JP4435591B2 - Curable composition - Google Patents

Description

  The present invention relates to a room temperature curable composition that cures with moisture. More specifically, the present invention relates to a curable composition containing an organic polymer having a reactive silicon-containing functional group that can be crosslinked by forming a siloxane bond.

  A method of curing an organic polymer having a reactive silicon group (reactive silicon-containing functional group capable of forming a siloxane bond by crosslinking through hydrolysis and condensation) and using it as a sealant, adhesive, etc. It is a well-known and industrially useful method.

  Among such compounds, oxyalkylene polymers, polyisobutylene polymers, and (meth) acrylic polymers having a main chain in particular are liquid at room temperature, and cured products have low modulus and high elongation characteristics. Therefore, it is used for sealing materials and adhesives.

  Examples of moisture curable resins having a reactive silicon group at the terminal include a resin in which a reactive silicon group-containing compound is introduced into an unsaturated terminal group of an oxyalkylene polymer by a hydrosilylation reaction (see Patent Document 1), oxy Examples thereof include a resin obtained by reacting a terminal hydroxyl group of an alkylene polymer with a reactive silicon group-containing isocyanate compound (see Patent Document 2).

  In general, various plasticizers and diluting solvents are blended in the composition containing these reactive silicon group-containing polymers for the purpose of imparting flexibility and ensuring good workability by reducing the viscosity. Therefore, when used as a sealing material, there is a problem that it causes bleeding on the surface of the sealing material and contamination around the sealing joint. Further, when a paint is applied to the surface of the sealing material, there is a problem that the plasticizer contaminates the paint.

  Similarly, when used for adhesives, in recent years, the sick house problem, the plasticizer such as TVOC, and the volatilization and scattering of the diluent solvent have become major problems.

  As a method for solving these problems, instead of a plasticizer, a method using a polyether having one end of a linear molecular chain blocked with an organic group and the other end having a reactive silicon group (patented) Reference 3), a method of using a polyether having a high molecular weight and a high reactive silicon group content per molecule together with a polyether having a low molecular weight and a low reactive silicon group content per molecule (Patent Literature) 4), a method of using a polyether having a high molecular weight and a reactive silicon group content of 50% or more per terminal group together with a polyether having a reactive silicon group content of less than 50% per terminal group (patent) Reference 5) has been proposed.

  However, even in these methods, a polyether having one end of a linear molecular chain blocked with an organic group and the other end having a reactive silicon group, or a low molecular weight reactive silicon per molecule By using a polyether having a small group content, the crosslink density of the cured product is lowered, resulting in a problem that the modulus is greatly lowered.

On the other hand, a cured product composed of an organic polymer alone having many reactive silicon groups having three hydrolyzable groups on silicon tends to be very fragile and tends to have low elongation. In addition, when the molecular weight is set to ensure elongation, there is a problem that the viscosity increases.
JP-A-3-72527 Japanese Patent Laid-Open No. 3-47825 JP-A-4-57850 JP-A-5-59267 JP-A-9-95609

  In view of the above problems, the problem of the present invention is that when the viscosity of the composition is low and the workability is good, the cured product has flexibility, and when it is used for a sealing agent, an adhesive, etc. Reactive silicon group with less spillage and volatilization of the cured product, contamination around the sealing joints, and less paint contamination when the coating is applied to the surface of the sealant. Furthermore, the cured product has good recovery, durability and creep resistance. It is to provide a room temperature curable composition.

As a result of intensive studies on the above problems, the present inventor has achieved the above-described problem by the following method. That is,
1) An organic polymer (A) containing a reactive silicon group represented by the following general formula (1) and an average of 0.5 reactive silicon groups represented by the following general formula (2) per molecule It relates to a curable composition comprising an organic polymer (B) containing ˜1.5.
-Si (R ¹ ) X ₂ (1)
(In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosiloxy group represented by (R ′) ₃ SiO—. And when two or more R ¹ are present, they may be the same or different, wherein R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ′ may be the same or different, X represents a hydroxyl group or a hydrolyzable group, and they may be the same or different.
-SiX ₃ (2)
(Wherein X is the same as that of general formula (1))
2) A reactive silicon group-containing compound in which the organic polymer (B) has a reactive silicon group represented by the general formula (2) and a functional group capable of reacting with the reactive group in the organic polymer, The curable composition according to 1), which is a polymer obtained by reacting 0.5 mol to 1.5 mol with respect to 1 mol of the polymer.
3) The curable composition according to 1) or 2), wherein the main chain skeletons of the organic polymers (A) and (B) are both oxyalkylene polymers.
4) The curable composition according to any one of 1) to 3), wherein the organic polymer (B) has substantially one reactive silicon group represented by the general formula (2). Relates to the composition.
5) It relates to the curable composition according to any one of 1) to 4), wherein the molecular weight of the organic polymer (B) is 8000 or less.

  The curable composition of the present invention has an uncured product when the viscosity of the composition is low and the workability is good, and the cured product has flexibility and is used as a sealing agent, an adhesive or the like. Room temperature with reactive silicon group that has less paint contamination when paint is applied to the surface of the sealing agent, and the surface around the sealing joint, and the cured product has good resilience, durability and creep resistance. It is a curable composition.

The reactive silicon group contained in the component (A) of the present invention is not particularly limited, and representative examples thereof include a group represented by the general formula (1).
-Si (R ¹ ) X ₂ (1)
(In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosiloxy group represented by (R ′) ₃ SiO—. And when two or more R ¹ are present, they may be the same or different, wherein R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ′ may be the same or different, X represents a hydroxyl group or a hydrolyzable group, and they may be the same or different.
The hydrolyzable group represented by X is not particularly limited, and any conventionally known hydrolyzable group can be suitably used. Specifically, for example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable. Alkoxy groups such as a methoxy group and an ethoxy group are particularly preferable because they are gentle and easy to handle.

  The reactive silicon group is not particularly limited, but is preferably an alkoxy group because of its high hydrolytic activity and mild hydrolyzability and ease of handling. Specific functional groups include methyldimethoxysilyl group and methyldiethoxy group. It is preferably at least one selected from the group consisting of a silyl group, a methyldiisopropenyloxysilyl group, an ethyldimethoxy group, an ethyldiethoxysilyl group, an ethyldiisopropenyloxysilyl group, and the like. Of these, a methyldimethoxysilyl group, a methyldiethoxysilyl group, and an ethyldiethoxysilyl group are particularly preferable from the viewpoint of reactivity and the flexibility of the resulting cured product.

  The average number of reactive silicon groups in the organic polymer (A) is preferably at least one per molecule, more preferably 1.1 to 5, and even more preferably 1.5 to 5. When the number of reactive silicon groups contained in one molecule of the organic polymer (A) is less than one, the curability becomes insufficient and good rubber elasticity is difficult to be obtained, and the restorability and durability of the cured product. In addition, the creep resistance is hardly exhibited. The reactive silicon group may exist at the end of the molecular chain of the organic polymer (A) or may exist inside. When the reactive silicon group is present at the end of the molecular chain, the effective network chain amount of the organic polymer (A) component contained in the finally formed cured product increases, so that it has high strength, high elongation, and low elasticity. It becomes easy to obtain a rubber-like cured product showing a rate.

(Introduction of reactive silicon groups)
The method for introducing the reactive silicon group into the polymer is not particularly limited, and various methods can be used. For example, a) a hydrosilylation method in which an organic polymer having an unsaturated group such as an alkenyl group is reacted with a reactive silicon group-containing hydrosilane compound in the presence of a group 8 transition metal catalyst, b) a hydroxyl group, an epoxy group, an isocyanate group A method in which a compound having both a functional group-reactive group and a reactive silicon group is reacted with an organic polymer having a functional group (for example, a reaction between an organic polymer having a hydroxyl group and an isocyanate silane), c) alkenyl And a method of reacting an organic polymer having an unsaturated group such as a group with a compound having both a reactive silicon group and a mercapto group.

  Among these, the method (i) is preferable from the viewpoints of removability of residual raw materials, reactivity, and the like.

For example, as a method for producing an organic polymer having an unsaturated group such as an alkenyl group at the terminal, a conventionally known method may be used. For example, a compound having an alkenyl group is reacted with a hydroxyl-terminated organic polymer to form an ether bond. , An ester bond, a urethane bond, a carbonate bond, and the like. For example, when an alkenyl group is introduced by an ether bond, the hydroxyl group end of the organic polymer is changed to an oxymetal group such as -ONa or -OK, and then the general formula (3):
CH ^₂ = CH-R ₂ -Y general formula (3)
Or general formula (4):
^{_{CH 2 = C (R 3)}} -R 2 -Y general formula (4)
(Wherein R ² is a divalent organic group having 1 to 20 carbon atoms, R ³ is a hydrocarbon group having 10 or less carbon atoms, and Y is a halogen atom). Can be mentioned.

Examples of the method for converting the terminal hydroxyl group into an oxymetal group include a method of reacting with an alkali metal such as Na and K; a metal hydride such as NaH; a metal alkoxide such as NaOCH ₃ ; and an alkali hydroxide such as NaOH and KOH. It is done.

Specific examples of the general formula (2) or unsaturated group-containing compound represented by (3), for example, _{CH 2 = CH-CH 2 -Cl} , CH 2 = CH-CH 2 -Br, CH 2 = CH-C _{2 H 4 -Cl, CH 2 =} CH-C 2 H 4 -Br, CH 2 = CH-C 3 H 6 -Cl, CH 2 = CH-C 3 H 6 -Br, CH 2 = C (CH 3) _{-CH 2 -Cl, CH 2 = C} (CH 3) -CH 2 -Br, CH 2 = C (CH 2 CH 3) -CH 2 -Cl, CH 2 = C (CH 2 CH 3) -CH 2 - _{br, CH 2 = C (CH} 2 CH (CH 3) 2) -CH 2 -Cl, CH 2 = C (CH 2 CH (CH 3) 2) -CH 2 -Br, and the like. particularly reactive in terms _{of, CH 2 = CH-CH 2} -Cl, CH 2 = C (CH 3) -CH 2 -Cl is preferred.

As a method for introducing an unsaturated group, addition to CH ₂ = CH-CH ₂ - using isocyanate compounds having a group such as a carboxylic acid compound, an epoxy compound or the like - group and _{CH 2 = C (CH 3)} -CH 2 You can also.

A reactive silicon group is further introduced into the organic polymer into which the alkenyl group has been introduced by the above compound by a hydrosilylation reaction. As the group 8 transition metal catalyst used at that time, a metal complex catalyst selected from group 8 transition metal elements such as platinum, rhodium, cobalt, palladium and nickel is used. For example, H ₂ PtCl ₆ .6H ₂ O, platinum-vinylsiloxane complex, platinum-olefin complex, Pt metal, RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , PdCl ₂ .2H ₂ O, NiCl _{2 and} the like can be used, but any of H ₂ PtCl ₆ .6H ₂ O, platinum-vinylsiloxane complex, and platinum-olefin complex can be used from the viewpoint of hydrosilylation reactivity. It is particularly preferable.

  Such manufacturing methods are disclosed in, for example, Japanese Patent No. 1396791, Japanese Patent No. 1727750, Japanese Patent No. 2135575, and Japanese Patent Laid-Open No. 3-72527.

  As the hydrosilane compound used in the hydrosilylation reaction, generally, halogenated silanes such as trichlorosilane and methyldichlorosilane; trialkoxysilanes such as trimethoxysilane and triethoxysilane; methyldimethoxysilane and ethyl Examples of the hydrosilane compound used for producing the polymer (A) having reactive silicon represented by the general formula (1) include alkyl dialkoxysilanes such as diethoxysilane. Examples include, but are not limited to, alkyl dialkoxysilanes such as dichlorosilane, methyldimethoxysilane, and ethyldiethoxysilane. Of these, alkyldialkoxysilanes are particularly preferred from the viewpoints of hydrolyzability, mildness of reaction, storage properties, and the like.

  Examples of (b) include, for example, a method of reacting a polymer having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive silicon group, such as the method disclosed in JP-A-3-47825. Is not to be done. Specific examples of the compound having an isocyanate group and a reactive silicon group generally include γ-isocyanatepropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-isocyanatepropyl. Examples of the compound used for producing the polymer (A) having reactive silicon represented by the general formula (1) include γ-isocyanatopropylmethyldimethoxysilane, γ, and the like. -Isocyanatopropylmethyldiethoxysilane and the like are not limited thereto.

  As a method of c), for example, a compound having a mercapto group and a reactive silicon group is introduced into an unsaturated bond site of an organic polymer by a radical addition reaction in the presence of a radical initiator and / or a radical source. Examples of the method include, but are not limited to. Specific examples of the compound having a mercapto group and a reactive silicon group generally include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropyl. Examples of the compound used for producing the polymer (A) having reactive silicon represented by the general formula (1) include γ-mercaptopropylmethyldimethoxysilane, γ, and the like. -Mercaptopropylmethyldiethoxysilane and the like, but not limited thereto.

  The reactive silicon group may be at the end or inside of the organic polymer molecular chain or at both. In particular, when the reactive silicon group is at the molecular end, the effective network chain amount of the organic polymer component contained in the finally formed cured product increases, so that a rubber-like cured product having high strength and high elongation is obtained. It is preferable from the viewpoint of being easily obtained.

  The main chain skeleton of the organic polymer (A) and organic polymer (B) having a reactive silicon group of the present invention is not particularly limited. For example, the main chain skeleton is a generally known oxyalkylene polymer, Organic polymers such as vinyl polymers, saturated hydrocarbon polymers, polyester polymers, and polyurethanes can be used.

  The main chain skeleton of the organic polymer (A) of the present invention is preferably an oxyalkylene polymer because it is liquid at room temperature, has good low-temperature characteristics, has low viscosity, and has good compatibility.

As a unit constituting the polymer main chain when the main chain skeleton of the organic polymer (A) is an oxyalkylene polymer, the general formula (5):
-R ⁴ -O- (5)
(Wherein, R ⁴ is a divalent alkylene group having 1 to ⁴ carbon atoms) can be used, but an oxypropylene polymer is more preferred from the viewpoint of easy availability.

  The oxyalkylene polymer may be linear or branched, or a mixture thereof. In addition, other monomer units and the like may be contained, but the structural unit represented by the above formula is an oxyalkylene from the viewpoint of moderately low viscosity and a cured product having appropriate flexibility. It is preferable that the polymer is present in an amount of 50% by weight or more, preferably 80% by weight or more.

  Although there is no restriction | limiting in particular in the molecular weight of an oxyalkylene type polymer, It is preferable that the number average molecular weights by polystyrene conversion in GPC measurement are 500-100,000. Furthermore, it is preferable that it is 1,000-70,000 from the ease of handling etc. When the number average molecular weight is less than 500, the cured product becomes brittle, and when the number average molecular weight exceeds 100,000, the viscosity of the polymer becomes too high.

  Furthermore, in this oxypropylene polymer, the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) is preferably 1.6 or less, more preferably 1.5 or less, and even more preferably 1 .4 or less. The molecular weight distribution can be measured by various methods, but is usually measured by a gel permeation chromatography (GPC) method. The composition using the oxypropylene polymer having a reactive silicon group having an Mw / Mn of 1.6 or less has a low viscosity and exhibits good workability.

  The method for producing the polymer main chain in the oxyalkylene polymer is not particularly limited, and examples thereof include a method obtained by ring-opening polymerization of a monoepoxide in the presence of an initiator and a catalyst. Specifically, for example, a transition metal compound represented by a complex obtained by reacting an organoaluminum compound and a porphyrin shown in JP-A-61-215623, for example, by a polymerization method using an alkali catalyst such as KOH -Polyphyrin complex-catalyzed polymerization methods, for example, Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, US Pat. No. 3,278,457, US Pat. No. 3,278,458, US Pat. No. 3,278,459, US Pat. No. 3,427,256, US Pat. Examples thereof include a polymerization method using a double metal cyanide complex catalyst disclosed in Japanese Patent No. 3427335, for example, a polymerization method using phosphazene disclosed in Japanese Patent Application Laid-Open No. 11-60723. Among them, the polymerization method using a double metal cyanide complex catalyst and the polymerization method using phosphazene are high in color because they are hardly colored, and a polyoxyalkylene polymer having a narrow molecular weight distribution can be obtained even with a high molecular weight. The molecular weight is preferable because an oxyalkylene polymer having a low viscosity is obtained.

In addition to this, the polymer main chain of the oxyalkylene polymer is a hydroxyl group-terminated polyoxyalkylene polymer in the presence of a basic compound such as KOH, NaOH, KOCH ₃ , NaOCH _3, or the like. It can also be obtained by chain extension with alkyl halides such as CH ₂ Cl ₂ and CH ₂ Br ₂ . In addition, a method of chain-extending a hydroxyl group-terminated polyoxyalkylene polymer with a bifunctional or trifunctional isocyanate compound is also exemplified.

  As the main chain skeleton of the organic polymer (A) of the present invention, a vinyl polymer having a reactive silicon group can be used in addition to the oxyalkylene polymer. The main chain of the vinyl polymer can be obtained by controlled radical polymerization or free radical polymerization.

  First, the case of controlled radical polymerization will be described.

  The inventors have so far made numerous inventions relating to vinyl polymers having various crosslinkable functional groups at the ends of the polymer, methods for producing the same, curable compositions, and uses (JP-A-11-080249). JP-A-11-080250, JP-A-11-005815, JP-A-11-116617, JP-A-11-116606, JP-A-11-080571, JP-A-11-080570, JP-A-11-130931, JP-A-11-1000043, Special (See Kaihei 11-116763, JP-A-9-272714, JP-A-9-272715, etc.). Although it does not specifically limit as a vinyl polymer, All the polymers disclosed by the invention illustrated above can be used suitably.

  It does not specifically limit as a vinyl-type monomer which comprises the principal chain of a vinyl-type polymer, Various things can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n- Butyl, isobutyl (meth) acrylate, (tert-butyl) (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl Acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) Phenyl acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate (Meth) acrylic acid-3-methoxybutyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid stearyl, (meth) acrylic acid glycidyl, (meth) 2-aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate , 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate , (Perfluoromethylmethyl) (meth) acrylate, (me T) 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluoro (meth) acrylate (Meth) acrylic monomers such as hexadecylethyl; aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and their salts; perfluoroethylene, perfluoropropylene, vinylidene fluoride Fluorine-containing vinyl monomers such as vinyl trimethoxysilane, vinyl triethoxysilane and other silicon-containing vinyl monomers; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl of fumaric acid Beauty treatment And maleic monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; and acrylonitriles such as acrylonitrile and methacrylonitrile Monomers; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; Alkenes such as ethylene and propylene; Butadiene and isoprene Conjugated dienes such as vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be used alone or a plurality of these may be copolymerized.

  The main chain of the vinyl polymer is mainly polymerized with at least one monomer selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and silicon-containing vinyl monomers. It is preferable that it is manufactured. Here, “mainly” means that 50 mol% or more, preferably 70% or more of the monomer units constituting the vinyl polymer are the above monomers.

  Of these, a styrene monomer and a (meth) acrylic acid monomer are preferable from the physical properties of the product. More preferred are acrylate monomers and methacrylate monomers, particularly preferred are acrylate monomers, and even more preferred is butyl acrylate. In the present invention, these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in that case, these preferred monomers are preferably contained in a weight ratio of 40% or more. . In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  Although not limited, it is preferable that the glass transition temperature of the vinyl polymer is lower than room temperature or use temperature for applications requiring rubber elasticity.

  The molecular weight distribution of the vinyl polymer, that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography is not particularly limited, but preferably 1. Is less than 8, more preferably 1.7 or less, even more preferably 1.6 or less, still more preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1. 3 or less. In the GPC measurement in the present invention, chloroform is usually used as the mobile phase, the measurement is performed with a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene.

  The number average molecular weight of the vinyl polymer is not particularly limited, but is preferably in the range of 500 to 1,000,000, more preferably 1,000 to 100,000, when measured by gel permeation chromatography. 000 to 50,000 is more preferable.

  As a method for synthesizing a vinyl polymer, living radical polymerization is preferable among controlled radical polymerizations, and among them, atom transfer radical polymerization is preferable.

  In atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl-position), or a sulfonyl halide. A compound or the like is used as an initiator.

  Next, the vinyl polymer produced by the free radical polymerization method will be described.

  It does not specifically limit as a vinyl-type monomer, Various things can be used and all the monomers used by the above-mentioned controlled radical polymerization can be used suitably.

  Although not limited, at least one main chain of the vinyl polymer is selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and silicon-containing vinyl monomers. It is preferable that it is produced mainly by polymerizing two monomers. Here, “mainly” means that 50 mol% or more, preferably 70% or more of the monomer units constituting the vinyl polymer are the above monomers.

  Of these, a styrene monomer and a (meth) acrylic acid monomer are preferable from the physical properties of the product. More preferred are acrylate monomers and methacrylate monomers. In the present invention, these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in that case, these preferred monomers are preferably contained in a weight ratio of 40% or more. . In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid. These may be used alone or a plurality of these may be copolymerized.

  In addition to the above monomer units such as a (meth) acrylic acid ester monomer, the vinyl polymer may contain a monomer unit having copolymerizability with these. For example, carboxylic acid groups such as (meth) acrylic acid, amide groups such as (meth) acrylamide and N-methylol (meth) acrylamide, epoxy groups such as glycidyl (meth) acrylate, diethylaminoethyl (meth) acrylate, aminoethyl vinyl ether A monomer containing an amino group such as can be expected to have a copolymerization effect in terms of moisture curability and internal curability. Other examples include monomer units derived from acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene, and the like.

  The number average molecular weight of the vinyl polymer in this case is not particularly limited, but when measured by gel permeation chromatography, those having a molecular weight of 500 to 100,000 are preferred from the viewpoint of ease of handling. Furthermore, the thing of 5,000-30,000 is more preferable from the weather resistance of a hardened | cured material, and workability | operativity being favorable.

  A method of synthesizing the main chain of the vinyl polymer by free radical polymerization can be obtained by a usual vinyl polymerization method, for example, a solution polymerization method by radical reaction. The polymerization is usually carried out by adding the above-mentioned monomer, a radical initiator, a chain transfer agent and the like and reacting at 50 to 150 ° C.

  Examples of the radical initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 4,4′-azobis (4-cyanovaleric) acid. , 1,1′-azobis (1-cyclohexanecarbonitrile), azobisisobutyric acid amidine hydrochloride, 2,2′-azobis (2,4-dimethylvaleronitrile) and other azo initiators, benzoyl peroxide, diperoxide Organic peroxide-based initiators such as -tert-butyl are exemplified, but use of azo-based initiators is preferable in that they are not affected by the solvent used for polymerization and have a low risk of explosion and the like.

  Examples of chain transfer agents include n-dodecyl mercaptan, tert-dodecyl mercaptan, lauryl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyl Examples include mercaptans such as diethoxysilane and halogen-containing compounds.

  The polymerization may be performed in a solvent. Examples of the solvent are preferably nonreactive solvents such as ethers, hydrocarbons, and esters.

  As the reactive silicon group of the vinyl polymer, the reactive silicon group represented by the aforementioned general formula (1) can be used in the same manner.

As a method for introducing a reactive silicon group into a vinyl polymer, in addition to the methods a), b) and c) described above, for example, a compound having both a polymerizable unsaturated bond and a reactive silicon group. Can be copolymerized with (meth) acrylic acid ester monomer units. As a compound having both a polymerizable unsaturated bond and a reactive silicon group, the general formula (6):
^{_{CH 2 = C (R 5)}} COOR 6 -Si (R 1 3-a) X a (6)
(Wherein R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a divalent alkylene group having 1 to ⁶ carbon atoms, R ¹ and X are the same as those in formula (1), a represents 1, 2 and 3.)
Or general formula (7):
^{_{CH 2 = C (R 5)}} -Si (R 1 3-a) X a (7)
(In the formula, R ⁵ , R ¹ , X and a are the same as above.)
Γ-methacryloxypropyl polyalkoxysilane such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane; Γ-acryloxypropyl polyalkoxysilanes such as loxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyltriethoxysilane; vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, etc. Vinylalkylpolyalkoxysilanes and the like are generally mentioned. As a monomer for introducing a reactive silicon group in which a is 2, γ-methacryloxy such as γ-methacryloxypropylmethyldimethoxysilane is used. B pills alkyl dialkoxy silane; .gamma.-acryloxypropyl .gamma. acryloxypropyl alkyl dialkoxy silane such as methyl dimethoxysilane; vinyl alkyl alkyl dialkoxy silane such as vinyl methyl dimethoxy silane.

  Next, the case where the main chain skeleton of the organic polymer (A) is a saturated hydrocarbon polymer will be described. The saturated hydrocarbon polymer having a reactive silicon group is a polymer that does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring. For example, polyethylene, polypropylene, polyisobutylene, hydrogenated polybutadiene, hydrogenated And polyisoprene.

  These saturated hydrocarbon polymers having a reactive silicon group can be used alone or in combination of two or more.

  The polymer constituting the skeleton of the saturated hydrocarbon polymer having a reactive silicon group used in the present invention is mainly composed of (1) an olefin compound having 1 to 6 carbon atoms such as ethylene, propylene, 1-butene, and isobutylene. It can be obtained by a method of polymerizing as a monomer, (2) homopolymerizing a diene compound such as butadiene or isoprene, or copolymerizing with the olefin compound and then hydrogenating. An isobutylene polymer or a hydrogenated polybutadiene polymer is preferable because it is easy to introduce a functional group at the terminal, easily control the molecular weight, and increase the number of terminal functional groups.

  In the isobutylene polymer, all of the monomer units may be formed from isobutylene units, and the monomer units copolymerizable with isobutylene are preferably 50% or less (% by weight, in the isobutylene polymer). The same shall apply hereinafter), more preferably 30% or less, particularly preferably 10% or less.

  Examples of such monomer components include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, and allyl silanes. Examples of such copolymer components include 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene, vinylcyclohexene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, β-pinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane Allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldichlorosilane, diallyldimethoxysilane, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyl Examples include dimethoxysilane.

  In addition, when vinyl silanes or allyl silanes are used as monomers that are copolymerizable with isobutylene, the silicon content increases and the number of groups that can act as a silane coupling agent increases. Will improve.

  In the hydrogenated polybutadiene polymer and other saturated hydrocarbon polymers, as in the case of the isobutylene polymer, other monomer units are contained in addition to the main monomer unit. May be.

  In addition, in the saturated hydrocarbon polymer having a reactive silicon group used in the present invention, double bonds such as polyene compounds such as butadiene and isoprene remain after polymerization within the range in which the object of the present invention is achieved. Such monomer units may be contained in a small amount, preferably 10% by weight or less, more preferably 5% by weight or less, and particularly 1% by weight or less.

  The number average molecular weight of the saturated hydrocarbon polymer, preferably isobutylene polymer or hydrogenated polybutadiene polymer, is preferably about 500 to 50,000, particularly about 1,000 to 20,000. It is preferable from the viewpoint of easy handling.

  Next, a method for producing a saturated hydrocarbon polymer having a reactive silicon group will be described.

  Among isobutylene polymers having a reactive silicon group, an isobutylene polymer having a reactive silicon group at the molecular chain end is a polymerization method called an inifer method (a specific method using both an initiator called an inifer and a chain transfer agent). It can be produced using a terminal functional type, preferably an all terminal functional type isobutylene polymer obtained by a cationic polymerization method using a compound. For example, polyisobutylene having an unsaturated group at the terminal was obtained by dehydrohalogenation reaction of this polymer or unsaturated group introduction reaction to the polymer as described in JP-A-63-105005. Thereafter, as in the case of the above-mentioned reactive silyl group-containing oxyalkylene polymer and vinyl polymer, the hydrosilane compound is subjected to an addition reaction called a hydrosilylation reaction using a platinum catalyst to convert the reactive silicon group into a polymer. The method of introduction is given. As the hydrosilane compound, the aforementioned compounds can be preferably used.

  Such a production method is described in, for example, each specification of Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-108928, Japanese Patent Publication No. 2512468, Japanese Patent Application Laid-Open No. 64-22904, and Japanese Patent Publication No. 2539445. ing.

  An isobutylene polymer having a reactive silicon group in the molecular chain is produced by adding vinylsilanes or allylsilanes having a reactive silicon group to a monomer mainly composed of isobutylene and copolymerizing them.

  Furthermore, in the production of an isobutylene polymer having a reactive silicon group at the molecular chain terminal, after copolymerizing vinylsilanes or allylsilanes having a reactive silicon group in addition to the main component isobutylene monomer. By introducing a reactive silicon group at the terminal, an isobutylene polymer having a reactive silicon group at the terminal and inside the molecular chain is produced.

  In the hydrogenated polybutadiene polymer, for example, first, the hydroxyl group of the terminal hydroxy hydrogenated polybutadiene polymer is changed to an oxymetal group such as -ONa or -OK, and then the general formulas (3) and (4) are used. A hydrogenated polybutadiene polymer having a terminal olefin group (hereinafter also referred to as a terminal olefin hydrogenated polybutadiene polymer) is produced by reacting the organic halogen compound shown.

  Examples of the method for converting the terminal hydroxyl group of the terminal hydroxy-hydrogenated polybutadiene polymer into an oxymetal group include alkali metals such as Na and K; metal hydrides such as NaH; metal alkoxides such as NaOCH 3; and alkali hydroxides such as NaOH and KOH. The method of reacting with a thing etc. is mention | raise | lifted.

  In the above method, a terminal olefin hydrogenated polybutadiene polymer having almost the same molecular weight as that of the terminal hydroxy hydrogenated polybutadiene polymer used as a starting material is obtained. Before reacting the organic halogen compound of formula (3) or general formula (4), two or more halogens are contained in one molecule such as methylene chloride, bis (chloromethyl) benzene, bis (chloromethyl) ether, etc. When reacted with a polyvalent organic halogen compound, the molecular weight can be increased, and then reacted with an organic halogen compound represented by general formula (3) or general formula (4) to provide a higher molecular weight and an olefin at the end. A hydrogenated polybutadiene polymer having a group can be obtained.

  Introducing a reactive silicon group into the terminal olefin-hydrogenated polybutadiene polymer is performed by adding a hydrosilane compound using a platinum catalyst in the same manner as in the case of an isobutylene polymer having a reactive silicon group at the molecular chain end. Manufactured.

  When the saturated hydrocarbon polymer having a reactive silicon group as described above does not substantially contain an unsaturated bond that is not an aromatic ring in the molecule, an organic polymer or an oxyalkylene type having an unsaturated bond The weather resistance is better than a film formed from a conventional rubber polymer such as a polymer. In addition, since the polymer is a hydrocarbon-based polymer, it has good moisture barrier properties and water resistance, has excellent adhesion performance to various inorganic substrates such as glass and aluminum, and has a coating with high moisture barrier properties. Form.

  In the case where the main chain skeleton of the component (A) is an oxyalkylene polymer, the curable composition of the present invention and the cured product containing the same have excellent low temperature characteristics, flexibility, and excellent compatibility with other components. Etc. can be given.

  Further, when the main chain skeleton of the component (A) is a vinyl polymer, in particular, a (meth) acrylic system, the weather resistance excellent in the curable composition of the present invention and the cured product containing the same by adjusting the monomer species, Flexibility, excellent compatibility with other components, and the like can be imparted.

  The main chain skeleton of the component (A) may be single, and by combining two or more kinds, it is possible to obtain a curable composition having the above characteristics and a cured product containing the same. For example, when an oxyalkylene polymer and a (meth) acrylic polymer are combined, in addition to the excellent low temperature characteristics, flexibility, and excellent compatibility with other components of the oxyalkylene polymer, Excellent weather resistance of the (meth) acrylic polymer can be imparted.

The organic polymer (B) containing an average of 0.5 to 1.5 reactive silicon groups represented by the following general formula (2) in the present invention is in the organic polymer (A) component. This forms a crosslinked structure with the reactive silyl group. Further, by using the low molecular weight organic polymer (B), it can function as a reactive plasticizer or diluent, and can be reduced in viscosity.
-SiX ₃ (2)
(Wherein X is the same as the general formula (1))
The reactive silicon group of the reactive silicon group-containing organic polymer (B) is not particularly limited, and the reactive silicon group represented by the general formula (2) can be used without any problem. Specific examples include a trichlorosilyl group, a trialkoxysilyl group, and the like. Among these, an alkoxysilyl group is preferable because it has a high hydrolysis activity and has a mild hydrolyzability and is easy to handle. Specifically, it is preferably at least one selected from the group consisting of a trimethoxysilyl group, a triethoxysilyl group, and a triisopropenyloxysilyl group.

  The main chain skeleton of the organic polymer (B) having a reactive silicon group of the present invention is not particularly limited. For example, the main chain skeleton is a generally known oxyalkylene polymer, vinyl polymer, saturated carbonization. Organic polymers such as hydrogen polymers, polyester polymers, and polyurethanes can be used. Specifically, those exemplified for the above-mentioned organic polymer (A) can be preferably used.

Other low molecular weight compounds having an unsaturated group such as 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and others having 20 or more carbon atoms A saturated hydrocarbon compound (B) in which a reactive silicon group is introduced into an α-olefin compound, 1,5-hexadiene, 1,9-decadiene, 1,17-octadecadiene or the like can also be suitably used. When such a low molecular weight compound , particularly a saturated hydrocarbon compound (B) in which a reactive silicon group is introduced into a saturated hydrocarbon compound having 20 or less carbon atoms, the compatibility is good and a small amount It is possible to reduce the viscosity of the organic polymer (A) by use.

  Among them, one having an unsaturated group at one end such as 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, etc. It is preferable from the point of property and reactivity.

  Among the organic polymers having the above main chain skeleton, an oxyalkylene polymer is preferable because it is liquid at room temperature, has good low-temperature characteristics, has a low viscosity, and has good compatibility.

  As a method for introducing a reactive silicon group into the organic polymer (B) of the present invention, the same methods a), b) and c) as the method for introducing the organic polymer (A) can be applied. 0.5 mol or more of the reactive silicon group-containing compound having a reactive silicon group represented by the formula (1) and a functional group capable of reacting with the reactive group in the organic polymer with respect to 1 mol of the organic polymer. It can introduce | transduce by making it react 1.5 mol or less.

  Specifically, in the method (a), the organic polymer having allyl groups at both ends is reacted with a hydrosilane compound in an amount of 0.5 to 1.5 equivalents. A method of reacting an isocyanate silane compound with 0.5 to 1.5 equivalents with respect to the polymer may be mentioned.

  In the method (a), among the trialkoxysilanes, trialkoxysilanes having a C 1 alkoxy group (methoxy group) such as trimethoxysilane may cause the disproportionation reaction to proceed rapidly, As the leveling reaction proceeds, a rather dangerous compound such as dimethoxysilane is formed. From the viewpoint of safety in handling, trialkoxysilane having an alkoxy group having 2 or more carbon atoms is preferably used. Triethoxysilane is the most preferable from the viewpoints of availability, safety in handling, restoration properties of the resulting curable composition, durability, and creep resistance.

  However, such disproportionation reaction does not proceed with γ-mercaptopropyltrimethoxysilane or γ-isocyanatopropyltrimethoxysilane. Therefore, when a trialkoxysilyl group having a methoxy group such as a trimethoxysilyl group is used as the silicon-containing group, it is preferable to use the synthesis method b) or c).

  In the method (b), for example, after introducing triethoxysilane into an organic polymer, the trimethoxysilyl group can be converted by transesterifying the ethoxy group with methanol and a transesterification catalyst.

  If the introduction rate of the reactive silicon group is less than 0.5 mol per molecule, the reactivity with the organic polymer (A) is not sufficient, and good cured product properties cannot be obtained. Moreover, when more than 1.5 mol, the cured | curing material physical property at the time of mixing with an organic polymer (A) will become weak.

  When a reactive silicon group is introduced by the above method, an average of a plurality of reactive silicon groups introduced in one molecule, one introduced, one not introduced at all are generated simultaneously. To do. In the case where a plurality of reactive silicon groups are introduced on average in one molecule, the effect of improving the brittleness of the cured product of the present invention is small, and the mechanical properties of the cured product of the organic polymer (A) alone are small. Maintain or improve the modulus. Those introduced by one or those not introduced at all can impart flexibility to the cured product of the present invention and lower the modulus in the mechanical properties of the cured product of the organic polymer (A) alone. However, those in which no reactive silicon group has been introduced are not reactive, and flow out from the cured product using the curable composition of the present invention over time, bleeding in the use of reeling materials and adhesives, May cause problems such as coating contamination.

  Therefore, it is preferable that the organic polymer (B) has substantially one reactive silicon group represented by the general formula (2), that is, one reactive group of the polymer and the general formula (2) It is preferably obtained by selectively reacting one represented reactive silicon group-containing compound. As these methods, for example, in the above-mentioned method of introducing reactive silyl groups a), b) and c), the precursor polymer has only one functional group capable of reacting with a reactive silicon group-containing compound. Can be used to selectively obtain an organic polymer (B) having one reactive silicon group.

  Polymerization of the precursor polymer having one reactive group is, for example, monovalent primary, secondary, tertiary alcohol such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, etc. Or an oxyalkylene polymer using a monovalent unsaturated group-containing alcohol such as allyl alcohol, methallyl alcohol, propenyl alcohol or the like as an initiator, and a polymer having a hydroxyl group only at one end, A group obtained by converting a hydroxyl group to an unsaturated group as described above, or a monovalent organic halide or the like as an initiator, and a terminal obtained by atom transfer radical polymerization using a transition metal complex as a catalyst is converted into a hydroxyl group or an unsaturated group. What was converted is mentioned.

  In addition, even in polymers having unsaturated groups and hydroxyl groups at different terminals, for example, if it is an isocyanate silane, it is introduced into the hydroxyl group. It is possible to introduce reactive silicon groups.

  In addition, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and other α-olefin compounds having 20 or more carbon atoms are not present at one end. It can be suitably used as a polymer having a saturated group.

  Although there is no restriction | limiting in the molecular weight of (B) component, Preferably it is 8,000 or less, More preferably, 5,000 or less is preferable from points, such as workability | operativity after mixing with (A) component. When the molecular weight is 8,000 or more, the effect of reducing the viscosity of the organic polymer (A) is reduced.

  Although there is no limitation in particular about the usage-amount of the reactive silicon group containing organic polymer (B) of this invention, it is 0.1 weight part-200 with respect to 100 weight part of organic polymer (A) which has a reactive silicon group. It is preferably used in the range of parts by weight, more preferably in the range of 1 to 100 parts by weight. When the amount used is less than 0.1 parts by weight, the effects of the present invention may not be obtained. When the amount used is more than 200 parts by weight, the composition may have more hydrolyzable groups and may impair curability. is there.

  Since the organic polymer (B) is reactive with the organic polymer and can form a crosslinked structure, when a low molecular weight organic polymer (B) is used, many conventional plasticizers are used. Compared to the case, the effect of improving the plasticizer contamination of the sealant can be expected. In addition, it can be expected to reduce the tack of the surface of the cured product and prevent dust and dust from being attached to the surface.

  In the present invention, the vinyl polymer (C) having a reactive silicon group capable of reacting with the reactive silicon group of the organic polymer (A) and the organic polymer (B) can be used in combination. It becomes possible to further provide weather resistance, tackiness, and adhesiveness.

  As the reactive silicon group of the vinyl polymer (C), those represented by the above general formula (1) and general formula (2) can be preferably used. Specifically, the above organic polymer (A) and organic polymer can be used. What was mentioned by the polymer (B) can be used similarly.

  As the polymerization method of the main chain skeleton of the vinyl polymer (C), the above-described polymerization method of the vinyl polymer, for example, controlled radical polymerization, free radical polymerization, and the like can be similarly applied.

  A vinyl polymer (C) having a number average molecular weight of 500 to 100,000 is preferred from the viewpoint of ease of handling. Furthermore, the thing of 1,000-30,000 and the thing of 2,000-20,000 are more preferable from the extended physical property of hardened | cured material being improved, and a weather resistance and workability | operativity being favorable. The number average molecular weight of the vinyl polymer (C) is measured as a polystyrene equivalent molecular weight by GPC.

  The number of reactive silicon groups per molecule of the vinyl polymer (C) is preferably 1.1-5.

  Although there is no limitation in particular about the usage-amount of a vinyl type polymer (C), it is 0.1 to 200 weight part with respect to 100 weight part of organic polymer (A) + (B) which has a reactive silicon group. It is preferable to use in a range, and a range of 1 to 100 parts by weight is more preferable. When the amount used is less than 0.1 parts by weight, the effects of weather resistance, tackiness and adhesiveness may not be obtained. When it is more than 200 parts by weight, workability, dust adhesion, etc. may be impaired. .

  The composition of the present invention can contain various known curing catalysts, fillers, and various additives. Further, if necessary, a plasticizer or the like can be contained.

  A conventionally well-known thing can be widely used for a curing catalyst. Specific examples thereof include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetraacetylacetonate; dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctate, dibutyltin diethylhexanolate, dibutyltin dimethyl maleate, dibutyltin Diethyl maleate, dibutyltin dibutyl maleate, dibutyltin dioctyl maleate, dibutyltin ditridecyl maleate, dibutyltin dibenzyl maleate, dibutyltin diacetate, dioctyltin diethyl maleate, dioctyltin dioctyl maleate, dibutyltin dimethoxide, dibutyltin dinonyl Phenoxide, dibutenyl tin oxide, dibutyltin diacetyl Tetravalent tin compounds such as setonate, dibutyltin diethyl acetoacetonate, reaction product of dibutyltin oxide and phthalate; divalent tin compounds such as tin octylate, tin naphthenate, tin stearate, tin versatate; aluminum Organoaluminum compounds such as trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium compounds such as zirconium tetraacetylacetonate; lead octylate; butylamine, octylamine, dibutylamine, monoethanol Amine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine , Diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1, Amine compounds such as 8-diazabicyclo (5,4,0) undecene-7 (DBU), or salts of these amine compounds with carboxylic acids, etc .; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids Reaction product of excess polyamine and epoxy compound; silane coupling agent having amino group such as γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane; silanol condensation catalyst such as And even other acidic touches , Known silanol condensation catalysts such as basic catalyst, and the like. These catalysts may be used alone or in combination of two or more.

  These curing catalysts are used in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the total amount of the organic polymer (A) having a reactive silicon group and the reactive silicon group-containing organic polymer (B). The degree is preferred. If the amount of the curing catalyst used is too small, the curing rate is slow, and the curing reaction is not sufficiently progressed. On the other hand, if the amount of the curing catalyst used is too large, local heat generation and foaming occur during curing, and it becomes difficult to obtain a good cured product, which is not preferable.

In the curable composition of the present invention, shown in order to enhance the activity of the condensation catalyst, the general formula _{^{R 1 4-a Si (OR}} 1) a ( wherein, R ^1, a is as defined above.) A silicon compound may be added. The silicon compound is not limited, but is directly connected to the Si atom in the general formula such as phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, triphenylmethoxysilane and the like. It is preferable that at least one R ¹ is an aryl group having 6 to 20 carbon atoms because the effect of accelerating the curing reaction of the composition is great. In particular, diphenyldimethoxysilane and diphenyldiethoxysilane are particularly preferable because of low cost and easy availability. The compounding amount of the silicon compound is preferably about 0.01 to 20 parts by weight with respect to 100 parts by weight of the total amount of the organic polymer (A) having a reactive silicon group and the reactive silicon group-containing organic polymer (B). 0.1 to 10 parts by weight is more preferable. When the compounding amount of the silicon compound is below this range, the effect of accelerating the curing reaction may be reduced. On the other hand, when the compounding amount of the silicon compound exceeds this range, the hardness and tensile strength of the cured product may decrease.

  To the composition of the present invention, a silane coupling agent, a reaction product of the silane coupling agent, or a compound other than the silane coupling agent can be added as an adhesion promoter. Specific examples of the silane coupling agent include isocyanate group-containing silanes such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatopropylmethyldimethoxysilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- ( 2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ-ureido Amino group-containing silanes such as propyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane Epoxy group-containing silanes such as lan; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane, etc. Carboxysilanes; vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyltriethoxysilane; γ-chloropropyltrimethoxy Examples include halogen-containing silanes such as silane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate. In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, and the like, which are derivatives of these, can also be used as silane coupling agents. . The silane coupling agent used in the present invention is usually 0.1 to 100 parts by weight of the total amount of the organic polymer (A) having a reactive silicon group and the reactive silicon group-containing organic polymer (B). It is used in the range of 20 parts by weight. In particular, it is preferably used in the range of 0.5 to 10 parts by weight.

  The effects of the silane coupling agent added to the curable composition of the present invention are various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, mortar, vinyl chloride, acrylic, polyester, When used for organic base materials such as polyethylene, polypropylene, polycarbonate, etc., it exhibits a remarkable adhesive improvement effect under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving adhesion to various adherends is particularly remarkable. Specific examples other than the silane coupling agent are not particularly limited, and examples thereof include epoxy resins, phenol resins, sulfur, alkyl titanates, and aromatic polyisocyanates. The adhesiveness-imparting agent may be used alone or in combination of two or more. By adding these adhesion-imparting agents, the adhesion to the adherend can be improved.

  The composition of the present invention can contain various fillers. Fillers include reinforcing silica such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate Diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, shirasu balloon, glass microballoon, phenolic resin and vinylidene chloride Examples thereof include fillers such as resin organic microballoons and resin powders such as PVC powder and PMMA powder; and fibrous fillers such as asbestos, glass fibers and filaments. When the filler is used, the amount used is 1 to 300 parts by weight with respect to 100 parts by weight of the total amount of the organic polymer (A) having a reactive silicon group and the reactive silicon group-containing organic polymer (B), Preferably it is 10-200 weight part.

  When you want to obtain a hardened product with high strength by using these fillers, mainly fume silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid and carbon black, surface treatment fine A filler selected from calcium carbonate, calcined clay, clay, activated zinc white and the like is preferable, and a total of 100 parts by weight of an organic polymer (A) having a reactive silicon group and an organic polymer (B) containing a reactive silicon group On the other hand, if it is used in the range of 1 to 200 parts by weight, preferable results can be obtained. In addition, when it is desired to obtain a cured product having a low strength and a large elongation at break, a filler mainly selected from titanium oxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon, etc. Is preferably used in an amount of 5 to 200 parts by weight based on 100 parts by weight of the total of the organic polymer (A) having a reactive silicon group and the reactive silicon group-containing organic polymer (B). In general, calcium carbonate has a greater effect of improving the breaking strength, breaking elongation, and adhesiveness of the cured product as the value of the specific surface area increases. Of course, these fillers may be used alone or in combination of two or more. Fatty acid surface-treated colloidal calcium carbonate can be used in combination with calcium carbonate having a particle size of 1 μm or more, such as heavy calcium carbonate that has not been surface-treated.

  In order to improve the workability (such as sharpness) of the composition and to make the surface of the cured product matt, it is preferable to add an organic balloon or an inorganic balloon. These fillers can be surface-treated, and may be used alone or in combination of two or more. In order to improve workability (such as sharpness), the balloon particle size is preferably 0.1 mm or less. In order to make the surface of the cured product matt, 5-300 μm is preferable.

  The composition of the present invention is suitably used for joints on the outer wall of a house such as a sizing board, particularly a ceramic sizing board, but it is desirable that the design of the outer wall and the design of the sealing material are harmonized. In particular, high-quality outer walls are used as outer walls due to the mixture of spatter coating, colored aggregates, and the like. When the composition of the present invention contains a scaly or granular substance having a diameter of 0.1 mm or more, preferably about 0.1 to 5.0 mm, the cured product is in harmony with such a high-quality outer wall. However, since the weather resistance is excellent, the appearance of the cured product is an excellent composition that lasts for a long time. When a granular material is used, the surface becomes sandy or sandstone-like rough, and when a scaly material is used, the surface becomes uneven.

  When the composition of this invention contains sealing material hardened | cured material particle | grains, hardened | cured material can form an unevenness | corrugation on the surface and can improve the designability. The preferable diameter, blending amount, material and the like of the cured sealant particles are as follows as described in JP-A-2001-115142. The diameter is preferably about 0.1 mm to 1 mm, more preferably about 0.2 to 0.5 mm. The blending amount is preferably 5 to 100% by weight, more preferably 20 to 50% by weight in the curable composition. Examples of the material include urethane resin, silicone, modified silicone, polysulfide rubber and the like, and are not limited as long as they are used for the sealing material, but a modified silicone-based sealing material is preferable.

  Although the plasticizer component can be added to the composition of the present invention as necessary, it is not always necessary. Although it does not specifically limit as a plasticizer, According to the objective, phthalic acid esters, such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate, etc .; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, Non-aromatic dibasic acid esters such as isodecyl succinate; Aliphatic esters such as butyl oleate and methyl acetylricinoleate; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Chlorinated paraffins; Hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; Process oils; Epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate; Polyester plasticizers; Acrylic acid Beauty treatment A plasticizer having an acrylic component such as a polymer of an acrylic monomer such as acrylamide or acrylamide; a polyether polymer such as polyoxypropylene glycol, polyoxypropylene triol, or a terminal alkyl ether derivative thereof alone or in combination They can be used in combination.

  Among these, acrylic monomer polymers and polyether polymers are preferred. The molecular weight of the acrylic monomer polymer and the polyether polymer is 3000 or more, preferably 5000 or more, and more preferably 10,000 or more. These plasticizers can also be blended at the time of polymer production.

  You may add the physical property modifier which adjusts the tensile characteristic of the hardened | cured material produced | generated as needed to the curable composition of this invention. Although it does not specifically limit as a physical property regulator, For example, alkyl alkoxysilanes, such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy Silanes, alkyl isopropenoxy silanes such as γ-glycidoxypropylmethyldiisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxy Silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxy Alkoxysilanes having a functional group such as a silane; silicone varnishes; polysiloxanes and the like. By using the physical property modifier, it is possible to increase the hardness when the composition of the present invention is cured, or to decrease the hardness and break elongation. The said physical property modifier may be used independently and may be used together 2 or more types.

  The physical property modifier is 0.1 to 20 parts by weight, preferably 0. 0 parts by weight based on 100 parts by weight of the total amount of the organic polymer (A) having a reactive silicon group and the reactive silicon group-containing organic polymer (B). It is used in the range of 5 to 10 parts by weight.

  A thixotropic agent (anti-sagging agent) may be added to the curable composition of the present invention as necessary to prevent sagging and improve workability. The sagging preventing agent is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more. The thixotropic agent is used in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the organic polymer (A) having a reactive silicon group and the reactive silicon group-containing organic polymer (B). Is done.

  In the composition of the present invention, a compound containing an epoxy group in one molecule can be used. When a compound having an epoxy group is used, the restorability of the cured product can be improved. Examples of the compound having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, di- (2-ethylhexyl) 4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate And epoxybutyl stearate. Of these, E-PS is particularly preferred. For the purpose of enhancing the restorability of the cured product, it is preferable to use a compound having one epoxy group in the molecule. The epoxy compound is used in the range of 0.5 to 50 parts by weight with respect to 100 parts by weight of the total amount of the organic polymer (A) having a reactive silicon group and the reactive silicon group-containing organic polymer (B). Good.

A photocurable material can be used in the composition of the present invention. When a photocurable material is used, a film of the photocurable material is formed on the surface of the cured product, and the stickiness of the cured product and the weather resistance of the cured product can be improved. A photocurable substance is a substance in which the molecular structure undergoes a chemical change in a very short time due to the action of light, resulting in a change in physical properties such as curing. Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as this type of compound, and any commercially available compound can be adopted. Representative examples include unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, and the like. Unsaturated acrylic compounds include monomers, oligomers or mixtures thereof having one or several acrylic or methacrylic unsaturated groups, including propylene (or butylene, ethylene) glycol di (meth) acrylate, neopentyl Examples thereof include monomers such as glycol di (meth) dimethacrylate and oligoesters having a molecular weight of 10,000 or less. Specifically, for example, special acrylate (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; (Trifunctional) Aronix M -305, Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, and (Multifunctional) Aronix M-400, etc., but especially contain acrylic functional groups The compound which contains 3 or more same functional groups on average in 1 molecule is preferable. (All Aronix is a product of Toa Gosei Chemical Co., Ltd.)
Examples of the polyvinyl cinnamates include photosensitive resins having a cinnamoyl group as a photosensitive group, and those obtained by esterifying polyvinyl alcohol with cinnamic acid, as well as many polyvinyl cinnamate derivatives. The azide resin is known as a photosensitive resin having an azide group as a photosensitive group. Usually, in addition to a rubber photosensitive solution in which a diazide compound is added as a photosensitive agent, “photosensitive resin” (March 17, 1972). There are detailed examples in Publishing, Publishing Society of Printing Press, page 93-, page 106-, page 117-), these may be used alone or in combination, and a sensitizer may be added as necessary. Can do. Note that the addition of a sensitizer such as ketones or nitro compounds or an accelerator such as amines may enhance the effect.

  The amount of the photocurable substance used is 0.01 to 20 parts by weight with respect to 100 parts by weight of the total amount of the organic polymer (A) having a reactive silicon group and the reactive silicon group-containing organic polymer (B). The range of 0.5 to 10 parts by weight is more preferable. If it is 0.01 parts by weight or less, the effect of increasing the weather resistance is small, and if it is 20 parts by weight or more, the cured product becomes too hard and cracks occur, which is not preferable.

  An oxygen curable substance can be used in the composition of the present invention. Examples of the oxygen curable substance include unsaturated compounds that can react with oxygen in the air. The oxygen curable substance reacts with oxygen in the air to form a cured film near the surface of the cured product. And prevents dust from adhering. Specific examples of the oxygen curable substance include drying oils typified by drill oil and linseed oil, various alkyd resins obtained by modifying the compounds; acrylic polymers and epoxy resins modified with drying oils , Silicone resin; 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymer obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc. Liquid polymers, liquid copolymers such as NBR and SBR obtained by copolymerizing monomers such as acrylonitrile and styrene copolymerizable with these diene compounds so that the main component is a diene compound, Further, various modified products thereof (maleinized modified products, boiled oil modified products, etc.) and the like can be mentioned. These may be used alone or in combination of two or more. Of these, drill oil and liquid diene polymers are particularly preferable. Moreover, the effect may be enhanced if a catalyst for promoting the oxidative curing reaction or a metal dryer is used in combination. Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, zirconium octylate, and amine compounds. The amount of the oxygen curable substance used is 0.1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the organic polymer (A) having a reactive silicon group and the reactive silicon group-containing organic polymer (B). It is good to use in the range, and more preferably 1-10 parts by weight. If the amount used is less than 0.1 parts by weight, the improvement of the contamination is not sufficient, and if it exceeds 20 parts by weight, the tensile properties of the cured product tend to be impaired. As described in JP-A-3-160053, the oxygen curable substance is preferably used in combination with a photocurable substance.

  An antioxidant (antiaging agent) can be used in the composition of the present invention. If an antioxidant is used, the weather resistance of the cured product can be increased. Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred. Similarly, hindered amine light stabilizers can also be used. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731. The usage-amount of antioxidant is the range of 0.1-10 weight part with respect to 100 weight part of total amounts of the organic polymer (A) which has a reactive silicon group, and a reactive silicon group containing organic polymer (B). The amount is preferably 0.2 to 5 parts by weight.

  A light stabilizer can be used in the composition of the present invention. Use of a light stabilizer can prevent photooxidation degradation of the cured product. Examples of the light stabilizer include benzotriazole, hindered amine, and benzoate compounds, with hindered amines being particularly preferred. The amount of the light stabilizer used is in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the organic polymer (A) having a reactive silicon group and the reactive silicon group-containing organic polymer (B). The amount is preferably 0.2 to 5 parts by weight. Specific examples of the light stabilizer are also described in JP-A-9-194731.

  When a photocurable substance is used in combination with the composition of the present invention, particularly when an unsaturated acrylic compound is used, a tertiary amine-containing hindered amine is used as a hindered amine light stabilizer as described in JP-A-5-70531. The use of a light stabilizer is preferred for improving the storage stability of the composition.

  An ultraviolet absorber can be used in the composition of the present invention. When the ultraviolet absorber is used, the surface weather resistance of the cured product can be enhanced. Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferable. The amount of the ultraviolet absorber used is in the range of 0.1 to 10 parts by weight relative to 100 parts by weight of the total amount of the organic polymer (A) having a reactive silicon group and the reactive silicon group-containing organic polymer (B). The amount is preferably 0.2 to 5 parts by weight. It is preferable to use a phenolic or hindered phenolic antioxidant, a hindered amine light stabilizer and a benzotriazole ultraviolet absorber in combination.

  An epoxy resin can be added to the composition of the present invention and used as an elastic adhesive or the like. Epoxy resins include epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame retardant type epoxy resin such as glycidyl ether of tetrabromobisphenol A, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A glycidyl ether type epoxy resin of propylene oxide adduct, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin, various alicyclic epoxy resins, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether Examples include glycidyl ethers of polyhydric alcohols such as glycerin, epoxidized products of unsaturated polymers such as hydantoin type epoxy resins, petroleum resins, etc., but are not limited to these and are generally used. Epoxy resins can be used. Those containing at least two epoxy groups in the molecule are preferred because they are highly reactive during curing and the cured product easily forms a three-dimensional network. More preferred are bisphenol A type epoxy resins or novolac type epoxy resins. The use ratio of the total amount of these epoxy resins, the organic polymer (A) having a reactive silicon group and the reactive silicon group-containing organic polymer (B) is ((A) + (B)) / Epoxy resin = 100/1 to 1/100. When the ratio of ((A) + (B)) / epoxy resin is less than 1/100, the effect of improving the impact strength and toughness of the ((A) + (B)) component of the cured epoxy resin can be obtained. When the ratio of ((A) + (B)) / epoxy resin exceeds 100/1, the strength improvement by the epoxy resin of the ((A) + (B)) component cured product becomes insufficient. The preferred use ratio varies depending on the use of the curable resin composition and cannot be determined unconditionally. For example, when improving the impact resistance, flexibility, toughness, peel strength, etc. of the cured epoxy resin The component (A) component + (B) component is used in an amount of 1 to 100 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the epoxy resin. On the other hand, when improving the strength of the cured product of component (A) + component (B), 1 to 200 parts by weight of epoxy resin, more preferably 100 parts by weight of component (A) + component (B), more preferably It is good to use 5 to 100 parts by weight.

  When an epoxy resin is used, a curing agent that cures the epoxy resin can be used in combination. There is no restriction | limiting in particular as an epoxy resin hardening | curing agent which can be used, The epoxy resin hardening | curing agent generally used can be used. Specifically, for example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperidine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, amine-terminated poly Primary and secondary amines such as ether; tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol and tripropylamine, and salts of these tertiary amines; polyamide resins; imidazole Dicyandiamides; boron trifluoride complex compounds, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecynyl succinic anhydride, pyromellitic anhydride, chlorenic anhydride, etc .; alcohols ; Fe Lumpur acids; carboxylic acids; but the compound of diketone complex compounds of aluminum or zirconium, or the like can be exemplified, but the invention is not limited thereto. Further, the curing agents may be used alone or in combination of two or more.

  When the epoxy resin curing agent is used, the amount used is in the range of 0.1 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin.

  Ketimine can be used as a curing agent for the epoxy resin. Ketimine is stably present in the absence of moisture, and is decomposed into primary amines and ketones by moisture, and the resulting primary amine becomes a room temperature curable curing agent for the epoxy resin. When ketimine is used, a one-component composition can be obtained. Such a ketimine can be obtained by a condensation reaction between an amine compound and a carbonyl compound.

  For the synthesis of ketimine, known amine compounds and carbonyl compounds may be used. For example, as amine compounds, ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane, 2,3-diaminobutane, Diamines such as pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, p-phenylenediamine, p, p'-biphenylenediamine; 1,2,3-triaminopropane, triaminobenzene, tris (2-amino Polyvalent amines such as ethyl) amine and tetra (aminomethyl) methane; polyalkylene polyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; polyoxyalkylene-based polyamines; γ-aminopropyltri Tokishishiran, N-(beta-aminoethyl)-.gamma.-aminopropyltrimethoxysilane, aminosilanes such as N-(beta-aminoethyl)-.gamma.-aminopropyl methyl dimethoxy silane; and it may be used. Examples of the carbonyl compound include aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, diethylacetaldehyde, glyoxal and benzaldehyde; cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone and trimethylcyclohexanone; acetone , Aliphatic ketones such as methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone; acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate , Β-dicarbonyl compounds such as diethyl malonate, methyl ethyl malonate, dibenzoylmethane And the like can be used.

  When an imino group is present in the ketimine, the imino group may be reacted with styrene oxide; glycidyl ether such as butyl glycidyl ether or allyl glycidyl ether; glycidyl ester or the like. These ketimines may be used alone or in combination of two or more, and are used in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin, and the amount used is the kind of epoxy resin and ketimine It depends on.

  Various additives may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include, for example, flame retardants, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, Examples include solvents and fungicides. These various additives may be used alone or in combination of two or more. Specific examples other than the specific examples of the additives listed in the present specification include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-62-2904, It is described in Japanese Laid-Open Patent Publication No. 2001-72854.

  The curable composition of the present invention can also be prepared as a one-component type in which all the blended components are pre-blended and sealed and cured by moisture in the air after construction. It is also possible to prepare a two-component type in which components such as a plasticizer and water are blended and the compounding material and the polymer composition are mixed before use.

  When the curable composition is of a one-component type, all the ingredients are pre-blended, so the water-containing ingredients are dehydrated and dried before use, or dehydrated during decompression or the like during compounding and kneading. Is preferred. When the curable composition is a two-component type, it is not necessary to add a curing catalyst to the main component containing a polymer having a reactive silicon group, so gelation is possible even if some moisture is contained in the compounding agent. However, when long-term storage stability is required, dehydration and drying are preferable. As the dehydration and drying method, a heat drying method is preferable in the case of a solid substance such as a powder, and a dehydration method using a reduced pressure dehydration method or a synthetic zeolite, activated alumina, silica gel or the like is preferable in the case of a liquid material. Alternatively, a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration. In addition to the dehydration drying method, lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ -Storage stability is further improved by adding an alkoxysilane compound such as glycidoxypropyltrimethoxysilane.

  The amount of the silicon compound capable of reacting with water, such as dehydrating agent, especially vinyltrimethoxysilane, is the total amount of organic polymer (A) having a reactive silicon group + reactive silicon group-containing organic polymer (B) of 100 weight. The range of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, is preferred with respect to parts.

  The curable composition of the present invention is particularly useful as an elastic sealant or adhesive, and can be used as a sealant or adhesive for buildings, ships, automobiles, roads and the like. In particular, it is useful for architectural sealants because it requires non-contamination of paint and non-contamination around joints when coating is applied to the surface. In particular, it is particularly useful as a sealant for sizing board joints and a sealant for stone joints. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, and resin moldings alone or with the help of a primer, it can be used as various types of adhesive compositions. It can be used as a raw material for contact adhesives as well as ordinary adhesives. Furthermore, it is also useful as a food packaging material, cast rubber material, molding material, and paint.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In the case of a hydroxyl group-containing oxyalkylene polymer, the number average molecular weight is determined as follows. Assuming that the terminal structure is a hydroxyl group and an unsaturated group, the amount of hydroxyl group is determined by a method based on JIS K1557, the amount of unsaturated group is determined by a method based on JIS K0070, and the molecular weight determined in consideration of the number of terminal ends of the initiator is calculated. It is defined as the number average molecular weight. GPC (gel permeation chromatography) peak top molecular weight (hereinafter referred to as GPCMp) and molecular weight distribution (Mw / Mn) were determined as polystyrene-equivalent values measured with a GPC analyzer using tetrahydrofuran as a solvent.

  The polymer viscosity was measured at 23 ° C. using a B-type viscometer, and the blend viscosity was measured at 23 ° C. using a BS-type viscometer.

When the hydrosilane compound is introduced into the polyoxypropylene having an allyl group at the end, the reaction proceeds by ¹ H-NMR with the peak of the terminal allyl group (4.97 ppm: = CH ₂ , 5.79 ppm: -CH = C). It was confirmed by decrease, disappearance, and decrease in the hydrosilyl group (Si—H) peak (around 4.6 ppm) of the dropped hydrosilane compound.

(Synthesis Example 1) Synthesis of Reactive Silicon Group-Containing Polyoxypropylene (A1) In a pressure-resistant glass reaction vessel equipped with a stirrer, the main chain skeleton was obtained using a double metal cyanide complex catalyst, and the terminal was allyl. A linear polypropylene oxide having a number average molecular weight of 10,000 (500 g) and 10 g of hexane were added and azeotropic dehydration was performed at 90 ° C. Hexane was distilled off under reduced pressure and then purged with nitrogen. To this, 20 μl of chloroplatinic acid catalyst (5% by weight isopropanol solution in terms of platinum) was added, and 12.0 g of DMS (dimethoxymethylsilane) was slowly added while stirring. And dripped. The mixed solution was reacted at 90 ° C. for 2 hours, and then unreacted DMS was distilled off under reduced pressure to obtain a polymer (A1) having an average of 1.6 dimethoxysilyl groups per molecule. The viscosity (23 ° C .: B-type viscometer) was 6.4 Pa · s.

(Synthesis Example 2) Synthesis of low functionalized reactive silicon group-containing polyoxypropylene (B1) In an autoclave, 0.16 g of zinc hexacyanocobaltate glyme complex as an epoxide polymerization catalyst and an alkoxy group terminal in one molecule as a polymerization initiator Polymerization reaction was carried out by charging 420 g of polyoxypropylene having a hydroxyl group (manufactured by Sanyo Chemical Co., Ltd .: Newpol LB285) and 50 g of propylene oxide for catalyst activation and heating to 100 ° C. After the induction period, the reaction component temperature increased rapidly and then decreased. After confirming the drop in the reaction component temperature, an additional 524 g of propylene oxide was added dropwise over about 3 hours to keep the internal temperature at 100-110 ° C. After completion of the dropwise addition, heating was continued for an additional hour, followed by removal of a trace amount of unreacted monomer by vacuum devolatilization. As a result, a polyoxypropylene polymer having an alkoxy group terminal and a hydroxyl group in one molecule was obtained. The number average molecular weight of the obtained polymer was 4300 by GPC measurement (polystyrene conversion).

  Subsequently, 7.8 parts by weight of sodium methoxide (30% methanol solution) was added to 100 parts by weight of the polyoxypropylene polymer obtained above, and methanol was removed under reduced pressure at 130 ° C. for 2 hours. Subsequently, 4.1 parts by weight of allyl chloride was added and reacted at the same temperature for 2 hours. Thereafter, unreacted allyl chloride was removed under reduced pressure.

  The obtained polymer was cooled, diluted with hexane, and washed thoroughly with water to remove sodium chloride. Thereafter, hexane was removed to obtain a polyoxypropylene polymer having an alkoxy group terminal and an allyl group at the terminal.

  The unsaturated group equivalent determined by iodine titration of the obtained polymer was 0.415 mmol / g.

  2 g of hexane was added to 100 parts by weight of a polyoxypropylene polymer containing an alkoxy group terminal and an allyl group in one molecule obtained above, and azeotropic dehydration was performed at 90 ° C. Hexane was distilled off under reduced pressure, and the atmosphere was replaced with nitrogen. To this, 20 μl of chloroplatinic acid catalyst (5% by weight isopropanol solution in terms of platinum) was added, and 6.9 g of TES (triethoxysilane) was slowly added while stirring. And dripped. The mixed solution was reacted at 90 ° C. for 2 hours, and then unreacted TES was distilled off under reduced pressure to obtain a polymer (B1) having substantially one triethoxysilyl group per molecule. The viscosity (23 ° C .: B-type viscometer) was 0.6 Pa · s.

(Synthesis Example 3) Synthesis of low functionalized reactive silicon group-containing polyoxypropylene (B2) Synthesis was performed on 100 parts by weight of a polyoxypropylene polymer having an alkoxy group terminal and an allyl group at the terminal obtained in Synthesis Example 2. In the same manner as in Example 2, 11.7 g of a trimethoxysilyl group-containing silane compound represented by the following formula (8) is reacted to obtain a polymer (B2) having substantially one trimethoxysilyl group per molecule. Obtained. The viscosity (23 ° C .: B-type viscometer) was 0.6 Pa · s.

(Synthesis Example 4) Synthesis of low functionalized reactive silicon group-containing polyoxypropylene (B3) In a pressure-resistant glass reaction vessel equipped with a stirrer, 500 g of linear polypropylene oxide having a number average molecular weight of 3,000 whose terminal is an allyl group, 10 g of hexane was added and azeotropic dehydration was performed at 90 ° C. Hexane was distilled off under reduced pressure, and the atmosphere was replaced with nitrogen. To this, 20 μl of chloroplatinic acid catalyst (5% by weight isopropanol solution in terms of platinum) was added, and 29.4 g of TES (triethoxysilane) was slowly added with stirring. And dripped. The mixed solution was reacted at 90 ° C. for 2 hours, and then unreacted TES was distilled off under reduced pressure to obtain a polymer (B3) having an average of 1.0 triethoxysilyl groups per molecule. The viscosity (23 ° C .: B-type viscometer) was 0.5 Pa · s.

(Synthesis Example 5) Synthesis of Reactive Silicon Group-Containing Hydrocarbon Compound (B4) 100 g of 1-octadecene and 4 g of hexane were weighed into a 500 ml three-necked flask, and equipped with a stirrer equipped with a vacuum seal, a three-way cock and a ball plug, and heated to 80 ° C. After azeotropic dehydration under reduced pressure, 12.7 μl of 20 g of dioxane and platinum-1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex (3 wt% toluene solution in terms of platinum) were added dropwise. Stir well. Subsequently, 65.3 g of TES (triethoxysilane) was slowly added dropwise under a nitrogen atmosphere, and then stirred until the terminal unsaturated group disappeared. The progress of the reaction was determined by the decrease or disappearance of terminal unsaturated groups (near 4.9 ppm: = CH ₂ , near 5.8 ppm: -CH = C) by ¹ H-NMR, and the hydrosilyl group (Si-H) of hydrosilane dropped. This was confirmed by a decrease in (around 4.6 ppm).

When the ¹ H-NMR of the obtained reaction product was measured, the peak showing the unsaturated group and the peak showing hydrosilane described above were sufficiently disappeared with respect to the initial terminal unsaturated group-containing compound. A peak of a horizontal methylene group (around 0.6 ppm: —CH ₂ —Si) was confirmed, and octadecane (B4) having a triethoxysilyl group at the terminal was obtained. When the introduction rate of the triethoxysilyl group was calculated from the increase or decrease of the peak, the introduction rate was about 90%.

(Synthesis Example 6) Synthesis of low functionalized reactive silicon group-containing polyoxypropylene (P1) Synthesis was performed on 100 parts by weight of a polyoxypropylene polymer having an alkoxy group terminal and an allyl group at the terminal obtained in Synthesis Example 2. In the same manner as in Example 2, 4.4 g of DMS (methyldimethoxysilane) was reacted to obtain a polymer (P1) having substantially one methyldimethoxysilyl group per molecule. The viscosity (23 ° C .: B-type viscometer) was 0.6 Pa · s.

(Synthesis Example 7) Synthesis of Reactive Silicon Group-Containing Hydrocarbon Compound (P2) 100 g of 1-octadecene and 4 g of hexane were weighed into a 500 ml three-necked flask, and equipped with a stirrer with a vacuum seal, a three-way cock, and a ball plug. After depressurizing and azeotropic dehydration, 12.7 μl of dioxane (20 g) and platinum-1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex (3 wt% toluene solution in terms of platinum) were added dropwise. Stir well. Subsequently, 42.2 g of methyldimethoxysilane was slowly added dropwise under a nitrogen atmosphere, and then the mixture was stirred until the terminal unsaturated group disappeared. The progress of the reaction is determined by ¹ H-NMR to decrease or disappear the terminal unsaturated group (near 4.9 ppm: = CH ₂ , near 5.8 ppm: —CH═C), and the hydrosilyl group (Si—H) of the dropped hydrosilane. This was confirmed by a decrease in (around 4.6 ppm).

When the ¹ H-NMR of the obtained reaction product was measured, the peak showing the unsaturated group and the peak showing hydrosilane described above were sufficiently disappeared with respect to the initial terminal unsaturated group-containing compound. A peak of the horizontal methylene group (around 0.6 ppm: —CH ₂ —Si) was confirmed, and octadecane (B3) having a methyldimethoxysilyl group at the terminal was obtained. When the introduction rate of the methyldimethoxysilyl group was calculated from the increase or decrease of the peak, the introduction rate was about 90%.

Measurement of viscosity and curability (gel fraction) of mixed composition
(Example 1)
As shown in Table 1, the low functionalized reactive silicon group-containing polyoxypropylene obtained in Synthesis Example 2 with respect to 70 parts by weight of the reactive silicon group-containing polyoxypropylene polymer (A1) obtained in Synthesis Example 1 (B1) 30 parts by weight were mixed. The viscosity of this mixture was 3.2 Pa · s. To this, 0.5 part by weight of a reactive silicon-based curing agent (U-220: manufactured by Nitto Kasei Co., Ltd.) was mixed and sufficiently stirred.

  This mixture was poured onto a polyethylene sheet into a 3 mm thick mold to produce a 3 mm thick sheet-like cured product. This sheet was cured at 23 ° C. for 4 days. The obtained cured product of about 1 cm square test piece was weighed on a 200 mesh wire net and wrapped so that insoluble matter would not flow out. These were immersed in a sufficient amount of hexane for 15 hours to extract the eluate, and then dried at 80 ° C. for 2 hours. The ratio with respect to the initial weight of the insoluble part at that time was made into the gel fraction (%) (Table 1).

(Examples 2 to 4 and Comparative Examples 1 to 4)
Each component was mixed in the ratio shown in Table 1 in the same manner as in Example 1, and the viscosity of the mixture and the gel fraction of the cured product were measured in the same manner as in Example 1 (Table 1).

  From the results shown in Table 1, when a component having a reactive silicon group is mixed as the component (B), it can be expected that the cured product has a high gel fraction and little unreacted component flows out. Those having 1 to 4 trialkoxy groups exhibit higher gel fractions than those having the methyldimethoxy group of Comparative Example 1. Moreover, since the low molecular weight component is used with respect to (A) component, favorable viscosity reduction is obtained.

Various physical properties of the compound (Example 5)
With respect to 155 parts by weight of the mixed polymer of A1 component / B1 component = 70/30 at a ratio shown in Table 2, 120 parts by weight of calcium carbonate (product name: CCR, manufactured by Shiroishi Kogyo Co., Ltd.), titanium oxide (Ishihara Sangyo ( Co., Ltd., trade name: R-820) 20 parts by weight, thixotropic agent (Enomoto Kasei Co., Ltd., trade name: D-6500) 2 parts by weight, benzotriazole UV absorber (Ciba Specialty Chemicals) Co., Ltd., trade name: Tinuvin 327) 1 part by weight, hindered amine light stabilizer (Sankyo Co., Ltd., trade name: Sanol LS770) 1 part by weight was weighed, mixed and kneaded well, then 3 The paint roll was passed 3 times. Thereafter, 2 parts by weight of vinyltrimethoxysilane, 3 parts by weight of an aminosilane compound (manufactured by Nippon Unicar Co., Ltd., trade name: A-1120), a curing accelerator (manufactured by Nitto Kasei Co., Ltd., trade name: U-220) 2 parts by weight were added and kneaded.

  After kneading in a substantially moisture-free state, the mixture was sealed in a moisture-proof container to obtain a one-component curable composition.

  While measuring the viscosity (23 ° C: BS viscometer 1 rpm, 2 rpm, 10 rpm) of the resulting blend, a 3 mm thick sheet was prepared for a dumbbell (JIS No. 3 type) tensile test. After curing at 50 ° C. for 4 days, physical properties after curing (50% modulus, breaking strength, elongation) were measured. In the tensile shear test, the curable composition was applied to an aluminum base material (100 mm × 25 mm × 2 mm: JIS A1050P) at a square of 25 mm, and then the two base materials were bonded together and cured at 23 ° C. for 3 days + 50 ° C. for 4 days. And a pulling speed of 50 mm / min, 23 ° C., 55% R.D. H. A tensile test was performed under the conditions.

  Further, 23 ° C., 55% R.D. H. Under the conditions, a sheet-like test body having a thickness of about 3 mm was prepared, and after 1 day and 7 days, the cured surface was touched with a finger to evaluate stickiness. > ◎ indicates that there is no stickiness at all, and the stickiness of the sample surface increases in the order of ◎, ○, ○ △, Δ, Δ ×, ×.

  Further, as an evaluation method of paint stain resistance, seven types of commercially available paints were applied to the sheet surface after curing the prepared 3 mm thick sheet at 23 ° C. for 3 days. After 3 days, the contamination of the paint was evaluated by applying volcanic ash and observing its adhesion (good: dirt is almost inconspicuous, slightly bad: dirt is slightly noticeable, bad: dirt is often attached, dirt is dirty stand out). Furthermore, the construction was performed on the marble joint, and the contamination state of the marble around the joint after 2 months was observed, and the width of the contaminated portion was measured. The results are shown in Table 2.

(Examples 6 and 7, Comparative Examples 5 to 8)
Similarly to Example 5, each polymer component and plasticizer component were mixed in the proportions shown in Table 2, and a one-component formulation was prepared in the same manner as in Example 5.

  The viscosity, tensile properties of the cured product, shear test, residual tack, and contamination were measured in the same manner as in Example 5. The results are shown in Table 2.

  In Table 2, Examples 5, 6, and 7 using the component (B) having a trialkoxysilyl group maintain a higher modulus of the cured product than Comparative Example 5 using the component (B) having a methyldimethoxysilyl group. The initial residual tack is also a good result. Also, compared to Comparative Examples 6 and 7 using PPG or DIDP having no reactive group, the paint contamination and the contamination around the joints are good. Further, by using the component (B) having a lower molecular weight than the component (A), the viscosity is lower than that of Comparative Example 8, and good workability is ensured.

(Example 8, Comparative Example 9)
Similarly to Example 5, each polymer component was mixed in the ratio shown in Table 3, and a one-component formulation was prepared in the same manner as in Example 5.

  The viscosity, tensile properties of the cured product, shear test, residual tack, and contamination were measured in the same manner as in Example 5. The results are shown in Table 3.

  In Table 3, Example 8 using triethoxysilyl group-terminated octadecane is equivalent in terms of soiling physical properties from the viewpoint of having both reactivity compared to Comparative Example 9 using methyldimethoxysilyl group-terminated octadecane. The tensile properties of Example 8 are maintained at a high modulus and have the same breaking strength. In particular, as compared with Comparative Example 8, the viscosity could be greatly reduced by blending the B4 component with the A1 component, and the tensile properties were equivalent.

  As mentioned above, the mixed composition of a dialkoxy group-containing organic polymer and a low-functionalized trialkoxy group-containing organic polymer from Tables 1, 2 and 3 contains a dialkoxy-group-containing organic polymer and a low-functionalized dialkoxy group. It can be seen that a gel fraction higher than the initial stage of curing can be obtained as compared with a mixed composition of organic polymers, and the tensile properties of the cured product can be maintained at a high modulus. Moreover, the viscosity can be lowered by using a low functionalized trialkoxy group-containing organic polymer having a low molecular weight.

  Therefore, the curable composition of the present invention has a modulus that does not decrease too much when the viscosity is lowered, it is easy to control the adjustment of the viscosity and the balance of physical properties, and the application having a relatively high modulus, such as an adhesive or an industrial product. It can be used for sealing materials. Furthermore, since the trialkoxysilyl group is incorporated at the cross-linking point, it can be expected to improve the restoration property, creep resistance and durability of the cured product.

Claims (4)

An organic polymer (A) in which the main chain skeleton containing a reactive silicon group represented by the following general formula (1) is an oxyalkylene polymer, and a reactive silicon group represented by the following general formula (2) Is represented by the following general formula (2), or an organic polymer having a number average molecular weight of 8000 or less, wherein the main chain skeleton containing 0.5 to 1.5 per molecule is an oxyalkylene polymer. A curable composition comprising a saturated hydrocarbon compound (B) having 20 or less carbon atoms containing one reactive silicon group per molecule ,
A curable composition containing 1 to 100 parts by weight of an organic polymer or a saturated hydrocarbon compound (B) with respect to 100 parts by weight of the organic polymer (A) .
-Si (R ¹ ) X ₂ (1)
(In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosiloxy group represented by (R ′) ₃ SiO—. And when two or more R ¹ are present, they may be the same or different, wherein R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ′ may be the same or different, X represents a hydroxyl group or a hydrolyzable group, and they may be the same or different.
-SiX ₃ (2)
(Wherein X is the same as that of general formula (1)) The organic polymer (B) is a reactive silicon group-containing compound having a reactive silicon group represented by the general formula (2) and a functional group capable of reacting with the reactive group in the organic polymer. The curable composition according to claim 1, wherein the curable composition is a polymer obtained by reacting 0.5 mol to 1.5 mol with respect to mol. The organic polymer (B) The curable composition according to claim 1 or 2, characterized in a Turkey that having a reactive silicon group represented by substantially one formula (2). The curable composition according to claim 1, wherein the component (B) is a saturated hydrocarbon compound having 20 or less carbon atoms containing one reactive silicon group represented by the general formula (2) per molecule.