synthesized. The obtained isocyanate group-containing urethane prepolymer PU-1 was a viscous liquid transparent at room temperature with an isocyanate group content of 2.1% by mass measured by titration and a viscosity at 25 ° C. of 22,000 mPa · s. The calculated content of acryloyl groups in the molecule is 0.16 mmol / g.

Synthesis Example 2 (Synthesis of urethane bond-containing oxazolidine compound O-1)
A reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube, ester tube and heating / cooling device is charged with 435 g of diethanolamine (molecular weight 105) and 183 g of toluene, and 328 g of isobutyraldehyde (molecular weight 72.1) with stirring. While flowing nitrogen gas, the mixture was heated and reflux dehydration reaction was continued at 110 to 150 ° C., and by-produced water (74.5 g) was taken out of the system. After completion of the reaction, the mixture was further heated under reduced pressure (50 to 70 hPa) to remove toluene and unreacted isobutyraldehyde to obtain N-hydroxyethyl-2-isopropyloxazolidine as an intermediate reaction product.
Next, 348 g of hexamethylene diisocyanate (molecular weight 168) was further added to 659 g of the obtained N-hydroxyethyl-2-isopropyloxazolidine, heated at 80 ° C. for 8 hours, and the NCO content actually measured by titration was reduced to 0.0 mass%. At that time, the reaction was terminated, and a urethane bond-containing oxazolidine compound O-1 having two oxazolidine rings in the molecule was obtained. The obtained urethane bond-containing oxazolidine compound O-1 was liquid at room temperature.

Synthesis Example 3 (Synthesis of carboxylic acid silyl ester compound CS-1)
To 133.3 g of stearic acid as the carboxylic acid component and 219.0 g of lauric acid as the carboxylic acid component, toluene was added to a concentration of 50% by mass, and then a 3% by mass platinum chloride isopropyl alcohol solution was added in a predetermined amount (Si 10 μL per 100 g of H-group-containing polysiloxane was added to prepare an 80 ° C. carboxylic acid mixed solution. Next, 100.0 g of an equivalent Si—H group-containing polysiloxane (KF99, Si—H 0.0156 equivalent / g, manufactured by Shin-Etsu Chemical Co., Ltd.) is slowly added dropwise to the prepared carboxylic acid mixed solution. The temperature was raised to 90 ° C. and stirred until no hydrogen evolution was observed. Then, carboxylic acid silyl ester compound CS-1 was obtained by distilling off toluene.

Preparation of Composition (A) Into a kneading vessel equipped with a stirrer, a heating and cooling device and a nitrogen seal tube, 100 g of the isocyanate group-containing urethane prepolymer PU-1 was charged, and 20 g of dioctyl phthalate was previously added to each of 100 to 110 while stirring. 50 g of organic fatty acid-treated calcium carbonate (product name: Shiraishi Kogyo Co., Ltd., trade name Hakujyo Hana CCR) with a moisture content of 0.05% by mass or less, and a heavy calcium carbonate (product made by Shiroishi Calcium Co., Ltd.) 60 g of trade name Whiteon B) was charged and mixed until the contents were uniform. Next, 0.26 g of phthalic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.), 0.79 g of carboxylic acid silyl ester compound CS-1, 2 g of dimethyl carbonate, hindered amine light stabilizer (manufactured by ADEKA, trade name ADK STAB LA- 1 g of 63P, high molecular weight type) and hindered phenol antioxidant {pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]} (manufactured by BASF, Irganox) 1010) and 10 g of urethane bond-containing oxazolidine compound O-1 were added and mixed until the contents were uniform, then degassed under reduced pressure at 50 to 100 hPa, filled into a container, and sealed to form a composition. A product (A) was prepared.

Preparation of composition (B) (preparation of composition (B) W-1)
9 g of water and 1 g of sodium chloride were charged in a mixing container, and uniformly mixed and dissolved to prepare composition (B) W-1.
(Preparation of composition (B) W-2)
9 g of water and 1 g of potassium chloride were charged into a mixing container, and uniformly mixed and dissolved to prepare composition (B) W-2.

  The obtained composition (A) and composition (B) were charged in the amounts shown in Table 1 and mixed uniformly to obtain the curable compositions of the present invention (Examples 1 to 4). For comparison, a composition (B) using only water was mixed uniformly with the composition (A) in the blending amounts shown in Table 1 to obtain comparative curable compositions (Comparative Examples 1-2). . In addition, the mixing time until the curable composition of Examples 1-4 and Comparative Examples 1-2 became uniform was 15 minutes.

<Evaluation of curable composition>
The following evaluation was performed using the curable composition of Examples 1-4 and Comparative Examples 1-2. The evaluation results are shown in Table 1.

[Tack Free Time]
On the slate plate, the curable compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were placed in a bead shape having a width of 20 mm × a height of 10 mm × a length of 100 mm, and 5 ° C. 40% RH or 23 ° C. 50 It was allowed to stand in an environment of% RH. A polyethylene film having a thickness of 0.1 mm was brought into contact with the surface of the curable composition, and the time until the curable composition did not adhere to the polyethylene film was measured.

[Deep part curability]
Two square backup materials made of polyethylene having a thickness of 10 mm were stacked to a thickness of 20 mm. Using this, a square frame of 50 mm length × 50 mm width was produced on the slate plate, and then Examples 1-4 and The curable compositions of Comparative Examples 1 and 2 were immediately cast and flattened with a spatula so as to have a thickness of 20 mm. The test specimen was left standing in an environment of 5 ° C. and 40% RH for a predetermined time, then cut with a cutter so that the cross section of the composition could be seen, the surface cured portion was taken out, and the thickness of the cured product was measured.

[hardness]
Two square backup materials made of polyethylene having a thickness of 10 mm were stacked to a thickness of 20 mm. Using this, a square frame of 50 mm length × 50 mm width was produced on the slate plate, and then Examples 1-4 and The curable compositions of Comparative Examples 1 and 2 were immediately cast and flattened with a spatula so as to have a thickness of 20 mm. The test specimen was allowed to stand in an environment of 5 ° C. and 40% RH for a predetermined time, and then Asker C hardness was measured according to Japan Rubber Association Standard (SRIS) 0101.

[Healing tape peelability]
An aluminum plate having a width of 12 mm, a thickness of 17 mm, and a length of 300 mm was arranged in parallel on the slate plate so that a joint having a width of 17 mm, a depth of 17 mm, and a length of 300 mm was formed. In this state, the aluminum plate was fixed to the slate plate. . Subsequently, a curing tape (masking tape, width: 17 mm, manufactured by Kamoi Paper Co., Ltd.) was applied to the aluminum plate along the joints to prepare a test body.
The curable compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were immediately placed on the joints of the test specimens, and the surface of the curable composition was flattened with a spatula, and then 5 ° C 40RH% or 23 ° C 50RH%. The curable composition was cured under the following conditions, and the curing tape was peeled off after 5 hours, 8 hours, and 24 hours. The situation when the curing tape was peeled off was visually confirmed, and the curing tape peeling property was evaluated according to the following evaluation criteria.
Standard ○: The curable composition on the curing tape peels off cleanly and does not cause design defects. △: The curable composition on the curing tape is partially pulled by the curing tape, resulting in slight burr at the joints. , Causing design defects ×: The curable composition on the curing tape is pulled to the curing tape and does not peel off cleanly, and if the curing tape is forcibly pulled, burrs are generated and burrs remain on the joints or joints. Cause the above bug

[Healing sheet peelability]
An aluminum plate having a width of 12 mm, a thickness of 17 mm, and a length of 300 mm was arranged in parallel on the slate plate so that a joint having a width of 17 mm, a depth of 17 mm, and a length of 300 mm was formed. In this state, the aluminum plate was fixed to the slate plate. . Next, a curing sheet (polymasker (cloth tape + polyethylene sheet, manufactured by Otsuka Brush Manufacturing Co., Ltd.)) was stuck on the aluminum plate along the joints to prepare a test specimen.
The curable compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were immediately placed on the joints of the test specimens, and the surface of the curable composition was flattened with a spatula, and then 5 ° C 40RH% or 23 ° C 50RH%. The curable composition was cured under the above environment, and the cured sheet was peeled off after 5 hours, 8 hours, and 24 hours. The condition when the curing sheet was peeled off was visually confirmed, and the curing sheet peeling property was evaluated according to the following evaluation criteria.
Standard ○: The curable composition on the curing sheet peels off cleanly and does not cause design defects. Δ: The curable composition on the curing sheet is partially pulled by the curing sheet, resulting in slight burr at the joints. , Causing design defects ×: The curable composition on the curing sheet is pulled to the curing sheet and does not peel off cleanly, and if the curing sheet is forcibly pulled, burrs are generated and burrs remain on the joints or joints. Cause the above bug

From the results of Table 1, the curable composition of the present invention has the same surface curability (tack free time) as the curable compositions of Comparative Examples 1 and 2, and can sufficiently ensure workability. I understand. Moreover, it turns out that the curable composition of this invention is excellent in the deep-part sclerosis | hardenability at the time of low temperature (5 degreeC40% RH) compared with the curable composition of Comparative Examples 1-2, and also the hardness at the time of low temperature is also high. Therefore, the curable composition of the present invention can shorten the curing period until it is internally cured, leading to a shortened construction period.
In addition, the curable compositions of the present invention (Examples 1 to 4) are cured tapes and sheets after 5 hours, 8 hours, and 24 hours in an environment of 5 ° C. and 40% RH and 23 ° C. and 50% RH. When the is peeled off, there is no unevenness in the surface curing, the curable composition is peeled off cleanly and no design defects occur, and the workability during construction is excellent. On the other hand, the curable compositions of Comparative Examples 1 and 2 are slow to cure in an environment of 5 ° C. and 40% RH, and when the curing tape or the curing sheet is peeled off, paste-like burrs are generated, resulting in a design defect. Moreover, since the curing is slow even in an environment of 23 ° C. and 50% RH, and the surface layer portion is cured, the inside is not cured, and therefore, when the curing tape or the curing sheet is peeled off, burrs are generated and a design defect occurs ( 5 hours and 8 hours later).

  As described above, the curable composition of the present invention can be suitably used for construction and civil engineering because it can sufficiently ensure workability and is excellent in deep-part curability and curing tape and curing sheet peeling. . Moreover, the curable composition of this invention can be used conveniently as a sealing material composition, a waterproofing material composition, an adhesive composition, and a coating material composition.

Claims (10)

  A curable composition comprising a composition (A) containing a curable resin and a composition (B) containing water containing metal ions.   The curable composition according to claim 1, wherein the curable resin is an isocyanate group-containing resin or a crosslinkable silyl group-containing resin.   The said composition (A) contains a block amine compound, The curable composition of Claim 1 or 2 characterized by the above-mentioned.   The curable composition according to any one of claims 1 to 3, wherein the block amine compound is at least one compound selected from an oxazolidine compound, an aluminidine compound, and a ketimine compound.   The said composition (A) contains a carboxylic anhydride compound and / or a carboxylic acid silyl ester compound, The curable composition as described in any one of Claims 1-4 characterized by the above-mentioned.   The curable composition according to claim 1, wherein the metal ion is an alkali metal ion and / or an alkaline earth metal ion.   Furthermore, an additive is contained, The curable composition as described in any one of Claims 1-6 characterized by the above-mentioned.   The curable composition according to any one of claims 1 to 7, wherein the amount of water containing the metal ions is 0.1 to 5 parts by mass with respect to 100 parts by mass of the curable resin. object.   The curable composition according to any one of claims 1 to 8, wherein the curable composition is a curable composition for construction or civil engineering.   The curable composition according to any one of claims 1 to 9, wherein the curable composition is a sealing material composition, a waterproof material composition, an adhesive composition, or a coating material composition.