JP4504068B2 - Curable composition with excellent weather resistance - Google Patents

Description

  The present invention relates to a curable composition, and particularly to a curable composition having excellent weather resistance.

  Conventionally, a stabilizer is blended in the sealing material in order to impart weather resistance. However, the whitening problem described below has nevertheless occurred, which is a major problem to be solved in the sealing material construction field. One of the problems with whitening is that if a masking tape is put away from the joint surface of the adherend due to a mistake when placing the sealing material, a thin layer will be formed after the spatula to flatten the surface of the sealing material at the joint. However, this thin layer portion deteriorates and whitens faster than the sealing material of the joint, which makes the appearance worse and makes the design of the building very worse.

  By the way, there is no technology for solving the whitening phenomenon of these thin layer portions (hereinafter collectively referred to as thin layer portions). In other words, as a stabilizer for a sealing material, a combination of a benzotriazole-based UV absorber and a hindered phenol-based antioxidant as shown in Patent Document 1 or a benzotriazole-based UV light as shown in Patent Document 2 so far. A combination of an absorber and a specific hindered amine light stabilizer, and a combination of a benzotriazole ultraviolet absorber and a hindered amine light stabilizer containing a specific triazine skeleton as shown in Patent Document 3, for example. However, these are effective for a sealing material of a joint portion having a thick layer (for example, a thickness of 5 mm or more) (hereinafter collectively referred to as a thick layer portion), but effective for a thin layer portion. There is no known stabilizer formulation that simultaneously improves the weather resistance of the thin layer portion.

From the above, in the field of sealing materials, there is a need for a sealing material designed so that the thin layer portion does not deteriorate and whiten faster than the thick layer portion, and at the same time the thick layer portion also exhibits excellent weather resistance. ing. In Patent Document 4, a combination of a benzotriazole ultraviolet absorber and a hindered amine compound having a molecular weight of 200 to 1000 as a light stabilizer and having no triazine skeleton in the molecule and a hindered amine compound having a triazine skeleton in the molecule Although it is a stabilizer blend with good weather resistance in the thick layer portion, it could not be said that the weather resistance was still sufficient.
JP-A-5-287186 JP-A-61-233043 JP-A-8-48888 JP 2001-271057 A Japanese Patent Publication No. 1-58219 Japanese Patent No. 3062625 JP-A-8-337713 JP 2003-138151 A Japanese Patent Laid-Open No. 11-12480 JP-A-52-73998 JP 55-9669 A JP 59-122541 A Japanese Unexamined Patent Publication No. 60-6747 Japanese Unexamined Patent Publication No. Sho 63-112642 JP-A-3-79627 JP-A-4-283259 JP-A-5-70531 Japanese Patent Laid-Open No. 11-80571 Japanese Patent Laid-Open No. 11-116763 JP-A-11-130931 Japanese Patent Laid-Open No. 2001-40037 Japanese Patent No. 3313360 JP 2004-51830 A JP 2004-59782 A JP 2001-329065 A JP 2001-271055 A WO96 / 30421 publication WO97 / 18247 WO98 / 01480 publication WO98 / 40415 publication JP-A-9-208616 Japanese Patent Laid-Open No. 8-41117 JP-A-4-132706 JP-A 61-271306 Japanese Patent No. 2594402 JP 54-47782 A J. Am. Chem. Soc., 1994, 116, 7943 Macromolecules, 1994, 27, 7228 J. Am. Chem. Soc., 1995, 117, 5614 Macromolecules, 1995, 28, 7901 Science, 1996, 272, 866 Macromolecules, 1995, 28, 1721 Macromolecules, 1999, 32, 2872

  An object of the present invention is to provide a curable composition having improved weather resistance in a thin layer portion and a thick layer portion.

In order to solve the above problems, the curable composition of the present invention comprises (A) a crosslinkable silyl group-containing organic polymer, (B) a UV absorber having a triazine skeleton and a hydroxyphenyl skeleton , and (C) a hindered amine system. Containing a light stabilizer, 0.1 to 10 parts by weight of the component (B) and 0.1 to 10 parts by weight of the component (C) with respect to 100 parts by weight of the component (A), (A) The crosslinkable silyl group-containing organic polymer contains 50 to 100% by weight of a (meth) acrylic polymer having a crosslinkable silyl group at the molecular chain end, and has the crosslinkable silyl group at the molecular chain end. The (meth) acrylic polymer is a (meth) acrylic polymer produced by a living radical polymerization method.

  The component (A) crosslinkable silyl group-containing organic polymer is a crosslinkable silyl group-containing polyoxyalkylene polymer, a crosslinkable silyl group-containing (meth) acryl-modified polyoxyalkylene polymer, and a crosslinkable silyl group-containing polymer. It is preferably one or more compounds selected from the group consisting of (meth) acrylic polymers, and a (meth) acrylic polymer having a crosslinkable silyl group at the end of the molecular chain, and the crosslinkable silyl group. A mixture of a (meth) acrylic polymer at the molecular chain terminal and a crosslinkable silyl group-containing polyoxyalkylene polymer is more preferred. In the present invention, acryl and methacryl are collectively referred to as (meth) acryl.

  The method for producing the (meth) acrylic polymer having a crosslinkable silyl group at the terminal is not particularly limited, but a controlled radical polymerization method is preferable, a living radical polymerization method is more preferable, and an atom transfer radical polymerization method is further preferable.

  It is preferable to further add (D) a compound that reacts with water to form an amine compound to the curable composition of the present invention.

  As the component (C) hindered amine light stabilizer, a hindered amine compound having a triazine skeleton or a hindered amine compound having no triazine skeleton can be used. Further, as the component (C) hindered amine light stabilizer, a mixture of a hindered amine compound having a triazine skeleton and a hindered amine compound not having a triazine skeleton may be used.

  ADVANTAGE OF THE INVENTION According to this invention, the curable composition which improved the weather resistance in a thin layer part and a thick layer part can be obtained. Furthermore, according to the present invention, it is also possible to obtain a curable composition having excellent weather resistance and non-staining properties.

  Embodiments of the present invention will be described below, but these embodiments are exemplarily shown, and it goes without saying that various modifications can be made without departing from the technical idea of the present invention.

The curable composition of the present invention is characterized by containing the following components (A), (B) and (C).
(A) Crosslinkable silyl group-containing organic polymer (B) Ultraviolet absorber having triazine skeleton (C) Hindered amine light stabilizer

  As the component (A), a silicon-containing group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond, that is, an organic polymer containing a crosslinkable silyl group is used. Is done. Examples of such a crosslinkable silyl group-containing organic polymer (A) include those disclosed in Patent Documents 1, 2, and 5-26. Specifically, the crosslinkable silyl group-containing organic polymer (A) specifically includes a crosslinkable silyl group, the main chain may each contain an organosiloxane, a polyoxyalkylene polymer, a vinyl-modified polymer. Examples thereof include polyoxyalkylene polymers, vinyl polymers, polyester polymers, (meth) acrylic acid ester polymers, copolymers and mixtures thereof.

  The crosslinkable silyl group is not particularly limited, but generally 1 to 6 crosslinkable silyl groups are contained in the molecule from the viewpoint of the curability of the composition and the physical properties after curing. Further, the crosslinkable silyl group is preferably one represented by the following general formula (1) which is easy to crosslink and easy to produce.

Wherein (1), R ¹ is a monovalent organic group having a substituted or unsubstituted 1 to 20 carbon atoms, an alkyl group, the number aryl group or C 6 to 20 carbon atoms having 1 to 20 carbon atoms 7 An aralkyl group of ˜20 is preferred, and a methyl group is most preferred. When a plurality of R ¹ are present, they may be the same or different. X is a hydroxyl group or a hydrolyzable group, and is a group selected from a halogen atom, hydrogen atom, hydroxyl group, alkoxy group, acyloxy group, ketoximate group, amide group, acid amide group, mercapto group, alkenyloxy group and aminooxy group Are preferred, alkoxy groups are more preferred, and methoxy groups are most preferred. When a plurality of X are present, they may be the same or different. a is 1, 2 or 3, and 2 is most preferable. ]

  In the crosslinkable silyl group-containing organic polymer (A), when a plurality of crosslinkable silyl groups are present, these may be the same or different, and the number of a in the formula (1) is also They can be the same or different. Two or more organic polymers having different crosslinkable silyl groups may be used.

  The main chain of the crosslinkable silyl group-containing organic polymer (A) is a polyoxyalkylene polymer which may contain an organosiloxane from the viewpoint of physical properties such as tensile adhesiveness after curing and modulus. A (meth) acryl-modified polyoxyalkylene polymer, a (meth) acrylic polymer, a copolymer or a mixture thereof is preferable.

  The crosslinkable silyl group-containing organic polymer (A) is particularly preferably a vinyl polymer having a crosslinkable silyl group at the end, and a (meth) acrylic polymer having a crosslinkable silyl group at the end, In addition, a mixture of the (meth) acrylic polymer having the crosslinkable silyl group and the polyoxyalkylene polymer having the crosslinkable silyl group is more preferable.

  The manufacturing method of the said crosslinkable silyl group containing organic polymer (A) is not specifically limited, A well-known synthesis method can be utilized. When the crosslinkable silyl group-containing organic polymer contains a crosslinkable silyl group and the main chain is a vinyl polymer such as an acrylic polymer, a vinyl polymer synthesized by a radical polymerization method is used. Is preferably used.

  The radical polymerization method uses a general radical polymerization method in which a monomer having a specific functional group and a vinyl monomer are simply copolymerized using an azo compound, a peroxide, or the like as a polymerization initiator. The control radical polymerization method can introduce a specific functional group at a controlled position. In the present invention, a vinyl polymer synthesized by a controlled radical polymerization method is more effective.

  The controlled radical polymerization method further includes a chain transfer agent method in which a vinyl polymer having a functional group at the terminal is obtained by polymerization using a chain transfer agent having a specific functional group, and a polymerization growth terminal is terminated. It can be divided into the living radical polymerization method that grows without causing etc.

  The living radical polymerization method has an arbitrary molecular weight, a molecular weight distribution is narrow, a polymer having a low viscosity can be obtained, and a monomer having a specific functional group can be introduced at an arbitrary position. Is particularly preferred. In the present invention, in addition to the polymerization in which the terminal always has activity and the molecular chain grows, the terminal inactivated and the activated one are grown while in equilibrium. Living polymerization is also included in living polymerization.

  Examples of the living radical polymerization method include a method using a cobalt porphyrin complex as disclosed in Non-Patent Document 1, a method using a radical scavenger such as a nitroxide compound as disclosed in Non-Patent Document 2, and the like. Atom transfer radical polymerization (Atom Transfer) in which vinyl monomers are polymerized using an organic halogen compound or a sulfonyl halide compound as disclosed in Patent Documents 3 to 6 and Patent Documents 27 to 32 as an initiator and a transition metal complex as a catalyst. Radical Polymerization (ATRP) method and the like. The living radical polymerization method is not particularly limited, but the atom transfer radical polymerization method is preferable. In the present invention, a reverse atom transfer radical polymerization method, that is, a high oxidation state when a normal atom transfer radical polymerization catalyst generates radicals, for example, Cu (II) when Cu (I) is used as a catalyst, is used. In addition, a method in which a general radical initiator such as a peroxide is allowed to act on, and as a result an equilibrium similar to that of atom transfer radical polymerization (see, for example, Non-Patent Document 7) is also used. Is included.

  Examples of the chain transfer agent method include a method of obtaining a halogen-terminated polymer using a halogenated hydrocarbon as disclosed in Patent Document 33 as a chain transfer agent, and Patent Documents 34 to 36. Examples thereof include a method for obtaining a hydroxyl-terminated polymer using such a hydroxyl group-containing mercaptan or a hydroxyl group-containing polysulfide as a chain transfer agent.

  Hereinafter, the atom transfer radical polymerization method will be described. As an initiator of the atom transfer radical polymerization method, 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). Alternatively, a sulfonyl halide compound or the like is used.

  Further, as an initiator of atom transfer radical polymerization, an organic halide having a functional group other than a functional group for initiating polymerization, such as an alkenyl group, a crosslinkable silyl group, a hydroxyl group, an epoxy group, an amino group, an amide group, or the like Halogenated sulfonyl compounds can also be used. In this case, a vinyl polymer having a functional group at one end of the main chain and a growth terminal structure of atom transfer radical polymerization at the other main chain end is synthesized. In the present invention, it is preferable to use an organic halide or sulfonyl halide compound having a crosslinkable silyl group. In this case, a polymer having a crosslinkable silyl group at one end and a halogen end at the other end is obtained, and a polymer having a crosslinkable silyl group at both ends is obtained by substituting the halogen end. be able to.

  Although it does not specifically limit as a vinyl-type monomer used in superposition | polymerization, In this invention, acrylic-type single quantities, such as (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, etc. The main component is preferably one or more of the body, and more preferably a main component is a (meth) acrylic acid ester such as alkyl (meth) acrylate and alkoxyalkyl (meth) acrylate.

  Although there is no limitation in particular as a transition metal complex used as a polymerization catalyst, the metal complex complex which uses a 7th, 8th, 9th, 10th, or 11th group element of a periodic table as a central metal is preferable, and a zerovalent A complex of copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel is more preferred, and a copper complex is particularly preferred.

  Examples of the monovalent copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, and the like. 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.

In addition, tristriphenylphosphine complex of divalent ruthenium chloride [RuCl ₂ (PP
h ₃ ) ₃ ] divalent iron bistriphenylphosphine complex [FeCl ₂ (PPh ₃ ) ₂ ], 2
Bivalent nickel bistriphenylphosphine complex [NiCl ₂ (PPh ₃ ) ₂ ] and 2
A bivalent bistributylphosphine complex of nickel [NiBr ₂ (PBu ₃ ) ₂ ] is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator.

  The polymerization can be carried out without solvent or in various solvents. The polymerization temperature is preferably in the range of 0 to 200 ° C, more preferably in the range of room temperature to 150 ° C.

  Acrylics having a halogen at the end by radical polymerization of vinyl monomers containing acrylic monomers as the main component, using organic halides or sulfonyl halides as initiators and transition metal complexes as catalysts. A polymer is produced. The (meth) acrylic polymer having a crosslinkable silyl group at the molecular chain end used in the present invention can be obtained by converting the halogen of the acrylic polymer having the halogen at the end to a crosslinkable silyl group. . The conversion method is not particularly limited, and a known method (for example, see Patent Documents 18 to 20, 23 to 26, etc.) can be used.

  In the present invention, the number-average molecular weight of the crosslinkable silyl group-containing organic polymer (A) is from 1,000 to 100,000, particularly those having a molecular weight distribution of 3000 to 50,000 are narrow and easy to handle because the viscosity before curing is low. Physical properties such as later strength, elongation, modulus, etc. are preferred. The crosslinkable silyl group-containing organic polymer (A) may be used alone or in combination of two or more.

  The component (B) is not particularly limited as long as it is a UV absorber having a triazine skeleton, and known compounds can be widely used. Specific examples of the (B) include triazine compounds as shown by the following formula (2).

[In Formula (2), R ^{2 to} R ⁷ are each independently a hydrogen atom, a hydroxyl group, a halogen atom, or a substituted or unsubstituted monovalent organic group, and include a hydrogen atom, a hydroxyl group, a halogen atom, and a carbon number. A C1-C18 alkyl group or a C1-C18 alkoxy group is preferable. ]

In particular, 2- (2-hydroxyphenyl) -1,3, wherein R ² in formula (2) is a hydrogen atom.
A 5-triazine compound or a polymerizable triazine compound as represented by the following general formula (3) is preferred.

[In Formula (3), R < ³ >, R < ⁵ > and R < ⁷ > are the same as the above, and a hydrogen atom or a C1-C6 alkyl group is preferable, R < ⁸ > shows a hydrogen atom or a methyl group, R <^9> is A substituted or unsubstituted divalent organic group, an alkylene group having 1 to 6 carbon atoms, a — (— CH ₂ CH ₂ —O—) m-group (m is an integer of 1 to 5), or —CH ₂ CH; (OH) —CH ₂ O— groups are preferred. ]

  Examples of the 2- (2-hydroxyphenyl) -1,3,5-triazine compound include 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine. 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4, 6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyl) Oxy Enyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4- Dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxy-propoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3 5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxy-phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5- G Azine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxy-propoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, the following formula 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6 represented by (4) -Diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxy-propoxy) phenyl] -1,3,5-triazine, 2- ( 2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2 -Hide Roxypropyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-methoxyphenyl) -4- (2 represented by the following formula (5) -Hydroxyphenyl) -6-phenyl-1,3,5-triazine, 2,4-bis (2-methoxyphenyl) -6- (2-hydroxyphenyl) -1,3 represented by the following formula (6) Examples include 5-triazine, compounds represented by the following general formulas (7) and (8), and the like.

[In Formula (7), R < ¹⁰ > and R < ¹¹ > is a methyl group or a C1-C8 alkoxy group, respectively, R < ¹² > is a hydrogen atom, a chlorine atom, a methyl group, or a methoxy group, R <^13> is carbon number. 1 to 8 alkoxy groups, and R ¹⁴ is a hydrogen atom or a methoxy group. ]

[In Formula (8), R < ¹⁴ > is the same as the above, and R < ¹⁵ > is a hydrogen atom or a methyl group. ]

  Examples of the polymerizable triazine compound include 2,4-diphenyl-6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-s-triazine, 2,4-diphenyl-6- [2-hydroxy. -4- (2-acryloyloxyethoxy)]-s-triazine, 2,4-bis (2-methylphenyl) -6- [2-hydroxy-4- (3-acryloyloxy-2-hydroxypropoxy)] -S-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-s-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-s-triazine, 2,4-bis (2-ethoxyphenyl) -6- [2-hydride Xyl-4- (2-acryloyloxyethoxy)]-s-triazine, 2,4-diphenyl-6- [2-hydroxy-4- (2-methacryloyloxyethoxy)]-s-triazine 2,4-bis ( 2-Methylphenyl) -6- [2-hydroxy-4- (2-methacryloyloxyethoxy)]-s-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- ( 2-methacryloyloxyethoxy)]-s-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- (2-methacryloyloxyethoxy)]-s-triazine, 2,4- Bis (2-ethoxyphenyl) -6- [2-hydroxy-4- (2-methacryloyloxyethoxy)]-s-triazine, 2,4-bis (2,4-di Toxiphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-s-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- ( 2-acryloyloxyethoxy)]-s-triazine, 2,4-bis (2,4-diethoxyphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-s-triazine, 2 , 4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-s-triazine and the like.

  The blending ratio of the component (B) is not particularly limited, but it is preferably 0.1 to 50 parts by weight, particularly 1.0 to 10 parts by weight based on 100 parts by weight of the component (A). . The ultraviolet absorber having the triazine skeleton may be used alone or in combination of two or more.

  The component (C) hindered amine light stabilizer may be a hindered amine compound (C1) having a triazine skeleton or a hindered amine compound (C2) having no triazine skeleton, and is not particularly limited. . These hindered amine light stabilizers may be used alone or in combination of two or more. When two or more types are used in combination, the combination is not particularly limited, and a mixture of a hindered amine compound having a triazine skeleton and a hindered amine compound having no triazine skeleton can also be used.

  Examples of the hindered amine compound (C1) having a triazine skeleton include 1,5,8,12-tetrakis [4,6-bis {N- (2,2,6,6-tetramethyl-4-piperidyl). Butylamino} -1,3,5-triazin-2-yl] -1,5,8,12-tetraazadodecane, N, N ′, N ″, N ″ ′-tetrakis- (4,6-bis ( Butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl- -Piperidyl) imino}], N, N′-bis (3-aminopropyl) ethylenediamine · 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) Amino] -6-chloro-1,3,5-triazine condensate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino- Linear or cyclic condensates with 2,6-dichloro-1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4 A linear or cyclic condensate with morpholino-2,6-dichloro-1,3,5-triazine, 2-chloro-4,6-di (4-n-butylamino-2,2,6,6- Tetramethylpiperidyl) -1,3,5- Condensation product of lyazine and 1,2-bis (3-aminopropylamino) ethane, 2-chloro-4,6-di (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane condensate, N, N′-bis- (2,2,6,6-tetramethyl-4-piperidyl) Condensation product of hexamethylenediamine and 4-chlorohexylamino-2,6-dichloro-1,3,5-triazine, 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro -1,3,5-triazine and the condensation product of 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Registry No. [136504-96-6]), dibutylamine 5-triazine N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamineN- (2,2,6,6-tetramethyl-4-piperidyl) Examples include hindered amine compounds containing a triazine skeleton in the molecule such as a polycondensate of butylamine. These hindered amine compounds containing a triazine skeleton in the molecule may be used alone or in combination of two or more.

  Examples of the hindered amine compound (C2) having no triazine skeleton include 2,2,6,6-tetramethyl-4-piperidyl stearate and 1,2,2,6,6-pentamethyl-4-piperidyl stearate. 2,2,6,6-tetramethyl-4-piperidylbenzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide, 1-[(3,5-di- Tert-butyl-4-hydroxyphenyl) propionyloxyethyl] -2,2,6,6-tetramethyl-4-piperidinyl- (3,5-ditert-butyl-4-hydroxyphenyl) propionate, bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl 1 2,2,6,6-pentamethyl-4-piperidyl sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl)- 4-hydroxyphenyl] methyl] butyl malonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidylsebacate Mixture, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, tetra (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, Tetra (1,2,2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) di Tridecyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2- { Tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 1- (2- Hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / dimethyl succinate condensate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine / Dibromoethane condensate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1-octyloxy-2,2,6) , 6-Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate , 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid condensate, tris (2,2,6,6-tetramethyl-4-piperidyl) Nitrilotriacetate, 1,1 '-(1,2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4 -Benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethylpiperidine Gil) -2-n-butyl-2- (2-hydroxy-3,5-di-tert-butyl-benzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3 , 8-triazaspiro [4.5] decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6) , 6-tetramethylpiperidyl) succinate, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 3- Dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl ) -Pyrrolidine-2,5-di , A mixture of 4-hexadecyloxy-2,2,6,6-tetramethylpiperidine and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, N- (1,2,2,6, 6-pentamethyl-4-piperidyl) -n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4,5 Reaction of decane, 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxo-spiro [4,5] decane with epichlorohydrin 1,1-bis (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) ethane, N, N′-bisformyl-N, N′-bis (2,2,6,6-tetrame Til-4-piperidyl) -hexamethylenediamine; diester of 4-methoxymethylenemalonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly [methylpropyl-3-oxy-4- ( 2,2,6,6-tetramethyl-4-piperidyl)] siloxane; maleic anhydride-α-olefin copolymer and 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6 , 6-pentamethyl-4-aminopiperidine reaction product, [decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidyl) ester, 1,1-dimethylethyl Reaction product of hydroperoxide and octane (70%)]-polypropylene (30%), 1- [2- [3- (3,5-di-tert-butyl) Ru-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, And hindered amine compounds. These hindered amine compounds having no triazine skeleton may be used alone or in combination of two or more.

  The mixing ratio of the component (C) is not particularly limited, but it is preferably 0.1 to 50 parts by weight, particularly 1.0 to 10 parts by weight with respect to 100 parts by weight of the component (A). .

  It is preferable to add (D) a compound that reacts with water to produce an amine compound to the curable composition of the present invention, since the non-staining property can be remarkably improved. Specific examples of the component (D) include an amine compound ketimine compound, enamine compound, and / or aldimine compound from the viewpoint of easy availability of raw materials, storage stability, and reactivity with water. As mentioned.

  The ketimine compound, enamine compound and aldimine compound can be obtained by dehydration reaction of (D1) amine compound and (D2) carbonyl compound, respectively. The manufacturing method of the said component (D) is not specifically limited, A well-known method can be used.

  The amine compound (D1) is not particularly limited, and examples thereof include primary and / or secondary amines and amine compounds having at least one alkoxysilyl group in one molecule. An amine compound having at least one alkoxysilyl group in the molecule is particularly preferable because of excellent adhesion.

  Examples of the primary amine include monoamines such as butylamine, hexylamine, heptylamine, 2-ethylhexylamine, octylamine, 3-methoxypropylamine, tetradecylamine, pentadecylamine, cetylamine, stearylamine, and trimethylcyclohexylamine. , Benzylamine, aniline and the like. Examples of the diamine include ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, 1,7-diaminoheptane, Trimethylhexamethylenediamine, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20- Diaminoeicosane, 1,2-diaminohenticosane, 1,2-diaminodocosane, 1,23-diaminotricosane, 1,24-diaminotetracosane, isophoronediamine, diaminodicyclohexylmethane, 3,9- Bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, xylenediamine, phenylenediamine, diaminodiphenylmethane, diaminodiethylphenylmethane, polyoxyethylenediamine, polyoxypropylenediamine, etc. To mention It can, as a polyamine, such as hexane tri (methylamino) can be exemplified. Examples of secondary amines include monoamines such as dilaurylamine, distearylamine, and methyllaurylamine, N, N'-dilaurylpropylamine, N, N'-distearylbutylamine, and N-butyl-N'-. Examples thereof include diamines such as laurylethylamine, N-butyl-N′-laurylpropylamine, and N-lauryl-N′-stearylbutylamine. Examples of the primary and secondary mixed amines include N-lauryl propylene diamine and N-stearyl propylene diamine. Examples of the primary and secondary mixed polyamines include diethylenetriamine, triethylenetetramine, and methylaminopropylamine.

  Examples of the amine compound having at least one alkoxysilyl group in one molecule include those represented by the following general formula (9).

[In formula (9), n = 0, 1, 2, R ¹⁶ and R ¹⁷ are the same or different and each is a hydrocarbon group having 1 to 4 carbon atoms, and R ¹⁸ is a hydrocarbon having 1 to 10 carbon atoms. The group Y represents a hydrogen atom or an aminoalkyl group having 1 to 4 carbon atoms. ]

Here, examples of R ¹⁶ and R ¹⁷ include alkyl groups such as methyl, ethyl, propyl, and butyl, and alkenyl groups such as vinyl, allyl, propenyl, and butenyl, and alkyl groups are particularly preferable. Examples of R ¹⁸ include alkylene groups such as methylene, ethylene, propylene, and butylene, arylene groups such as phenylene, alkylene arylene groups, and the like, and alkylene groups are particularly preferable. n is preferably 0 or 1.

  Specific examples include compounds represented by the following formulas (10) to (17), N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyl. Examples include aminosilanes typified by methyldimethoxysilane. Among these, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane and the like are adhesive. Is particularly preferable.

  Examples of the carbonyl compound (D2) include known compounds such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-amylaldehyde, isohexylaldehyde, diethylacetaldehyde, glyoxal, benzaldehyde, phenylacetaldehyde and the like. Aldehydes; cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone, methylcyclohexanone, trimethylcyclohexanone; acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl tert-butyl ketone, diethyl ketone, Aliphatic keto such as dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone Aromatic ketones such as acetophenone, benzophenone, propiophenone; and the following general formula (18) such as acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate, diethyl malonate, methyl ethyl malonate, dibenzoylmethane However, it is not limited to these. Among these, methyl isobutyl ketone, dipropyl ketone, phenylacetaldehyde, and a β-dicarbonyl compound having an active methylene group [compound represented by the following general formula (18)] are more preferable.

[In the formula (18), R ¹⁹ and R ²⁰ are the same or different and each is an alkyl group having 1 to 16 carbon atoms (for example, methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, nonyl, decyl, undecyl). Hexadecyl, etc.), an aryl group having 6 to 12 carbon atoms (for example, phenyl, tolyl, hexyl, naphthyl, etc.), or an alkoxyl group having 1 to 4 carbon atoms (for example, methoxy, ethoxy, prooxy, putoxy, etc.). means. ]

  In the component (D) of the present invention, the compound that reacts with water to produce an amine compound having at least one alkoxysilyl group in one molecule is not particularly limited, and a compound obtained by a known production method is used. Although the monomer purity is 50 to 95%, preferably 70 to 95%, more preferably 80 to 95%, and the amino group blocking ratio is 90% or more, preferably 95% or more. Used for.

  The blending ratio of the component (D) is not particularly limited, but the component (D) is 0.05 to 50 parts by weight, particularly 0.1 to 20 parts by weight with respect to 100 parts by weight of the component (A). It is preferable to blend in. The compound which reacts with water to produce an amine compound may be used alone or in combination of two or more.

  In addition, it is preferable to further add (D1) an amine compound and (D2) a carbonyl compound to the curable composition of the present invention in order to improve non-staining properties. As the component (D1) and the component (D2), the amine compounds and carbonyl compounds mentioned in the description of the component (D) can be used in the same manner. The component (D1) and the component (D2) cause a dehydration reaction in the blend. The dehydration reaction may be carried out by a reaction treatment such as a heat treatment as necessary, but can be progressed over time without performing a special step.

  The blending ratio of the components (D1) and (D2) is not particularly limited, but the components (D1) and (D2) are each 0.05 to 50 parts by weight, particularly 0. It is preferable to mix | blend so that it may become 1-20 weight part. Furthermore, [molar amount of component (D1)] / [molar amount of component (D2)] is preferably in the range of 0.1 to 5.0, and preferably in the range of 0.5 to 2.0. Further preferred. The amine compound and the carbonyl compound may be used alone or in combination of two or more.

  The curable composition of the present invention comprises, in addition to the above-described components, an adhesion-imparting agent, a physical property modifier, a filler, a curing catalyst, a plasticizer, a thixotropic agent, a dehydrating agent (a storage stability improving agent). ), Tackifiers, sagging inhibitors, antioxidants, flame retardants, colorants, radical polymerization initiators, and various solvents such as toluene and alcohol, or other compatible polymers May be blended. In addition, the curable composition of the present invention includes a benzotriazole-based, triazine-based, benzophenone-based, benzoate-based, salicylic acid-based component (B) a UV absorber other than the triazine-based component and a component (C) a light-stable component other than the hindered amine-based component. An agent may be further added.

  As the other compatible polymer, various polyethers are particularly preferable, and particularly, polyethers having a silicon functional group are exemplified.

  Examples of the adhesion-imparting agent include various silane coupling agents such as aminosilanes such as aminoethylaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, aminoethylaminopropylmethylmethoxysilane, and γ-glycidoxypropyltrimethyl. Examples include epoxy silanes such as methoxysilane, acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, mercaptosilanes such as γ-mercaptopropyltrimethoxysilane, and isocyanate silanes such as γ-isocyanatopropyltrimethoxysilane. It is done. The said adhesion grant agent may be used independently and may be used together 2 or more types.

  The physical property modifier is added for the purpose of improving the tensile physical properties. Examples of the physical property adjusting agent include a silicon compound having one silanol group in one molecule, and examples thereof include triphenylsilanol, trialkylsilanol, dialkylphenylsilanol, diphenylalkylsilanol, and the like. Various silane coupling agents such as silicon compounds that can be decomposed to produce a compound having one silanol group in one molecule, such as triphenylmethoxysilane, trialkylmethoxysilane, dialkylphenylmethoxysilane, diphenylalkylmethoxy Silane, triphenylethoxysilane, trialkylethoxysilane, etc. are mentioned. The physical property modifiers may be used alone or in combination of two or more.

  The filler is added for the purpose of reinforcing the cured product. Examples of the filler include calcium carbonate, magnesium carbonate, diatomaceous earth hydrous silicic acid, hydrous silicic acid, anhydrous silicic acid, calcium silicate, silica, titanium dioxide, clay, talc, carbon black, slate powder, mica, kaolin, and zeolite. Of these, calcium carbonate is preferable, and fatty acid-treated calcium carbonate is more preferable. In addition, glass beads, silica beads, alumina beads, carbon beads, styrene beads, phenol beads, acrylic beads, porous silica, shirasu balloons, glass balloons, silica balloons, saran balloons, acrylic balloons, etc. can be used. Among them, an acrylic balloon is more preferable from the viewpoint that the decrease in elongation after curing of the composition is small. The above fillers may be used alone or in combination of two or more.

  The plasticizer is added for the purpose of improving the elongation physical properties after curing or enabling low modulus. Examples of the plasticizer include phosphate esters such as tributyl phosphate and tricresyl phosphate; phthalate esters such as dioctyl phthalate (DOP), dibutyl phthalate and butyl benzyl phthalate; fatty acid monobases such as glycerin monooleate Acid esters; fatty acid dibasic acid esters such as dibutyl adipate and dioctyl adipate; glycol esters such as polypropylene glycol; aliphatic esters; epoxy plasticizers; polyester plasticizers; polyethers; Is mentioned. The said plasticizer may be used independently or may use 2 or more types together.

  Examples of the thixotropic agent include inorganic thixotropic agents such as colloidal silica and asbestos powder, organic thixotropic agents such as organic bentonite, modified polyester polyol, and fatty acid amide, hydrogenated castor oil derivative, fatty acid amide wax, and aluminum stearylate. And barium stearylate. The thixotropic agents may be used alone or in combination of two or more.

  The dehydrating agent is added for the purpose of removing moisture during storage. Examples of the dehydrating agent include silane compounds such as vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane.

  The antioxidant is used to prevent oxidation of the cured sealant and improve weather resistance, and examples thereof include hindered phenol-based antioxidants. Examples of the hindered phenol antioxidant include pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene-bis [3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropioamide], benzenepropanoic acid 3,5-bis (1,1-dimethylethyl) -4-hydroxyC7-C9 side chain alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1- Methylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexane-tert-butyl-4-a, a ′, a ″-(mesitylene-2, 4,6-tolyl) tri-p-cresol, calcium diethylbis [[[3,5-bis- (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate], 4,6-bis (octyl) Thiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5- Liazine-2,4,6- (1H, 3H, 5H) -trione, reaction product of N-phenylbenzenamine and 2,4,4-trimethylpentene, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol and the like, but are not limited to these.The antioxidant may be used alone. Alternatively, two or more types may be used in combination.

  The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.

(Synthesis example 1) The synthesis | combination of the polymer 1 The temperature was maintained at 200 degreeC in the pressure-type stirring tank reactor of the capacity | capacitance of 1000 ml provided with the electrothermal heater. Next, while maintaining the reactor pressure constant, 84 parts of butyl acrylate as an acrylate monomer, 16 parts of γ-methacryloxypropyltrimethoxysilane as a hydrolyzable silyl group-containing monomer, a polymerization initiator As a monomer mixture consisting of 1 part of ditertiary butyl peroxide, a continuous feed from the raw material tank to the reactor was started at a constant feed rate (80 g / min, residence time: 12 minutes). The reaction liquid corresponding to the supply amount was continuously extracted from the outlet.

  Immediately after the start of the reaction, the reaction temperature was once lowered and then a temperature increase due to the heat of polymerization was observed, but the reaction temperature was maintained at 250 to 251 ° C. by controlling the heater. The time when the temperature became stable from the start of the supply of the monomer mixture was taken as the collection start point of the reaction solution, and the reaction was continued for 25 minutes. As a result, 2 kg of the monomer mixture was supplied and 1.9 kg of the reaction solution was added. It was collected. Thereafter, the reaction solution was introduced into a thin film evaporator to separate volatile components such as unreacted monomers to obtain a concentrated solution. From the gas chromatographic analysis, no unreacted monomer was present in the concentrate. Tetrahydrofuran was used as a solvent, the number average molecular weight in terms of polystyrene measured by gel permeation chromatography was 2000, and the weight average molecular weight was 4800. The number of crosslinkable silyl groups per molecule of the polymer was 1.29. On average, Polymer 1 having 1.29 crosslinkable silyl groups in one molecule was obtained.

(Synthesis Example 2)
The synthesis was performed using the compounding substances and the compounding amount (g) shown in Table 1. The primary amine dissolved by heating was placed in a heating apparatus and a stirring vessel equipped with an ester tube, and then the carbonyl compound was added with stirring. Toluene was further added thereto, followed by heating and stirring at 110 to 150 ° C. for 3 hours, and water was dehydrated through an ester tube. Subsequently, the pressure was reduced to remove excess carbonyl compound and toluene to obtain a ketimine compound.

The amount of each compounding substance in Table 1 is indicated by (g), and * 1 and * 2 are as follows. * 1: Stearylamine (Kao Co., Ltd., Farmin 80, amine value 207)
* 2: Methyl isobutyl ketone (4-methyl-2-pentanone, molecular weight: 100.2)

Example 1
As shown in Table 2, as component (A) crosslinkable silyl group-containing organic polymer, modified silicone polymer SA100S (manufactured by Kaneka Chemical Co., Ltd.), component (B) as triazine-based ultraviolet absorber 1577FF (Ciba Specialty Chemicals), CHIMASSORB 119FL (manufactured by Ciba Specialty Chemicals), plasticizer, filler and dehydrating agent as a light stabilizer, respectively, are charged in predetermined amounts, and heated under reduced pressure for 2 hours at 110 ° C. After a while, the compounded material was dehydrated. Furthermore, a ketimine compound obtained in Synthesis Example 2 as component (D), dibutyltin diacetylacetonate as a curing catalyst, and an aminosilane compound as a silane coupling agent are added in predetermined amounts, and mixed with stirring to obtain a curable composition. Prepared.

The compounding amounts of the compounding substances in Table 2 are shown in parts by weight, and * 3 to * 20 are as follows.
* 3: Crosslinkable silyl group-containing acrylic polymer synthesized by living radical polymerization method (trade name: SA100S, manufactured by Kaneka Chemical Co., Ltd.)
* 4: Crosslinkable silyl group-containing acrylic polymer 1 obtained in Synthesis Example 1
* 5: Crosslinkable silyl group-containing acrylic modified polyoxyalkylene polymer (trade name; S911, manufactured by Kaneka Chemical Co., Ltd.)
* 6: Crosslinkable silyl group-containing polyoxyalkylene polymer (trade name; S203, manufactured by Kaneka Chemical Co., Ltd.)
* 7: Triazine UV absorber (trade name: 1577FF, manufactured by Ciba Specialty Chemicals)
* 8: Benzotriazole UV absorber (trade name: LA36, manufactured by Asahi Denka Co., Ltd.)
* 9: A hindered amine compound having a triazine skeleton (trade name: CHIMASSORB 119FL, manufactured by Ciba Specialty Chemicals)
* 10: A hindered amine compound having a triazine skeleton (trade name: CHIMASSORB2020FDL, manufactured by Ciba Specialty Chemicals)
* 11: A hindered amine compound having a triazine skeleton (trade name: CHIMASSORB 944FD, manufactured by Ciba Specialty Chemicals)
* 12: A hindered amine compound having no triazine skeleton (containing -NCH ₃ group, trade name: LA62, manufactured by Asahi Denka Co., Ltd.)
* 13: Hindered amine compound without triazine skeleton (containing -NOR group, trade name: Tinuvin 123, manufactured by Ciba Specialty Chemicals)
* 14: Ketimine compound obtained in Synthesis Example 2 * 15: Antioxidant (trade name; AO-20, manufactured by Asahi Denka Co., Ltd.)
* 16: Acrylic polymer (trade name: UP1000, manufactured by Toagosei Co., Ltd.)
* 17: Calcium carbonate (trade name; CCR, manufactured by Shiroishi Kogyo Co., Ltd.)
* 18: Moisture absorber (trade name: KBM1003, manufactured by Shin-Etsu Chemical Co., Ltd.)
* 19: Aminosilane compound (trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.)
* 20: Dibutyltin diacetylacetonate (trade name; Neostan U220, manufactured by Nitto Kasei Co., Ltd.)

(Example 2)
As shown in Table 2, as the component (A) crosslinkable silyl group-containing organic polymer, 50 parts by weight of modified silicone polymer SA100S (manufactured by Kaneka Chemical Co., Ltd.) and modified silicone polymer S203 (Kanebuchi Chemical Industry Co., Ltd.) )) A curable composition was prepared in the same manner as in Example 1 except that 50 parts by weight were blended.

(Example 3)
As shown in Table 2, a curable composition was prepared in the same manner as in Example 1 except that the component (D) ketimine compound was not blended.

Example 4
As shown in Table 2, a curable composition was prepared in the same manner as in Example 3 except that LA62 (manufactured by Asahi Denka Co., Ltd.) was blended in place of CHIMASSORB119FL as the component (C) light stabilizer.

(Example 5)
As shown in Table 2, a curable composition was prepared in the same manner as in Example 3 except that CHIMASSORB2020FDL (manufactured by Ciba Specialty Chemicals) was blended instead of CHIMASSORB119FL as the component (C) light stabilizer.

(Example 6)
As shown in Table 2, a curable composition was prepared in the same manner as in Example 3 except that CHIMASSORB 944FD (manufactured by Ciba Specialty Chemicals) was blended in place of CHIMASSORB 119FL as the component (C) light stabilizer.

(Example 7)
As shown in Table 2, a curable composition was prepared in the same manner as in Example 3 except that CHIMASSORB 119FL and LA62 were blended as the component (C) light stabilizer.

(Example 8)
As shown in Table 2, a curable composition was prepared in the same manner as in Example 3 except that Tinuvin 123 (manufactured by Ciba Specialty Chemicals) was blended instead of CHIMASSORB 119FL as the component (C) light stabilizer.

Example 9
As shown in Table 2, a curable composition was prepared in the same manner as in Example 8 except that AO-20 (manufactured by Asahi Denka Co., Ltd.) was added as an antioxidant.

(Comparative Example 1)
As shown in Table 2, a curable composition was prepared in the same manner as in Example 4 except that LA36 (manufactured by Asahi Denka Co., Ltd.) was blended in place of Tinuvin 1577FF as an ultraviolet absorber.

(Comparative Example 2)
As shown in Table 2, as the component (A) crosslinkable silyl group-containing organic polymer, the crosslinkable silyl group-containing compound obtained in Synthesis Example 1 was used instead of the modified silicone polymer SA100S (manufactured by Kaneka Chemical Co., Ltd.). A curable composition was prepared in the same manner as in Comparative Example 1 except that the acrylic polymer 1 was blended.

(Comparative Example 3)
As shown in Table 2, as the component (A) crosslinkable silyl group-containing organic polymer, modified silicone polymer S911 (Kanebuchi Chemical Industry Co., Ltd.) instead of modified silicone polymer SA100S (manufactured by Kaneka Chemical Co., Ltd.) A curable composition was prepared in the same manner as in Comparative Example 1 except that the product was blended.

(Comparative Example 4)
As shown in Table 2, as the component (A) crosslinkable silyl group-containing organic polymer, modified silicone polymer S203 (Kanebuchi Chemical Industry Co., Ltd.) instead of modified silicone polymer SA100S (manufactured by Kaneka Chemical Co., Ltd.) A curable composition was prepared in the same manner as in Comparative Example 1 except that the product was blended.

  The following performance test was done about the obtained curable composition. The results are shown in Table 3.

1) Weather resistance test The curable composition was molded into a sheet having a thickness of 5 mm, and cured at 23 ° C for 7 days and subsequently at 30 ° C for 7 days to obtain a thick layer portion of the cured product sheet. Further, a vapor curable composition is formed into a 0.2 mm thick sheet using a metal spacer of a 0.2 mm thick sheet, and cured at 23 ° C. for 7 days, followed by 30 ° C. for 7 days. A thin layer was obtained. The resulting thick layer portion and thin layer portion were irradiated on a die plastic metal weather (Daipura Wintes Co., Ltd., model KU-R4-A), and surface deterioration was visually observed over time.

Evaluation criteria of weather resistance test The thin layer portion was evaluated for the time until complete whitening.
×: Less than 200 hours, Δ: 200 hours or more and less than 500 hours, ○: 500 hours or more and less than 1000 hours, ◎: 1000 hours or more.
The thick layer portion was evaluated for the time until crack generation.
×: Less than 500 hours, Δ: 500 hours or more and less than 800 hours, ○: 800 hours or more and less than 1200 hours, ◎: 1200 hours or more.

2) Non-contamination test The curable composition was formed into a sheet having a thickness of 10 mm, exposed outdoors at 45 ° south for 6 months, and visually checked for surface contamination. The case where the contamination was severe was evaluated as x, the case where there was almost no contamination, and the case where there was no contamination as ◎.

As shown in Table 3, the curable compositions of Examples 1 to 9 exhibited excellent weather resistance not only in the layer thickness part but also in the thin layer part. Further, in Examples 1 and 2 to which the ketimine compound was added, the non-staining property was remarkably improved.

Claims (6)

(A) a crosslinkable silyl group-containing organic polymer,
(B) an ultraviolet absorber having a triazine skeleton and a hydroxyphenyl skeleton , and (C) a hindered amine light stabilizer,
0.1 to 10 parts by weight of the component (B) and 0.1 to 10 parts by weight of the component (C) are blended with respect to 100 parts by weight of the component (A),
The (A) crosslinkable silyl group-containing organic polymer contains 50 to 100% by weight of a (meth) acrylic polymer having a crosslinkable silyl group at the molecular chain end,
The (meth) acrylic polymer having a crosslinkable silyl group at the molecular chain end is a (meth) acrylic polymer produced by a living radical polymerization method, and has a weatherable curable composition. object.   The curable composition according to claim 1, wherein the polymer (A) is a (meth) acrylic polymer produced by an atom transfer radical polymerization method.   2. The polymer (A) is a mixture of a (meth) acrylic polymer having a crosslinkable silyl group at a molecular chain terminal and a crosslinkable silyl group-containing polyoxyalkylene polymer. Or the curable composition of 2.   (D) The compound which reacts with water and produces | generates an amine compound is further added, The curable composition of any one of Claims 1-3 characterized by the above-mentioned.   The curable composition according to any one of claims 1 to 4, wherein the component (C) hindered amine light stabilizer is a hindered amine compound having a triazine skeleton or a hindered amine compound having no triazine skeleton. object.   The curing according to any one of claims 1 to 4, wherein the component (C) hindered amine light stabilizer is a mixture of a hindered amine compound having a triazine skeleton and a hindered amine compound having no triazine skeleton. Sex composition.