JP5421106B2 - Curable composition - Google Patents

Description

  The present invention relates to a curable composition useful as a sealing material or an adhesive in construction, DIY, electrical / electronic, industrial applications and the like.

  An organic polymer having at least one reactive silicon group in the molecule is crosslinked at the room temperature by the formation of a siloxane bond accompanied by a hydrolysis reaction of the reactive silicon group due to moisture or the like, and becomes a rubber-like cured product. It has been known.

  Among these polymers having a reactive silicon group, polyoxyalkylene polymers and (meth) acrylic acid alkyl ester copolymers whose main chain skeleton are already industrially produced are used as sealing materials and adhesives. It is widely used for applications such as injection material, putty material, and coating material (for example, Patent Documents 1 to 4).

  Various properties such as workability, curability, adhesion, and mechanical properties are required for curable compositions used for sealants and adhesives and rubber-like cured products obtained by curing, and various studies have been conducted. ing.

When adhering and sealing a curable composition using an organic polymer having a reactive silicon group to a transparent substrate such as glass, polycarbonate, or acrylic, it maintains a sense of unity with the substrate and ensures design. In view of this, transparency may be required for the cured composition. In response to these requirements, examples of improvements by using specific compounding materials (for example, Patent Documents 5 to 8) can be seen, but the balance between transparency and adhesiveness, and yellowing resistance when exposed to the outdoors for a long period of time. However, the level has not yet reached a sufficient level, and improvements are desired.
Patent No. 1396791 Japanese Patent No. 1682540 Japanese Patent No. 1611744 Japanese Patent No. 1517827 JP-A-9-316339 Japanese Patent Laid-Open No. 11-302527 JP 2000-38560 A JP 2003-313421 A

  The object of the present invention is to provide transparency, adhesion, and resistance of a curable composition using an organic polymer having a reactive silicon group, which is used in various fields such as architecture, DIY, electrical / electronic, and industrial applications. It is to improve the balance of yellowing.

  As a result of intensive studies by the present inventors in order to solve the above problems, the following components, that is, a reactive silicon group-containing organic polymer, a compound having a specific reactive silicon group and an amino group, hydrophobic finely divided silica, curing It has been found that a curable composition containing a catalyst is effective.

That is, the present invention
(A) The following general formula (1):
-Si (R ¹ _3-a ) X _a (1)
(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, X represents a hydroxyl group or a hydrolyzable group. 100 parts by weight of an organic polymer having a reactive silicon group represented by
(B) In one molecule, the following general formula (2):
-SiX ₃ (2)
(Wherein X represents a hydroxyl group or a hydrolyzable group) and the compound (b1) having a reactive silicon group and one amino group represented by the following general formula ( 3):
-Si (R ¹ ) X ₂ (3)
(Wherein R ¹ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and X represents a hydroxyl group or a hydrolyzable group). 0.01 to 30 parts by weight of the compound (b2) having a reactive silicon group and amino group,
(C) 2 to 70 parts by weight of hydrophobic fine powder silica,
(D) 0.01 to 20 parts by weight of a curing catalyst,
It relates to the curable composition containing this.

More preferably, the component (B) is represented by the following general formula (2):
-SiX ₃ (2)
(Wherein X represents a hydroxyl group or a hydrolyzable group) and relates to a curable composition that is a compound (b1) having a reactive silicon group and one amino group.

  More preferably, it relates to a curable composition in which the hydrolyzable group of the component (b1) is a methoxy group.

  More preferably, it relates to (E) a curable composition containing 0.01 to 20 parts by weight of a phosphorus stabilizer.

  More preferably, the component (A) is composed of a polyoxyalkylene polymer (a1) and / or a vinyl polymer (a2) having a reactive silicon group represented by the general formula (1). The present invention relates to a curable composition.

  More preferably, the phosphorus stabilizer of component (E) relates to a curable composition comprising phosphites.

  More preferably, it relates to a curable composition wherein the hydrophobic silica of component (C) is fumed silica.

  The present invention relates to a sealing material or an adhesive comprising the curable composition.

  According to the present invention, it is possible to provide a sealing material, an adhesive, an injection material, a putty material, a coating material, and the like, which are excellent in balance of transparency, adhesiveness, and yellowing resistance.

  The curable composition of the present invention comprises 0.01 to 30 weight percent of the compound (B) having a specific reactive silicon group and amino group with respect to 100 weight parts of the organic polymer (A) having a reactive silicon group. Part, hydrophobic fine powder silica (C) 2 to 70 parts by weight, curing catalyst (D) 0.01 to 20 parts by weight, a curable composition having an organic polymer having a reactive silicon group ( Depending on the type of A), it is possible to develop characteristics unique to the polymer.

  The organic polymer (A) having a reactive silicon group is not particularly limited. For example, the main chain skeleton thereof is an organic material such as a generally known polyoxyalkylene polymer, vinyl polymer, or polyester polymer. Polymers can be used. In particular, the polyoxyalkylene polymer (a1) having a reactive silicon group and / or the vinyl polymer (a2) having a reactive silicon group are suitable for the workability and curability of the composition, the mechanical properties of the cured product, It is preferable because it is easy to secure a balance of physical properties such as adhesiveness.

The reactive silicon group of the reactive silicon group-containing polyoxyalkylene polymer (a1) that can be used as the component (A) of the present invention is not particularly limited. And a group represented by the general formula (1).
-Si (R ¹ _3-a ) X _a (1)
(R ¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, X represents a hydroxyl group or a hydrolyzable group, and a represents 1, 2 or 3 is shown.)
The hydrolyzable group represented by X is not particularly limited, and any conventionally known hydrolyzable group can be suitably used. Specific examples include 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. Alkoxy groups such as a methoxy group are particularly preferred from the viewpoint of mildness and easy handling.

  1 to 3 hydroxyl groups or hydrolyzable groups can be bonded to one silicon atom. When two or more hydroxyl groups are present in a reactive silicon group, they may be the same or different. good.

Specific examples of R ¹ in the general formula (1) include alkyl groups such as a methyl group and an ethyl group, cycloalkyl groups such as a cyclohexyl group, aryl groups such as a phenyl group, and aralkyl groups such as a benzyl group. . R ¹ is particularly preferably a methyl group.

  Although it does not restrict | limit especially as a reactive silicon group, A dimethylmonomethoxysilyl group, a methyldimethoxysilyl group, a trimethoxysilyl group, a methyldiethoxysilyl from the point with a high hydrolytic activity and a moderate hydrolyzability and easy to handle. It is preferably at least one selected from the group consisting of a group, an ethyldiethoxysilyl group, and a triethoxysilyl group.

  The main chain structure of the polyoxyalkylene polymer (a1) having a reactive silicon group according to the present invention may be a polymer having a structure represented by -RO- as a repeating unit. May be any divalent organic group having 1 to 20 carbon atoms containing one or more selected from the group consisting of hydrogen, oxygen, and nitrogen as constituent atoms. Moreover, the homopolymer in which all the repeating units are the same may be sufficient, and the copolymer containing a 2 or more types of repeating unit may be sufficient. Further, the main chain may have a branched structure.

  The main chain polymer of the polyoxyalkylene polymer (a1) having a reactive silicon group is a monoepoxy compound in the presence of various polymerization catalysts, starting from dihydric alcohol or polyhydric alcohol and various oligomers having a hydroxyl group. Is obtained by ring-opening polymerization.

  Specific examples of the initiator include, for example, ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, methallyl alcohol, hydrogenated bisphenol A, neopentyl glycol, polybutadiene diol, diethylene glycol, triethylene glycol, polyoxyethylene glycol, poly Examples thereof include oxypropylene glycol, polyoxypropylene triol, polyoxypropylene tetraol, dipropylene glycol, glycerin, trimethylol methane, trimethylol propane, pentaerythritol, polyoxypropylene diol and polyoxypropylene triol. In particular, the use of polypropylene glycol or polypropylene triol is preferable from the viewpoint of ease of production, but other materials may be used.

  Specific examples of the monoepoxy compound include ethylene oxide, propylene oxide, α-butylene oxide, β-butylene oxide, hexene oxide, cyclohexene oxide, styrene oxide, α-methylstyrene oxide and other alkylene oxides, and methyl. Examples thereof include alkyl or allyl or aryl glycidyl ethers such as glycidyl ether, ethyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, and phenyl glycidyl ether. In particular, it is preferable to use propylene oxide because it is easy to ensure workability of the finally obtained component (a1), flexibility after curing, adhesion, and the like, but other components may be used. .

  Specific examples of the polymerization catalyst include alkali catalysts such as KOH and NaOH, acidic catalysts such as trifluoroborane-etherate, double metal cyanide complex catalysts such as aluminoporphyrin metal complexes and cobalt cyanide zinc-glyme complex catalysts. Already known ones such as are used. In particular, the use of a zinc hexacyanocobaltate glyme complex catalyst, which is a complex metal cyanide complex catalyst with few side reactions, is preferred, but other than that may be used.

  Specific examples of such polymerization are represented by, for example, a polymerization method using an alkali catalyst such as KOH, for example, a complex obtained by reacting an organoaluminum compound and porphyrin described in JP-A-61-215623. Polymerization method using transition metal compound-porphyrin complex catalyst, 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. No. 3, U.S. Pat. No. 3,427,335, and a polymerization method using a double metal cyanide complex catalyst, for example, a polymerization method using phosphazene disclosed in JP-A-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 polyoxyalkylene polymer having a low molecular weight but a low viscosity is preferable because it has a feature.

In addition to this, the main chain polymer of the polyoxyalkylene polymer (a1) containing a reactive silicon group is a hydroxyl group-terminated polyoxyalkylene polymer obtained from a basic compound such as KOH, NaOH, KOCH ₃ , NaOCH _3. Can be obtained by chain extension with a bifunctional or higher functional alkyl halide such as CH ₂ Cl ₂ or CH ₂ Br ₂ . Moreover, the method etc. which chain-extend a hydroxyl-terminated polyoxyalkylene polymer with a bifunctional or trifunctional isocyanate compound are also mentioned.

  The method for introducing the reactive silicon group into the polymer terminal of the polyoxyalkylene polymer is not particularly limited, and various methods can be used. In particular, a method in which a polyoxyalkylene polymer having an alkenyl group at the terminal and a reactive silicon group-containing hydrosilane compound is reacted in the presence of a group 8 transition metal catalyst is preferred.

  Examples of the hydrosilane compound include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, and phenyldimethoxysilane. Alkoxysilanes; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; ketoximatesilanes such as bis (dimethylketoxymate) methylsilane and bis (cyclohexylketoxymate) methylsilane However, it is not limited to these. Of these, halogenated silanes and alkoxysilanes are particularly preferable.

  In addition to this, addition of a reactive silicon group-containing isocyanate compound to a hydroxyl group-terminated polyoxyalkylene polymer, reaction of an isocyanate group-terminated polyoxyalkylene polymer with a reactive silicon group-containing amine compound, It can also be obtained by reacting an oxyalkylene polymer with a reactive silicon group-containing mercaptan compound.

As a method for producing a polyoxyalkylene polymer having an alkenyl group at the terminal, a conventionally known method may be used. For example, a hydroxyl group-terminated polyoxyalkylene polymer is reacted with a compound having an alkenyl group to form an ether bond, Examples of the method include bonding by an ester bond, a urethane bond, and a carbonate bond. For example, when an alkenyl group is introduced by an ether bond, the polyoxyalkylene polymer is terminated with a hydroxyl group terminal such as -ONa or -OK, and then the general formula (4):
^{_{CH 2 = CH-R 2 -Y}} (4)
Or general formula (5):
^{_{CH 2 = C (R 3)}} -R 2 -Y (5)
(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 (4) or unsaturated group-containing compound represented by _{(5), 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, etc. from the _{point, 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 - group and _{CH 2 = C (CH 3)} -CH 2 - isocyanate compound having a group such as a carboxylic acid, the use of the epoxy compounds You can also.

As the group 8 transition metal catalyst, 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.

  The polyoxyalkylene polymer (a1) having a reactive silicon group 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 a polyoxy group from the viewpoint of moderately low viscosity and a cured product having appropriate flexibility. It is preferable that 50% by weight or more, preferably 80% by weight or more is present in the alkylene polymer.

  Although there is no restriction | limiting in particular in the molecular weight of the polyoxyalkylene type polymer (a1) which has a reactive silicon group, 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.

  Further, in the contained polyoxyalkylene polymer (a1) having a reactive silicon group, the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight is preferably 1.6 or less, more preferably. Is 1.5 or less, 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 polyoxyalkylene polymer having a reactive silicon group with Mw / Mn of 1.6 or less has a low viscosity and exhibits good workability.

  Next, the vinyl polymer (a2) having a reactive silicon group that can be used as the component (A) of the present invention will be described. The main chain of the vinyl polymer (a2) 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 (a2) of this invention, 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 the vinyl-type polymer (a2) of this invention, 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- (methacryloyloxy) propyltrimethoxysilane, 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; 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 (a2) is 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 the polymer is mainly produced by polymerization. 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 (a2) is lower than room temperature or use temperature for applications requiring rubber elasticity.

  The molecular weight distribution of the vinyl polymer (a2), 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 Is less than 1.8, more preferably not more than 1.7, still more preferably not more than 1.6, still more preferably not more than 1.5, particularly preferably not more than 1.4, most preferably Is 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 (a2) is not particularly limited, but when measured by gel permeation chromatography, the range of 500 to 1,000,000 is preferable, and 1,000 to 100,000 is more preferable. 5,000 to 50,000 are more preferable.

  As the controlled radical polymerization for synthesizing the main chain of the vinyl polymer (a2), living radical polymerization is preferable, 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. In order to obtain a polymer having two or more growth terminal structures in one molecule, it is preferable to use an organic halide having two or more starting points or a sulfonyl halide compound as an initiator. Specific examples of such an initiator include diethyl 2,5-dibromoadipate.

  There is no restriction | limiting in particular as a vinyl-type monomer used in this superposition | polymerization, All already illustrated can be used suitably.

Although it does not specifically limit as a transition metal complex used as a polymerization catalyst, Preferably it is a metal complex which uses a periodic table group 7, 8, 9, 10, or 11 element as a central metal. More preferred are complexes having a central metal of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. is there. When a copper compound is used, 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity A ligand such as a polyamine is added. A preferred ligand is a nitrogen-containing compound, a more preferred ligand is a chelate-type nitrogen-containing compound, and a more preferred ligand is N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine. It is. A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Further, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine A complex (NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

  The polymerization can be carried out without solvent or in various solvents. Solvent types include hydrocarbon solvents such as benzene and toluene, ether solvents such as diethyl ether and tetrahydrofuran, halogenated hydrocarbon solvents such as methylene chloride and chloroform, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Solvents, alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, t-butyl alcohol, nitrile solvents such as acetonitrile, propionitrile, benzonitrile, ester solvents such as ethyl acetate, butyl acetate, Examples thereof include carbonate solvents such as ethylene carbonate and propylene carbonate, and these can be used alone or in admixture of two or more.

  Moreover, although not limited, superposition | polymerization can be performed in 0 to 200 degreeC, Preferably it is 50 to 150 degreeC.

  The atom transfer radical polymerization of the present invention includes so-called reverse atom transfer radical polymerization. Reverse atom transfer radical polymerization is a high oxidation state when a normal atom transfer radical polymerization catalyst generates radicals, for example, peroxidation with respect to Cu (II ′) when Cu (I) is used as a catalyst. In this method, a general radical initiator such as a compound is allowed to act, and as a result, an equilibrium state similar to that of atom transfer radical polymerization is produced (see Macromolecules 1999, 32, 2872).

  The vinyl polymer (a2) has at least one crosslinkable silyl group. Further, from the viewpoint of the curability of the composition and the physical properties of the cured product, the number of crosslinkable silyl groups is preferably 1.1 or more and 4.0 or less, more preferably 1.2 or more and 3.5 or less on average. It is as follows.

  When a rubber property is particularly required for a cured product obtained by curing the curable composition of the present invention, the molecular weight between crosslinking points that greatly affects rubber elasticity can be increased. One is preferably at the end of the molecular chain. More preferably, it has all crosslinkable functional groups at the molecular chain ends.

  A method for producing a vinyl polymer having at least one crosslinkable silyl group at its molecular terminal, in particular, a (meth) acrylic polymer is disclosed in Japanese Patent Publication No. 3-14068, Japanese Patent Publication No. 4-55444, No. 6-211922 and the like. However, since these methods are free radical polymerization methods using the above "chain transfer agent method", the resulting polymer has a relatively high proportion of crosslinkable functional groups at the molecular chain ends, while Mw / Mn The value of the molecular weight distribution represented by is generally as large as 2 or more, and the viscosity is increased. Therefore, in order to obtain a vinyl polymer having a narrow molecular weight distribution and a low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high ratio, the above “living radical polymerization method” is used. It is preferable.

  As the reactive silicon group of the vinyl polymer (a2), the reactive silicon group represented by the general formula (1) can be used in the same manner.

  Hereinafter, a method for introducing a silyl group into a vinyl polymer will be described, but the method is not limited thereto.

As a synthesis method of the vinyl polymer (a2) having at least one reactive silicon group,
(I) Method of adding a hydrosilane compound having a reactive silicon group to a vinyl polymer having at least one alkenyl group in the presence of a hydrosilylation catalyst (II) One molecule per vinyl polymer having at least one hydroxyl group A method of reacting a compound having a group capable of reacting with a reactive silicon group and a hydroxyl group such as an isocyanate group. (III) When a vinyl polymer is synthesized by radical polymerization, a polymerizable alkenyl group is contained in one molecule. (IV) Method of using a chain transfer agent having a reactive silicon group when synthesizing a vinyl polymer by radical polymerization (V) Highly reactive carbon-halogen Method of reacting a vinyl polymer having at least one bond with a compound having a reactive silicon group and a stable carbanion in one molecule And the like.

  Next, the vinyl polymer (a2) produced by the free radical polymerization method will be described.

  It does not specifically limit as a vinyl-type monomer, A various thing can be used and all the above-mentioned monomers can be used suitably.

  Although not limited, the main chain of the vinyl polymer (a2) 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 at least one monomer. 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.

  The vinyl polymer (a2) may contain a monomer unit having copolymerizability with the above monomer unit such as a (meth) acrylic acid ester monomer. 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 (a2) in this case is not particularly limited, but when measured by gel permeation chromatography, those 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 favorable weather resistance of a hardened | cured material, and workability | operativity.

  A method for synthesizing the main chain of the vinyl polymer (a2) 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 can be mentioned, but the use of azo-based initiators is preferred from the viewpoint of being not affected by the solvent used for polymerization and having 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 non-reactive solvents such as ethers, hydrocarbons, and esters.

  In this case, the number of reactive silicon groups of the vinyl polymer (a2) is not particularly limited, but it is preferable to have one or more on average from the viewpoints of curability of the composition and physical properties of the cured product, More preferably 1.1 or more, still more preferably 1.2 or more, and still more preferably 1.5 or more.

  As the reactive silicon group of the vinyl polymer (a2), the reactive silicon group represented by the general formula (1) can be used in the same manner.

Examples of the method for introducing a reactive silicon group into the vinyl polymer (a2) of the present invention include a compound having both a polymerizable unsaturated bond and a reactive silicon group as a (meth) acrylic acid ester monomer. The method of copolymerizing with a unit is mentioned. The compound having both a polymerizable unsaturated bond and a reactive silicon group is represented by the general formula (6):
^{_{CH 2 = C (R 4)}} COOR 5 -Si (R 1 3-a) X a (6)
(In the formula, R ⁴ represents a hydrogen atom or a methyl group. R ⁵ represents a divalent alkylene group having 1 to 6 carbon atoms. R ¹ , X, and a are the same as those in the general formula (1).)
Or general formula (7):
^{_{CH 2 = C (R 4)}} -Si (R 1 3-a) X a (7)
(In the formula, R ⁴ , R ¹ , X and a are the same as above.)
Monomers such as γ-methacryloxypropyl trimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyl polyalkoxysilane such as γ-methacryloxypropyltriethoxysilane, and γ-acrylic. Γ-acryloxypropyl polyalkoxysilane such as loxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, etc. Examples thereof include vinyl alkyl polyalkoxysilane.

  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.

In the curable composition of the present invention, the following general formula (2):
-SiX ₃ (2)
(Wherein X represents a hydroxyl group or a hydrolyzable group) and the compound (b1) having a reactive silicon group and one amino group represented by the following general formula ( 3):
-Si (R ¹ ) X ₂ (3)
(Wherein R ¹ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and X represents a hydroxyl group or a hydrolyzable group). It is preferable to add a compound having a reactive silicon group and an amino group.

The following general formula (2) per molecule
-SiX ₃ (2)
Specific examples of the compound (b1) having a reactive silicon group and one amino group represented by (wherein X represents a hydroxyl group or a hydrolyzable group) include, for example, γ-aminopropyltrimethoxysilane. , Γ-aminopropyltriethoxysilane, β-aminoethyltrimethoxysilane, β-aminoethyltriethoxysilane, α-aminomethyltrimethoxysilane, α-aminomethyltriethoxysilane, 4-aminobutyltrimethoxysilane, 4 -Aminobutyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltrimethoxysilane and the like.

Moreover, the following general formula (3):
-Si (R ¹ ) X ₂ (3)
(Wherein R ¹ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and X represents a hydroxyl group or a hydrolyzable group). Specific examples of the compound (b2) having a reactive silicon group and an amino group are, for example, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-β- (aminoethyl) -γ. -Aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldiethoxysilane, β-aminoethylmethyldimethoxysilane, β-aminoethylmethyldiethoxysilane, α-aminomethylmethyldimethoxysilane , Α-aminomethylmethyldiethoxysilane, 4-aminobutylmethyldimethoxysilane, 4-aminobutyl Examples thereof include methyldiethoxysilane, N- (6-aminohexyl) aminopropylmethyldimethoxysilane, N- (6-aminohexyl) aminopropylmethyldiethoxysilane, and the like.

  As the component (B) of the present invention, the component (b1) may be used alone or in combination. Further, the component (b2) may be used alone or in combination. It is also possible to use the component (b1) and the component (b2) in combination.

  By using this component (B), it is possible to ensure adhesion to various adherends without significantly reducing the transparency of the cured product. In particular, it is effective to use the component (b1) in order to keep the balance of transparency, adhesiveness, and fast curability of the present composition moderately. Among the components (b1), a compound having a trimethoxysilyl group is preferable from the viewpoint that quick curability can be obtained.

  The amount of component (B) used is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of component (A). If it is less than 0.01 part by weight, the adhesiveness is lowered, and if it exceeds 30 parts by weight, curing inhibition may occur.

  It is preferable to add hydrophobic fine silica as the component (C) to the curable composition of the present invention. Specific examples of the hydrophobic fine powder silica include fine powder silica such as fumed silica (fumed silica). Fumed silica is silicon dioxide vaporized from silicon tetrachloride and hydrolyzed in a hot flame. Aggregated particles or agglomerated particles are formed which are composed of spherical primary particles without pores, but are strongly agglomerated in the production process. Siloxane and silanol groups are present on the surface of these particles, and hydrophobicity is imparted by chemically reacting silanes or silazanes with the silanol groups. Specific examples of the surface treatment agent include dimethyldichlorosilane, silicone oil, hexamethyldisilazane, octylsilane, hexadecylsilane, aminosilane, methacrylsilane, octamethylcyclotetrasiloxane, and polydimethylsiloxane. . Hydrophobizing the surface reduces water adsorption and facilitates dispersion in an organic polymer having a reactive silicon group as component (A).

  Specific product names include Aerosil DT4, Aerosil NA200Y, Aerosil NA50H, Aerosil NA50Y, Aerosil NAX50, Aerosil R104, Aerosil R106, Aerosil R202, Aerosil R202W90, Aerosil R504, Aerosil R711, Aerosil R700, Aerosil R7200, Aerosil R805VV90, Aerosil R812, Aerosil R812S, Aerosil R816, Aerosil R8200, Aerosil R972, Aerosil R972V, Aerosil R974, Aerosil RA200HS, Aerosil RX200, Aerosil RX300Y, Aerosil RX200Y, Aerosil RR200Y Degussa's products such as 0 can be exemplified.

The particle size of the hydrophobic fine powder silica is not particularly limited, but the specific surface area (according to the BET adsorption method) is preferably 10 m ² / g or more, more preferably 30 to 500 m ² / g, still more preferably 50 to 300 m ^2. Silica in the form of ultrafine powder of about / g. The BET adsorption method is a method in which an inert gas molecule whose adsorption occupation area is known is physically adsorbed on the surface of powder particles at the temperature of liquid nitrogen, and the specific surface area of the sample is obtained from the amount.

  These components (C) may be used alone or in combination of two or more. By using this component (C), not only the workability of the composition and the toughness of the cured product are improved, but also the transparency of the composition can be greatly improved. The amount of component (C) used is preferably 2 to 70 parts by weight, more preferably 5 to 50 parts by weight per 100 parts by weight of component (A). If it is less than 2 parts by weight, workability, toughness and transparency are lowered, and if it exceeds 70 parts by weight, the viscosity of the system is increased and workability is lowered.

  It is preferable to add a curing catalyst to the curable composition of the present invention as the component (D). Specific examples of the curing catalyst include titanium compounds such as tetrabutyl titanate, tetraisopropyl titanate, titanium tetraacetylacetonate; dibutyltin dilaurate, bis (dibutyltin laurate) oxide, dibutyltin malate, dibutyltin phthalate, dibutyltin dioctate, Dibutyltin diethylhexanoate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutylmalate, dibutyltin dioctylmalate, dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin diacetate, dioctyltin diethylmalate, dioctyltin Dioctyl malate, dibutyltin dimethoxide, dibutyltin dinonylphenoxide, dibutenyl 4 such as dioxide, dibutyltin bisacetylacetonate, dibutyltin bisethylacetoacetonate, reaction product of dibutyltin oxide and phthalate, reaction product of dibutyltin oxide and maleate, reaction product of dibutyltin oxide and ethyl silicate, etc. Divalent tin compounds; divalent tin compounds such as tin octylate, tin naphthenate, tin stearate, tin versatate; organics such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate Aluminum compounds; zirconium compounds such as zirconium tetraacetylacetonate; bismuth tris (2-ethylhexanoate); zinc octylate; butylamine, o Tylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, laurylamine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, phenylguanidine, diphenylguanidine , Tolylbiguanide, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo [5,4,0] undecene-7 ( DBU) and other amine compounds, or salts of these amine compounds with carboxylic acids, etc .; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids Excess reaction product of a polyamine and an epoxy compound, more other acidic catalysts, basic catalysts such as known silanol condensation catalysts, and the like.

  These components (D) may be used alone or in combination of two or more. The amount of component (D) used is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of component (A). If it is less than 0.01 part by weight, the curability required for actual use cannot be obtained, and if it exceeds 20 parts by weight, bleeding to the interface occurs and the adhesiveness is lowered.

In the curable composition of the present invention, in order to further enhance the activity of the condensation catalyst, it is represented by the general formula R ¹⁴ _-a Si (OR ¹ ) _a (wherein R ¹ and a are the same as 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, more preferably 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. 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.

  A phosphorus-based stabilizer can be added to the curable composition of the present invention as the component (E) as necessary. Specific examples of phosphorus stabilizers include phosphites and phosphates classified as phosphorus antioxidants. Specific examples include, for example, tris (decyl) phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tricresyl phosphite, triethyl phosphite , Tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, trioleyl phosphite, trilauryl trithiophosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (biphenyl) ) Phosphite, tristearyl phosphite, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, phenyl bis (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl (2-ethyl) Xyl) phosphite, diphenyldecylphosphite, diphenylisodecylphosphite, diphenylmono (tridecyl) phosphite, bis (nonylphenyl) mono (dinonylphenyl) phosphite, bis (dinonylphenyl) mono (nonylphenyl) phosphine Phyto, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, tris [2-[[2,4,8,10-tetra-tert-butyldibenzo [d, f] [1 , 3,2] dioxaphosphine-6-yl] oxy] ethyl] amine, tetraalkyl-4,4′-isopropylidene diphenyl diphosphite (alkyl: C12-C15 alkyl), tetraphenyldipropylene glycol di Phosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphine Bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenyl-bisphenol A pentaerythritol diphosphite, tetrakis (tridecyl) -4,4′-butylidenebis (3-methyl-6) -Tert-butylphenyl) diphosphite, 4,4'-butylidenebis [3-methyl-6-tert-butylphenylbis (tridecyl) phosphite], hexakis (tridecyl) -1,1,3-tris (2-methyl- 4-hydroxy 5-t-butylphenyl) butane triphosphite, hydrogenated bisphenol A-pentaerythritol phosphite polymer, hydrogenated bisphenol A phosphite polymer, diethyl hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite Phyto, tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite, 3,5-di-tert-butyl-4-hydroxybenzyl phosphite Phosphites such as diethyl ester, 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide, 1,3-bis (diphenoxyphosphonoxy) benzene, sodium bis (4- te t- butylphenyl) phosphate, sodium-2,2'-methylene - bis (4,6-di -tert- butylphenyl) phosphate include phosphoric acid esters and the like.

  These (E) components may be used independently and may be used together 2 or more types. By using this component (E), yellowing resistance of the cured product over a long period of time can be improved. (E) As for the usage-amount of component, 0.01-20 weight part is preferable with respect to 100 weight part of (A) component, More preferably, it is 0.1-10 weight part. If it is less than 0.01 part by weight, the yellowing resistance is lowered, and if it exceeds 20 parts by weight, bleeding to the interface occurs and adhesiveness is lowered.

  If necessary, a plasticizer, a silane coupling agent, a thixotropic agent, a reactive diluent, a stabilizer, a colorant, and the like can be added to the curable composition of the present invention.

  Specific examples of plasticizers include phthalates such as dibutyl phthalate, di (2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate, butyl benzyl phthalate; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate, etc. Non-aromatic dibasic acid esters; aliphatic esters such as butyl oleate and methyl acetylricinoleate; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate and pentaerythritol ester; Phosphate esters such as zircyl phosphate and tributyl phosphate; trimellitic acid esters; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile Lil, polychloroprene; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and hydroxyl groups of polyether polyols Derivatives such as derivatives converted to ester groups, ether groups, etc .; Epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate; Dibasic acids such as sebacic acid, adipic acid, azelaic acid, and phthalic acid Polyester plasticizers obtained from dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, etc .; various vinyl monomers including acrylic plasticizers Vinyl polymers and the like obtained by polymerizing by law and the like. These plasticizers may be used alone or in combination of two or more. Although the usage-amount in the case of using a plasticizer is not limited, It is 5-100 weight part with respect to 100 weight part of (A) component, Preferably it is 10-80 weight part. If it is less than 5 parts by weight, the effect as a plasticizer is not exhibited, and if it exceeds 100 parts by weight, the mechanical strength of the cured product is insufficient, which is not preferable.

  Specific examples of the silane coupling agent include, for example, mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-mercaptopropylmethyldiethoxysilane. Epoxy groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Containing silanes; carboxysilanes such as β-carboxylethylphenylbis (2-methoxyethoxy) silane, N-β- (N-carboxylmethylaminoethyl) -γ-aminopropyltrimethoxysilane; amino group-containing silanes; each Ketiminated silanes obtained by dehydration condensation with seed ketones; reaction product of amino group-containing silanes and epoxy group-containing silanes; reaction product of mercapto group-containing silanes and epoxy group-containing silanes; amino group-containing silanes Reaction product of alkenyl and epoxy resin; reaction product of mercapto group-containing silane and epoxy resin; ethyl silicates such as tetraethoxysilane, tetraethoxysilane tetramer, tetraethoxysilane hexamer; vinyltrimethoxysilane; And vinyl silanes such as vinyltriethoxysilane and vinyltriacetoxysilane; and methacryloxysilanes such as 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane. These silane coupling agents may be used alone or in combination of two or more. Moreover, the usage-amount is the range of about 0.1-20 weight part normally with respect to 100 weight part of (A) component, Preferably the range of about 0.2-10 weight part is preferable. If it is less than 0.1 part by weight, the adhesiveness and storage stability will be lowered, and if it exceeds 20 parts by weight, curing inhibition will occur.

  Specific examples of the thixotropic agent include hydrogenated castor oil, organic amide wax, organic bentonite, calcium stearate and the like. These thixotropic agents may be used alone or in combination of two or more. May be.

  Specific examples of the stabilizer include an antioxidant, a light stabilizer, and an ultraviolet absorber.

  When antioxidant is used, the heat resistance of hardened | cured material can be improved. Examples of the antioxidant include hindered phenols, amines, and polyphenols, with hindered phenols being particularly preferred.

  It is preferable to use 0.1-10 weight part with respect to 100 weight part of (A) component, and, as for the usage-amount of antioxidant, it is more preferable to use 0.2-5 weight part.

  When a light stabilizer is used, photooxidation deterioration of the cured product can be prevented. Examples of the light stabilizer include benzotriazole-based, hindered amine-based, and benzoate-based compounds, and hindered amine-based compounds are particularly preferable.

  It is preferable to use 0.1-10 weight part with respect to 100 weight part of (A) component, and, as for the usage-amount of a light stabilizer, it is more preferable to use 0.2-5 weight part.

  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.

  It is preferable to use 0.1-10 weight part with respect to 100 weight part of (A) component, and, as for the usage-amount of a ultraviolet absorber, it is more preferable to use 0.2-5 weight part.

  Furthermore, you may add various additives to the curable composition of this invention as needed for the purpose of adjustment of various physical properties of a curable composition or hardened | cured material. Examples of such additives include, for example, flame retardants, curability modifiers, radical inhibitors, metal deactivators, antiozonants, lubricants, pigments, foaming agents, solvents, fungicides and the like. It is done. These various additives may be used alone or in combination of two or more.

  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.

  The method for preparing the curable composition of the present invention is not particularly limited. For example, the above-described components are blended and kneaded using a mixer, roll, kneader or the like at room temperature or under heating, or a small amount of a suitable solvent is used. Ordinary methods such as dissolving and mixing the components can be used.

  The curable composition of this invention is demonstrated based on an Example. EXAMPLES Hereinafter, the present invention will be specifically described with reference to synthesis examples and examples, but the present invention is not limited to these synthesis examples and examples.

(Synthesis Example 1)
A polyoxypropylene diol having a number average molecular weight of 2,000 is used as an initiator, and propylene oxide is polymerized using a zinc hexacyanocobaltate glyme complex catalyst to obtain a poly having a number average molecular weight of 25,500 (polystyrene conversion value determined from GPC). Oxypropylene diol was obtained. After the obtained polyoxypropylene diol and sodium methoxide were reacted, allyl chloride was reacted to convert the terminal hydroxyl group into an unsaturated group. A number average having a dimethoxymethylsilyl group at the molecular end by reacting 0.7 mol of dimethoxymethylsilane in the presence of a platinum divinyldisiloxane complex with respect to 1 mol of the unsaturated group of this unsaturated group-terminated polyoxypropylene polymer. A polyoxypropylene polymer having a molecular weight of 26,000 (polystyrene conversion value determined from GPC) and a molecular weight distribution of 1.30 was obtained (Polymer A).

(Synthesis Example 2)
In 42 g of toluene heated to 105 ° C., 14.5 g of methyl methacrylate, 68.5 g of butyl acrylate, 15 g of stearyl methacrylate, 2 g of 3-methacryloxypropyldimethoxymethylsilane and 2,2′-azobis as a polymerization initiator A solution prepared by dissolving 0.48 g of isobutyronitrile in 18.7 g of toluene was added dropwise over 5 hours, followed by stirring for 2 hours. Furthermore, by adding a solution prepared by dissolving 0.02 g of 2,2′-azobisisobutyronitrile in 6.3 g of toluene and stirring for 1 hour, the solid content concentration was 60% by weight and the number average molecular weight was 19,000. A dimethoxymethylsilyl group-containing acrylic copolymer (Polystyrene conversion value determined from GPC) was obtained (Polymer B).

(Synthesis Example 3)
Deoxygenated n-butyl acrylate was prepared. The inside of the stainless steel reaction vessel with a stirrer was deoxygenated, and 0.84 parts by weight of cuprous bromide and 20 parts by weight of n-butyl acrylate were charged and stirred with heating. 8.79 parts by weight of acetonitrile and 1.76 parts by weight of diethyl 2,5-dibromoadipate as an initiator were added and mixed. At the stage where the temperature of the mixture was adjusted to about 80 ° C., pentamethyldiethylenetriamine (hereinafter abbreviated as triamine). ) Was added to initiate the polymerization reaction. 80 parts by weight of n-butyl acrylate was sequentially added to proceed the polymerization reaction. During the polymerization, triamine was appropriately added to adjust the polymerization rate. As the polymerization proceeds, the internal temperature rises due to the heat of polymerization, so the polymerization was allowed to proceed while adjusting the internal temperature to about 80 ° C to about 90 ° C. When the monomer conversion rate (polymerization reaction rate) was about 95% or more, volatile components were removed by devolatilization under reduced pressure to obtain a polymer concentrate. The total amount of triamine used was 0.15 parts by weight.

  To the concentrate, 21 parts by weight of 1,7-octadiene and 35 parts by weight of acetonitrile were added, and 0.34 part by weight of triamine was added. While adjusting the internal temperature to about 80 ° C. to about 90 ° C., the mixture was heated and stirred for several hours to react the octadiene with the polymer terminal. Acetonitrile and unreacted octadiene were removed by devolatilization under reduced pressure to obtain a concentrate containing a polymer having an alkenyl group at the terminal.

  The above concentrate is diluted with toluene, 1.0 part by weight of a filter aid, and 0.5 parts by weight of an adsorbent (KYOWARD 700SEN: manufactured by Kyowa Chemical) and hydrotalcite (KYOWARD 500SH: manufactured by Kyowa Chemical)) Was added, and the mixture was heated and stirred at about 80 to 100 ° C., and then the solid component was filtered off. The filtrate was concentrated to obtain a crude polymer product.

  The above-mentioned crude polymer purified product, 0.2 parts by weight of a heat stabilizer (Sumilyzer GS: manufactured by Sumitomo Chemical Co., Ltd.), and an adsorbent (Kyoward 700SEN, Kyoward 500SH) are added, devolatilized under reduced pressure, and heated and stirred. The temperature was raised while heating, stirring and vacuum devolatilization for about several hours at a high temperature of about 170 ° C to about 200 ° C. Add adsorbents (KYOWARD 700SEN, KYOWARD 500SH), add about 10 parts by weight of toluene to the crude polymer, and stir for about several hours at a high temperature of about 170 ° C to about 200 ° C. did. The total amount of adsorbents used (KYOWARD 700SEN, KYOWARD 500SH) was 1.5 parts by weight. The treatment liquid was further diluted with toluene, and the adsorbent was filtered off. The filtrate was concentrated to obtain a polymer having alkenyl groups at both ends.

  Polymer obtained by the above method, 1.7 parts by weight of methyldimethoxysilane (DMS), 0.9 parts by weight of methyl orthoformate (MOF), platinum catalyst [bis (1,3-divinyl-1,1,3, 3-tetramethyldisiloxane) platinum complex catalyst in isopropanol: hereinafter referred to as platinum catalyst] 0.0007 parts by weight were mixed and heated to about 100 ° C. with stirring. After heating and stirring for about 1 hour, volatile components such as unreacted DMS were distilled off under reduced pressure to obtain a polymer (polymer C) having methoxysilyl groups at both ends. The number average molecular weight of the obtained polymer was 24,700 according to GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.3. The average number of methoxysilyl groups introduced per molecule of the polymer was determined by 1H-NMR analysis and found to be 1.9.

(Examples 4 to 12 , 14 and Comparative Examples 1 to 11 )
Using the polymers obtained in Synthesis Examples 1 to 3, a one-component curable composition having the composition shown in Table 1 was prepared, and the following evaluation was performed.
(1) Workability: Using a BS viscometer, the viscosity of the curable composition was measured at 1 rpm and 10 rpm (No. 7 rotor, temperature 23 ° C.). The structural viscosity index was determined by dividing the 1 rpm viscosity value by the 10 rpm viscosity value. In the determination, a case where the 10 rpm viscosity was 3,000 Pa · s or less and the structural viscosity index was 2.0 or more was evaluated as “◯”, and a case where it was less than 2.0 was evaluated as “X”.
(2) Curability: The curable composition was discharged onto a metal can, the surface of the composition was touched with a spatula over time, and the time until the composition did not adhere to the spatula was measured. Evaluation is 23 ° C., 50% R.D. H. (Relative humidity) It implemented. In the determination, the case of less than 30 minutes was indicated by ◯, the case of 30 minutes or more and less than 60 minutes was indicated by Δ, and the case of 60 minutes or more was indicated by ×.
(3) Adhesiveness: A curable composition was applied onto a polycarbonate and glass plate in a bead shape (width: about 15 mm, thickness: 4-8 mm), and after about 1 week, a notch of about 10 mm was put into the adhesive interface with a razor blade, The fractured state when pulled in the direction of about 180 degrees was observed. All operations were 23 ° C., 50% R.D. H. (Relative humidity) It implemented. In the determination, the case of cohesive failure was indicated by ◯, the case of interfacial failure was indicated by ×, and the case where cohesive failure and interfacial failure were mixed was indicated by △.
(4) Transparency of cured product: Pour the curable composition into a 2 mm thick formwork, 23 ° C., 50% R.D. H. The mixture was allowed to stand for 3 days under the above conditions, and then allowed to stand for 4 days in a dryer at 50 ° C. for curing. Using a haze meter (Color Quest CQ, manufactured by Hunter Lab), the transparency of the resulting cured sheet was measured. In the determination, a case where the haze value was less than 30 was evaluated as ◯, a case where it was 30 or more and less than 50 was evaluated as Δ, and a case where it was 50 or more was evaluated as ×. In addition, in order to evaluate the durability, a 90 ° C. heat test (7 days) and a QUV weather resistance test (420 Hr) were performed, and the transparency of the sheet was measured.
QUV weather resistance test: apparatus; QUV / se, Q-PANEL (manufactured by LAB PRODUCTS), test conditions: QUV-A (wavelength 295 to 365 nm) × 70 ° C. × 8 Hr + 50 ° C./100% R.V. H. (No UV irradiation) x 4 Hr repetition.
(5) Yellowing of hardened material: About the hardened material sheet produced by the above-mentioned method, the yellowing degree was visually evaluated in five stages. ○: Low yellowness, ○ △: Low yellowness to medium, Δ: Medium yellowness, Δ ×: Yellowness medium to large, ×: High yellowness.

  The evaluation results are shown in Table 1.

  As described above, the curable compositions described in the examples have good workability and high transparency, are well adhered to various adherends after curing, and are also yellowed by an accelerated test assuming long-term use. The degree was low. On the other hand, in the composition of the comparative example, a system that expresses these physical properties in a well-balanced manner was not found.

  The curable composition of the present invention is not limited, but is a sealing material for building or DIY, an adhesive, a coating material, a gasket, a casting material, various molding materials, an artificial marble, and a meshed glass or a laminated glass. Used for rust prevention and waterproof sealing materials for end faces (cut parts), anti-vibration / vibration-proof / sound-proof / isolation materials used in automobiles, ships, home appliances, etc., automotive parts, electrical parts, various machine parts, etc. It can be used for various applications such as liquid sealants. Especially, when performing adhesion | attachment and sealing of a transparent polycarbonate plate, an acrylic board, a glass plate, etc., it can utilize as a suitable material.

Claims (8)

(A) The following general formula (1):
—Si (R ¹ _3-a ) X _a (1)
(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, X represents a hydroxyl group or a hydrolyzable group. 100 parts by weight of an organic polymer having a reactive silicon group represented by
(B) In one molecule, the following general formula (2):
-SiX ₃ (2)
(Wherein X represents a hydroxyl group or a hydrolyzable group) and the compound (b1) having a reactive silicon group and one amino group represented by the following general formula ( 3):
-Si (R ¹ ) X ₂ (3)
(Wherein R ¹ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and X represents a hydroxyl group or a hydrolyzable group). 0.01 to 30 parts by weight of a compound having a reactive silicon group and amino group (b2)
(C) 2 to 70 parts by weight of hydrophobic fine powder silica,
(D) 0.01 to 20 parts by weight of a curing catalyst, and
(E) A curable composition containing 0.01 to 20 parts by weight of a phosphorus-based stabilizer . The component (B) is represented by the following general formula (2):
-SiX ₃ (2)
2. The curing according to claim 1, wherein the compound is a compound (b1) having a reactive silicon group represented by (wherein X represents a hydroxyl group or a hydrolyzable group) and one amino group. Sex composition. The curable composition according to claim 2, wherein the hydrolyzable group of the component (b1) is a methoxy group. The component (A) is a polyoxyalkylene polymer (a1) and / or a vinyl polymer (a2) having a reactive silicon group represented by the general formula (1). The curable composition according to any one of to 3 . The curable composition according to any one of claims 3 to 4 , wherein the phosphorus stabilizer as the component (E) is composed of phosphites. (C) Hydrophobic fine powder silica of a component consists of fumed silica, The curable composition in any one of Claims 1-5 characterized by the above-mentioned. The sealing material which consists of a curable composition as described in any one of Claims 1-6 . The adhesive agent which consists of a curable composition as described in any one of Claims 1-6 .