JPWO2006077887A1 - Curable composition - Google Patents

Abstract

The object of the present invention is to provide a wide range of elastic bodies from hard to soft when cured, while being excellent in storage stability and low viscosity as a curable composition, and weather resistance and heat resistance The present invention provides a curable composition that is excellent in resistance, improves the hard and brittle properties of an epoxy resin, has rubber elasticity, and has high adhesive strength. The present invention contains a vinyl polymer (I) having at least one crosslinkable silyl group on average, an epoxy resin (II), and a room temperature curable latent curing agent (III). It relates to a sex composition.

Description

The present invention relates to a curable composition. More specifically, the present invention relates to a curable composition containing a vinyl polymer (I) having at least one crosslinkable silyl group on average, an epoxy resin (II), and a room temperature curable latent curing agent (III).

Epoxy resin adhesives are used for automobiles, vehicles, aircraft, shipbuilding, electronics, architecture, reliability from excellent adhesive strength and durability to a wide range of materials such as metal, plastic, wood, glass, ceramic, stone, and concrete. Used in a wide range of industrial fields such as civil engineering.
However, the cured product generally has a drawback of being hard and brittle because of its high elastic modulus and low energy absorption capability. For this reason, problems remain in the adhesion of materials with greatly different linear expansion coefficients and the adhesion of members that are repeatedly displaced by heat cycles, such as building materials.
In order to solve this problem, so-called modified silicone elastic adhesives obtained by blending an epoxy resin with a polyether polymer having at least one crosslinkable silyl group have been widely used. Elastic adhesives based on polyether polymer blends have various problems such as poor compatibility and low degree of freedom in blend ratio, weather resistance derived from polyether polymers, lack of heat resistance, etc. have.
In order to solve these points, a curable composition having an epoxy resin and a crosslinkable silyl group-containing (meth) acrylic polymer has been disclosed (see Patent Documents 1 and 2), but has excellent storage stability. Was not obtained.
Japanese Patent Laid-Open No. 02-214759 Japanese Patent Laid-Open No. 11-100433

The present invention is excellent in storage stability as a curable composition and has a low viscosity, but a cured product obtained by curing it gives a wide elastic body from hard to soft, and is excellent in weather resistance and heat resistance. An object of the present invention is to provide a curable composition that improves the hard and brittle nature of an epoxy resin and has rubber elasticity and high adhesive strength.

As a result of intensive studies in view of the above-mentioned present situation, the following three components: vinyl polymer (I) having at least one crosslinkable silyl group on average, epoxy resin (II), and room temperature curable latent curing agent The present inventors have found that the above problems can be solved by using a curable composition containing (III), and have reached the present invention.

That is, the present invention comprises a vinyl polymer (I) having an average of at least one crosslinkable silyl group, an epoxy resin (II), and a room temperature curable latent curing agent (III). It relates to a curable composition.

The curable composition of this invention is explained in full detail below.
<< Vinyl polymer (I) >>
<Main chain>
The present inventors have so far made numerous inventions relating to vinyl polymers having various crosslinkable functional groups at the polymer terminals, their production methods, curable compositions, and applications (Japanese Patent Laid-Open No. Hei 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-11-100033, (See Japanese Patent Laid-Open Nos. 11-116763, 9-272714, 9-272715, etc.).
Although it does not specifically limit as vinyl-type polymer (I) 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 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 isononyl, (meth) acrylic acid decyl, (meth) Dodecyl acrylate, phenyl (meth) acrylate, tolyl (meth) acrylate, benzyl (meth) acrylate, (meth) a 2-methoxyethyl toluate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, (meth ) Glycidyl acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, (meth) 2-trifluoromethylethyl acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, perfluoroethylperfluorobutylmethyl (meth) acrylate, (meth) acrylic acid 2 -Perfluoroethyl-2-perfluorobutyl ethyl , Perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethyl methyl (meth) acrylate, 2,2-diperfluoromethylethyl (meth) acrylate, (meth) acryl Perfluoromethyl perfluoroethyl methyl acid, 2-perfluoromethyl-2-perfluoroethyl ethyl (meth) acrylate, 2-perfluorohexyl methyl (meth) acrylate, 2-perfluorohexyl ethyl (meth) acrylate , 2-perfluorodecylmethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylmethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate (Meth) acrylic monomers such as styrene, vinyl Aromatic vinyl monomers such as ene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, vinylidene fluoride; vinyltrimethoxysilane, vinyltri Silicon-containing vinyl monomers such as ethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide , Maleimide monomers such as butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohexyl maleimide; Acrylonitrile monomers such as nitrile and methacrylonitrile; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate; ethylene, Alkenes such as propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. These may be used alone or a plurality of these may be copolymerized.

The main chain of the vinyl polymer is mainly polymerized with at least one monomer selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and silicon-containing vinyl monomers. It is preferable that it is manufactured.
Here, “mainly” means 30 mol% or more of monomer units constituting the vinyl polymer, and preferably 50 mol% or more.

Of these, a styrene monomer and a (meth) acrylic acid monomer are preferable from the physical properties of the product. More preferred are acrylic ester monomers and methacrylic ester monomers, and particularly preferred are acrylic ester monomers. For general architectural use and the like, a butyl acrylate monomer is more preferable from the viewpoint that physical properties such as low viscosity of the blend, low modulus of the cured product, high elongation, weather resistance, and heat resistance are required. On the other hand, in applications that require oil resistance, such as automobile applications, copolymers based on ethyl acrylate are more preferred. This polymer mainly composed of ethyl acrylate is excellent in oil resistance but tends to be slightly inferior in low temperature characteristics (cold resistance). Therefore, in order to improve the low temperature characteristics, a part of ethyl acrylate is converted into butyl acrylate. It is also possible to replace it. However, as the ratio of butyl acrylate is increased, the good oil resistance is impaired, so that the ratio is preferably 80 mol% or less depending on the application for which oil resistance is required, and 60 mol% or less. More preferably, it is 40 mol% or less, more preferably 30 mol% or less. It is also preferable to use 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, or the like in which oxygen is introduced into the side chain alkyl group in order to improve low-temperature characteristics and the like without impairing oil resistance. However, since heat resistance tends to be inferior due to the introduction of an alkoxy group having an ether bond in the side chain, when heat resistance is required, the ratio is preferably 60 mol% or less, and 40% or less. Is more preferable. In accordance with various uses and required purposes, it is possible to obtain suitable polymers by changing the ratio in consideration of required physical properties such as oil resistance, heat resistance and low temperature characteristics. For example, although not limited, examples of excellent physical property balance such as oil resistance, heat resistance, and low-temperature characteristics include ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate (molar ratio of 40-50 / 20- 30 / 20-30) and the like.

In addition, since the cured product when the curable composition containing the vinyl polymer of the present invention and the epoxy resin is cured is transparent, the vinyl polymer is compatible with the epoxy resin. For example, a polymer or copolymer having a higher polarity than the butyl acrylate homopolymer is preferable, and the main chain of the vinyl polymer has a repeating unit structure represented by the general formula (i). More preferably, it is a polymer or copolymer.
_{- [CH 2 -CR (COOR '} )] - (i)
(In the formula, R is hydrogen or a methyl group, and R ′ is the same or different and is an alkoxyalkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 3 carbon atoms.)

The polymer or copolymer having higher polarity than the butyl acrylate homopolymer is not particularly limited, and examples thereof include a copolymer of butyl acrylate and a monomer having higher polarity than butyl acrylate. Here, examples of the monomer having higher polarity than butyl acrylate include ethyl acrylate and 2-methoxyethyl acrylate. For example, a copolymer of ethyl acrylate / butyl acrylate / acrylic acid 2-methoxyethyl (molar ratio 40-50 / 20-30 / 30-20) is easily compatible with various epoxy resins, and is a transparent cured product. Since it is easy to obtain, it is suitable.

Copolymerizes monomers with long-chain alkyl groups such as stearyl groups and lauryl groups to improve compatibility with other polymers such as modified silicone resins (oxyalkylene polymers having crosslinkable silyl groups) You may let them. Although there is no particular limitation, for example, 5-30 mol% of stearyl acrylate or lauryl acrylate is copolymerized so that the compatibility with the modified silicone resin becomes very good. Since the compatibility varies depending on the molecular weight of each polymer, it is preferable to select the proportion of the monomer to be copolymerized accordingly. In this case, block copolymerization may be performed. The effect may be manifested in a small amount.

The curable composition containing a vinyl polymer having a functional silyl group may be slow in curability due to storage, that is, the storage stability may be lowered. For example, it may be possible to suppress a decrease in storage stability by copolymerizing methyl acrylate. Moreover, when it is desired to improve the strength of the cured product, a polymer or copolymer having a higher polarity than butyl acrylate may be used. Also in this case, the ratio of monomers to be copolymerized may be selected according to the molecular weight and / or block copolymerized.

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.

The molecular weight distribution of the vinyl polymer of the present invention, 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. The molecular weight distribution is preferably less than 1.8, and particularly preferably 1.3 or less from the viewpoint of workability. 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 in the present invention is not particularly limited. In addition, when measured by gel permeation chromatography, 500 to 1,000,000, particularly 5,000 to 50,000 are preferable from the viewpoint of workability and physical properties. Of course, the smaller the molecular weight, the easier it is to be compatible with the epoxy resin, and the resulting cured product tends to have a high modulus and low elongation, while the larger the molecular weight, the opposite is the case.

<Method of synthesizing the main chain>
The method for synthesizing the vinyl polymer in the present invention is not limited, and free radical polymerization may be used. However, controlled radical polymerization is preferable, living radical polymerization is more preferable, and atom transfer radical polymerization is particularly preferable. These will be described below.

Controlled radical polymerization The radical polymerization method uses an azo compound, a peroxide, or the like as a polymerization initiator to simply copolymerize a monomer having a specific functional group and a vinyl monomer. It can be classified into “polymerization method” and “controlled radical polymerization method” in which a specific functional group can be introduced at a controlled position such as a terminal.

The “general radical polymerization method” is a simple method. However, in this method, a monomer having a specific functional group is introduced into the polymer only in a probabilistic manner, so an attempt is made to obtain a polymer having a high functionalization rate. In such a case, it is necessary to use this monomer in a considerably large amount. On the contrary, if the monomer is used in a small amount, there is a problem that the proportion of the polymer in which this specific functional group is not introduced becomes large. Moreover, since it is free radical polymerization, there is also a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.

The “controlled radical polymerization method” further includes a “chain transfer agent method” in which a vinyl polymer having a functional group at a terminal is obtained by polymerization using a chain transfer agent having a specific functional group, It can be classified as a “living radical polymerization method” in which a polymer having a molecular weight almost as designed is obtained by growing the terminal without causing a termination reaction or the like.

In the “chain transfer agent method”, a polymer having a high functionalization rate can be obtained, but a chain transfer agent having a considerably large amount of a specific functional group with respect to the initiator is required. There is an economic problem. Further, like the above-mentioned “general radical polymerization method”, there is also a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained because of free radical polymerization.

Unlike these polymerization methods, the “living radical polymerization method” is a radical polymerization that is difficult to control because the polymerization rate is high and a termination reaction due to coupling between radicals is likely to occur. It is difficult to obtain a polymer having a narrow molecular weight distribution (Mw / Mn is about 1.1 to 1.5), and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.
Accordingly, the “living radical polymerization method” can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and a monomer having a specific functional group can be introduced at almost any position of the polymer. The method for producing the vinyl polymer having the specific functional group is more preferable.

In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity and the molecular chain grows, but in general, the terminal is inactivated and the terminal is activated. It also includes pseudo-living polymerization that grows in an equilibrium state. The definition in the present invention is also the latter.

The “living radical polymerization method” has been actively researched by various groups in recent years. Examples thereof include those using a cobalt porphyrin complex as shown in, for example, Journal of American Chemical Society (J. Am. Chem. Soc.), 1994, 116, 7943, Macromolecules. (Macromolecules), 1994, Vol. 27, p. 7228, using a radical capping agent such as a nitroxide compound, etc., “atom transfer radical polymerization” using an organic halide as an initiator and a transition metal complex as a catalyst ( Atom Transfer Radical Polymerization (ATRP).

Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” for polymerizing vinyl monomers using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above “living radical polymerization method”. In addition to the features of ”, it has a halogen, which is relatively advantageous for functional group conversion reaction, at the end, and has a high degree of freedom in designing initiators and catalysts, so the production of vinyl polymers having specific functional groups More preferable as a method. As this atom transfer radical polymerization method, for example, Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614, Macromolecules (1995), 28, 7901, Science 1996, 272, 866, WO96 / 30421, WO97 / 18247, WO98 / 01480, WO98 / 40415, or Sawamoto et al., Macromolecules. Macromolecules 1995, 28, 1721, JP-A-9-208616, JP-A-8-41117, and the like.
In the present invention, there is no particular restriction as to which of these living radical polymerization methods is used, but an atom transfer radical polymerization method is preferred.

The living radical polymerization will be described in detail below, but before that, one of the controlled radical polymerizations that can be used for the production of vinyl polymers described later, the polymerization using a chain transfer agent will be described. To do. Although it does not specifically limit as radical polymerization using a chain transfer agent (telomer), The following two methods are illustrated as a method of obtaining the vinyl polymer which has the terminal structure suitable for this invention.

JP-A-4-132706 discloses a method for obtaining a halogen-terminated polymer by using a halogenated hydrocarbon as a chain transfer agent, JP-A-61-271306, JP-A-2594402, This is a method for obtaining a hydroxyl-terminated polymer by using a hydroxyl group-containing mercaptan or a hydroxyl group-containing polysulfide as a chain transfer agent as disclosed in JP-A-54-47782.

Below, living radical polymerization is demonstrated.
First, a method using a radical capping agent such as a nitroxide compound will be described. In this polymerization, a stable nitroxy free radical (= N—O.) Is generally used as a radical capping agent. Examples of such compounds include, but are not limited to, 2,2,6,6-substituted-1-piperidinyloxy radical, 2,2,5,5-substituted-1-pyrrolidinyloxy radical, and the like. Nitroxy free radicals from cyclic hydroxyamines are preferred. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group or an ethyl group is suitable. Specific nitroxy free radical compounds include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl-1- Piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1, Examples include 1,3,3-tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamineoxy radical, and the like. Instead of the nitroxy free radical, a stable free radical such as a galvinoxyl free radical may be used.

The radical capping agent is used in combination with a radical generator. It is considered that the reaction product of the radical capping agent and the radical generator serves as a polymerization initiator and the polymerization of the addition polymerizable monomer proceeds. The combination ratio of both is not particularly limited, but 0.1 to 10 mol of the radical generator is suitable for 1 mol of the radical capping agent.

Although various compounds can be used as the radical generator, a peroxide capable of generating a radical under polymerization temperature conditions is preferred. Examples of the peroxide include, but are not limited to, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, diisopropyl peroxydicarbonate, bis There are peroxycarbonates such as (4-t-butylcyclohexyl) peroxydicarbonate, alkyl peresters such as t-butylperoxyoctate and t-butylperoxybenzoate. Benzoyl peroxide is particularly preferable. Furthermore, radical generators such as radical-generating azo compounds such as azobisisobutyronitrile may be used instead of peroxide.

Macromolecules 1995, 28, P.M. As reported in 2993, instead of using a radical capping agent and a radical generator in combination, an alkoxyamine compound as shown below may be used as an initiator.

When an alkoxyamine compound is used as an initiator, if it has a functional group such as a hydroxyl group as represented by the above formula, a polymer having a functional group at the terminal can be obtained. When this is used in the method of the present invention, a polymer having a functional group at the terminal can be obtained.
Polymerization conditions such as a monomer, a solvent, and a polymerization temperature used in polymerization using a radical capping agent such as the above nitroxide compound are not limited, but may be the same as those used for atom transfer radical polymerization described below.

Atom transfer radical polymerization Next, an atom transfer radical polymerization method more preferable as the living radical polymerization of the present invention will be described.
In this 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 halogenated compound. A sulfonyl compound or the like is used as an initiator.

For example,
_{C 6 H 5 -CH 2 X,} C 6 H 5 -C (H) (X) CH 3, C 6 H 5 -C (X) (CH 3) 2
(However, in the above chemical formula, C ₆ H ₅ is a phenyl group, X is chlorine, bromine, or iodine)
^{_{R 3 -C (H) (X}} ) -CO 2 R 4, R 3 -C (CH 3) (X) -CO 2 R 4, R 3 -C (H) (X) -C (O) R 4 _{^{, R 3 -C (CH 3)}} (X) -C (O) R 4,
(Wherein R ³ and R ⁴ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, X is chlorine, bromine, or iodine)
R ³ —C ₆ H ₄ —SO ₂ X
(Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and X is chlorine, bromine, or iodine)
Etc.

As an initiator of atom transfer radical polymerization, an organic halide or a sulfonyl halide compound having a functional group other than the functional group for initiating polymerization can also be used. In such a 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 produced. Examples of such functional groups include alkenyl groups, crosslinkable silyl groups, hydroxyl groups, epoxy groups, amino groups, amide groups, and the like.

It does not limit as an organic halide which has an alkenyl group, For example, what has a structure shown in General formula (2) is illustrated.
^{R 6 R 7 C (X)} -R 8 -R 9 -C (R 5) = CH 2 (2)
(Wherein R ⁵ is hydrogen or a methyl group, R ⁶ and R ⁷ are hydrogen, or a monovalent alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, or interconnected at the other end. things, ^{R 8} is, -C (O) O- (ester group), - C (O) - ( keto group), or o-, m-, p-phenylene, ^{R 9} is a direct bond or carbon atoms 1 to 20 divalent organic groups which may contain one or more ether bonds, X is chlorine, bromine or iodine)
Specific examples of the substituents R ⁶ and R ⁷ include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, pentyl group, hexyl group and the like. R ⁶ and R ⁷ may be linked at the other end to form a cyclic skeleton.

Specific examples of the organic halide having an alkenyl group represented by the general formula (2) include
_{XCH 2 C (O) O (} CH 2) n CH = CH 2, H 3 CC (H) (X) C (O) O (CH 2) n CH = CH 2, (H 3 C) 2 C (X _{) C (O) O (CH} 2) n CH = CH 2, CH 3 CH 2 C (H) (X) C (O) O (CH 2) n CH = CH 2,

(In the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20)
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m CH = CH 2, H 3 CC (H) (X) C (O) O (CH 2) n O (CH 2) m CH = _{CH 2, (H 3 C)} 2 C (X) C (O) O (CH 2) n O (CH 2) m CH = CH 2, CH 3 CH 2 C (H) (X) C (O) O _{(CH 2) n O (CH} 2) m CH = CH 2,

(In the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -CH = CH 2, o, m, p-CH 3 C (H) (X) -C 6 H 4 - (CH 2) _{n -CH = CH 2, o,} m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) n -CH = CH 2,
(In the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -O- (CH 2) m -CH = CH 2, o, m, p-CH 3 C (H) (X) -C _{6 H 4 - (CH 2)} n -O- (CH 2) m -CH = CH 2, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) _{n -O- (CH 2) m CH} = CH 2,
(In the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -CH = CH 2, o, m, p-CH 3 C (H) (X) -C 6 H 4 -O- _{(CH 2) n -CH = CH} 2, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) n -CH = CH 2,
(In the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2, o, m, p-CH 3 C (H) (X) _{-C 6 H 4 -O- (CH 2} ) n -O- (CH 2) m -CH = CH 2, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 - O— (CH ₂ ) _n —O— (CH ₂ ) _m —CH═CH ₂ ,
(In the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)

Examples of the organic halide having an alkenyl group further include a compound represented by the general formula (3).
_{^{H 2 C = C (R 5}} ) -R 9 -C (R 6) (X) -R 10 -R 7 (3)
(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁹ and X are the same as above, R ¹⁰ is a direct bond, —C (O) O— (ester group), —C (O) — (keto group) Or represents an o-, m-, p-phenylene group)
R ⁹ is a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds), but in the case of a direct bond, carbon to which a halogen is bonded Is a halogenated allylic compound. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, it is not always necessary to have a C (O) O group, a phenylene group or the like as R ¹⁰ , and a direct bond may be used. When R ⁹ is not a direct bond, R ¹⁰ is preferably a C (O) O group, a C (O) group, or a phenylene group in order to activate the carbon-halogen bond.

If the compound of general formula (3) is specifically illustrated,
_{CH 2 = CHCH 2 X, CH} 2 = C (CH 3) CH 2 X, CH 2 = CHC (H) (X) CH 3, CH 2 = C (CH 3) C (H) (X) CH 3, _{CH 2 = CHC (X) (} CH 3) 2, CH 2 = CHC (H) (X) C 2 H 5, CH 2 = CHC (H) (X) CH (CH 3) 2, CH 2 = CHC ( _{H) (X) C 6 H} 5, CH 2 = CHC (H) (X) CH 2 C 6 H 5, CH 2 = CHCH 2 C (H) (X) -CO 2 R, CH 2 = CH (CH _{2) 2 C (H) (} X) -CO 2 R, CH 2 = CH (CH 2) 3 C (H) (X) -CO 2 R, CH 2 = CH (CH 2) 8 C (H) ( _{X) -CO 2 R, CH 2} = CHCH 2 C (H) (X) -C 6 H 5, CH 2 = CH (CH 2) 2 C (H) (X) -C 6 _{H 5, CH 2 = CH (} CH 2) 3 C (H) (X) -C 6 H 5,
(In the above formulas, X is chlorine, bromine, or iodine, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group)
Etc.

If the specific example of the sulfonyl halide compound which has an alkenyl group is given,
_{o-, m-, p-CH 2} = CH- (CH 2) n -C 6 H 4 -SO 2 X, o-, m-, p-CH 2 = CH- (CH 2) n -O-C ₆ H ₄ -SO ₂ X,
(In the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20)
Etc.

It does not specifically limit as said organic halide which has a crosslinkable silyl group, For example, what has a structure shown in General formula (4) is illustrated.
^{R 6 R 7 C (X)} -R 8 -R 9 -C (H) (R 5) CH 2 - [Si (R 11) 2-b (Y) b O] m -Si (R 12) 3- _a (Y) _a (4)
(In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are the same as above, R ¹¹ and R ¹² are all alkyl groups having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms. Group, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same. And may be different), when two or more R ¹¹ or R ¹² are present, they may be the same or different, Y may be a hydroxyl group or A hydrolyzable group, when two or more Y are present, they may be the same or different, a being 0, 1, 2, or 3 and b being 0, 1, 1; Or 2. m is an integer of 0 to 19, provided that a + mb ≧ 1 is satisfied.

If the compound of general formula (4) is specifically illustrated,
_{XCH 2 C (O) O (} CH 2) n Si (OCH 3) 3, CH 3 C (H) (X) C (O) O (CH 2) n Si (OCH 3) 3, (CH 3) 2 _{C (X) C (O)} O (CH 2) n Si (OCH 3) 3, XCH 2 C (O) O (CH 2) n Si (CH 3) (OCH 3) 2, CH 3 C (H) _{(X) C (O) O} (CH 2) n Si (CH 3) (OCH 3) 2, (CH 3) 2 C (X) C (O) O (CH 2) n Si (CH 3) (OCH ₃ ) ₂ ,
(In the above formulas, X is chlorine, bromine, iodine, and n is an integer of 0 to 20)
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m Si (OCH 3) 3, H 3 CC (H) (X) C (O) O (CH 2) n O (CH 2) m Si (OCH ₃ ) ₃ , (H ₃ C) ₂ C (X) C (O) O (CH ₂ ) _n O (CH ₂ ) _m Si (OCH ₃ ) ₃ , CH ₃ CH ₂ C (H) (X _{) C (O) O (CH} 2) n O (CH 2) m Si (OCH 3) 3, XCH 2 C (O) O (CH 2) n O (CH 2) m Si (CH 3) (OCH 3 ) ₂ , H ₃ CC (H) (X) C (O) O (CH ₂ ) _n O (CH ₂ ) _m —Si (CH ₃ ) (OCH ₃ ) ₂ , (H ₃ C) ₂ C (X) _{C (O) O (CH 2} ) n O (CH 2) m -Si (CH 3) (OCH 3) 2, CH 3 CH 2 C (H) (X) C (O) O (CH _{2) n O (CH 2)} m -Si (CH 3) (OCH 3) 2,
(In the above formulas, X is chlorine, bromine, iodine, n is an integer of 1-20, m is an integer of 0-20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3, o, m, p-CH 3 C (H) (X) -C 6 H 4 - (CH 2 _{) 2 Si (OCH 3) 3} , o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3, o, m, p- _{XCH 2 -C 6 H 4 - (} CH 2) 3 Si (OCH 3) 3, o, m, p-CH 3 C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3 _{) 3, o, m, p} -CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3, o, m, p-XCH 2 -C 6 H _{4 - (CH 2) 2 -O-} (CH 2) 3 Si (OCH 3) 3, o, m, p-CH 3 C (H) (X) -C 6 H 4 - (CH 2) 2 -O − _{CH 2) 3 Si (OCH 3} ) 3, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH _{3) 3, o, m,} p-XCH 2 -C 6 H 4 -O- (CH 2) 3 Si (OCH 3) 3, o, m, p-CH 3 C (H) (X) -C 6 _{H 4 -O- (CH 2) 3} Si (OCH 3) 3, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) 3 -Si ( _{OCH 3) 3, o, m} , p-XCH 2 -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 -Si (OCH 3) 3, o, m, p-CH 3 _{C (H) (X) -C} 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3, o, m, p-CH 3 CH 2 C (H) ( X) _{C 6 H 4 -O- (CH 2} ) 2 -O- (CH 2) 3 Si (OCH 3) 3,
(In the above formulas, X is chlorine, bromine, or iodine)
Etc.

Examples of the organic halide having a crosslinkable silyl group further include those having a structure represented by the general formula (5).
_{^{(R 12) 3-a (}} Y) a Si- [OSi (R 11) 2-b (Y) b] m -CH 2 -C (H) (R 5) -R 9 -C (R 6) ( X) -R ¹⁰ -R ⁷ (5)
(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , a, b, m, X, Y are the same as above)

If such a compound is specifically illustrated,
_{(CH 3 O) 3 SiCH 2} CH 2 C (H) (X) C 6 H 5, (CH 3 O) 2 (CH 3) SiCH 2 CH 2 C (H) (X) C 6 H 5, (CH _{3 O) 3 Si (CH 2} ) 2 C (H) (X) -CO 2 R, (CH 3 O) 2 (CH 3) Si (CH 2) 2 C (H) (X) -CO 2 R, _{(CH 3 O) 3 Si (} CH 2) 3 C (H) (X) -CO 2 R, (CH 3 O) 2 (CH 3) Si (CH 2) 3 C (H) (X) -CO 2 _{R, (CH 3 O) 3} Si (CH 2) 4 C (H) (X) -CO 2 R, (CH 3 O) 2 (CH 3) Si (CH 2) 4 C (H) (X) - _{CO 2 R, (CH 3 O} ) 3 Si (CH 2) 9 C (H) (X) -CO 2 R, (CH 3 O) 2 (CH 3) Si (CH 2) 9 C (H) (X _{) -CO 2 R, (CH 3} O) 3 Si (CH 2) 3 C (H) (X) -C 6 H 5, (CH 3 O) 2 (CH 3) Si (CH 2) 3 C (H _{) (X) -C 6 H 5} , (CH 3 O) 3 Si (CH 2) 4 C (H) (X) -C 6 H 5, (CH 3 O) 2 (CH 3) Si (CH 2) ₄ C (H) (X) -C ₆ H ₅ ,
(In the above formulas, X is chlorine, bromine, or iodine, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group)
Etc.

The organic halide having a hydroxyl group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.
_{HO- (CH 2) n -OC (} O) C (H) (R) (X)
(Wherein X is chlorine, bromine or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
The organic halide having an amino group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.
_{H 2 N- (CH 2) n} -OC (O) C (H) (R) (X)
(Wherein X is chlorine, bromine or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
The organic halide having the epoxy group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.

(Wherein X is chlorine, bromine or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)

In order to obtain a polymer having two or more growth terminal structures in one molecule, an organic halide having two or more starting points or a sulfonyl halide compound is preferably used as an initiator. For example,

Etc.
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. Further preferred are complexes having zero-valent copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel as the central metal. 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. Furthermore, 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, tert-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, which 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).

<Functional group>
Number of crosslinkable silyl groups The vinyl polymer (I) has an average of at least one crosslinkable silyl group in the molecule. The number of crosslinkable silyl groups is more preferably 1.1 or more and 4.0 or less on average in the molecule from the viewpoint of the curability of the composition and the physical properties of the cured product, and still more preferably 1. 2 or more and 3.5 or less.

Position of the crosslinkable silyl group When a rubber-like 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 is used. It is preferable that at least one of the crosslinkable silyl groups is at the end of the molecular chain because it can be taken large. 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 the molecular chain end, in particular, a (meth) acrylic polymer is disclosed in Japanese Patent Publication No. 3-14068, Japanese Patent Publication No. 4-55444, This is disclosed in, for example, Kaihei 6-221922. However, since these methods are free radical polymerization methods using the above-mentioned “chain transfer agent method”, the resulting polymer has a relatively high proportion of crosslinkable silyl 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 silyl group at the molecular chain terminal at a high ratio, the above “living radical polymerization method” is used. However, it is not limited to a polymer having a narrow molecular weight distribution.

These functional groups will be described below.
Crosslinkable silyl group As the crosslinkable silyl group of the vinyl polymer (I) in the present invention, the general formula (1);
^{_{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
{Wherein R ¹ and R ² are the same or different and are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) _3. A triorganosiloxy group represented by SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). When two or more R ¹ or R ² are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. }
The group represented by these is mentioned.

Examples of the hydrolyzable group include commonly used groups such as a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, an alkoxy group, an amide group, and an aminooxy group are preferable, but an alkoxy group is particularly preferable in terms of mild hydrolyzability and easy handling.
Among the alkoxy groups, those having a smaller number of carbon atoms have higher reactivity, and the reactivity decreases in the order of methoxy group> ethoxy group> propoxy group, and can be selected according to the purpose and application.

Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3, and (a + Σb) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silyl group, they may be the same or different. The number of silicon atoms forming the crosslinkable silyl group is one or more, but in the case of silicon atoms linked by a siloxane bond or the like, it is preferably 20 or less. In particular, the general formula (6)
—Si (R ² ) _3-a (Y) _a (6)
A crosslinkable silyl group represented by the formula (wherein R ² and Y are the same as described above, and a is an integer of 1 to 3) is preferable because it is easily available.

Although not particularly limited, a is preferably 2 or more in consideration of curability.
As such a vinyl polymer having a crosslinkable silyl group, a polymer having a hydrolyzable silicon group formed by bonding two hydrolyzable groups per silicon atom is often used. When a very fast curing rate is required, such as when used at low temperatures, etc., the curing rate is not sufficient, and if it is desired to provide flexibility after curing, it is necessary to reduce the crosslinking density. For this reason, the crosslink density is not sufficient, and stickiness (surface tack) may occur. In that case, it is preferable that a is 3 (for example, a trimethoxy functional group).

Further, those having a of 3 (for example, trimethoxy functional group) cure faster than those having a of 2 (for example, dimethoxy functional group). May be better. In order to balance the curability and physical properties, those having a of 2 (for example, dimethoxy functional group) and those having 3 (for example, trimethoxy functional group) may be used in combination.
For example, when Y is the same, the greater the a, the higher the reactivity of Y. Therefore, by variously selecting Y and a, it is possible to control the curability and the mechanical properties of the cured product. It can be selected according to the application. A compound having a of 1 is used as a chain extender mixed with a polymer having a crosslinkable silyl group, specifically, at least one polymer comprising a polysiloxane, polyoxypropylene or polyisobutylene. it can. It is possible to obtain a composition having low viscosity before curing, high elongation at break after curing, low bleeding, low surface contamination, and excellent paint adhesion.

Introduction method <br/> the following crosslinkable silyl group, will be described method of introducing the crosslinkable silyl group into the vinyl polymer of the present invention (I), but is not limited thereto.
First, a method for introducing a crosslinkable silyl group, alkenyl group, and hydroxyl group by terminal functional group conversion will be described. Since these functional groups can be precursors to each other, they are described in the order from the crosslinkable silyl group.

As a method for synthesizing a vinyl polymer having at least one crosslinkable silyl group,
(A) A method in which a hydrosilane compound having a crosslinkable silyl group is added to a vinyl polymer having at least one alkenyl group in the presence of a hydrosilylation catalyst. (B) One molecule per vinyl polymer having at least one hydroxyl group. A method in which a compound having a group capable of reacting with a hydroxyl group, such as a compound having a crosslinkable silyl group and an isocyanate group, is reacted. (C) When a vinyl polymer is synthesized by radical polymerization, polymerization is performed in one molecule. A method of reacting a compound having both a functional alkenyl group and a crosslinkable silyl group (D) a method of using a chain transfer agent having a crosslinkable silyl group when synthesizing a vinyl polymer by radical polymerization (E) A compound having a crosslinkable silyl group and a stable carbanion in one molecule in a vinyl polymer having at least one high carbon-halogen bond And the like; a method of reacting.

The vinyl polymer having at least one alkenyl group used in the method (A) can be obtained by various methods. Although the synthesis method is illustrated below, it is not necessarily limited to these.
(Aa) When synthesizing a vinyl polymer by radical polymerization, for example, a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule as shown in the following general formula (9) To react as a second monomer.
_{^{H 2 C = C (R 14}} ) -R 15 -R 16 -C (R 17) = CH 2 (9)
(Wherein R ¹⁴ represents hydrogen or a methyl group, R ¹⁵ represents —C (O) O—, or o-, m-, p-phenylene group, and R ¹⁶ represents a direct bond, 20 represents a divalent organic group having 20 and may contain one or more ether bonds, R ¹⁷ is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 carbon atoms. Represents -20 aralkyl groups)
There is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule. It is preferable to react as the second monomer at the end or after completion of the reaction of the predetermined monomer.

(Ab) When synthesizing a vinyl polymer by living radical polymerization, for example, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer. A method of reacting a compound having at least two alkenyl groups having low polymerizability such as
(Ac) Various organometallic compounds having an alkenyl group such as organotin such as allyltributyltin and allyltrioctyltin on a vinyl polymer having at least one highly reactive carbon-halogen bond A method of replacing halogen by reaction.

(Ad) A method of substituting halogen by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a stabilized carbanion having an alkenyl group as shown in the general formula (10). .
^{M + C - (R 18)} (R 19) -R 20 -C (R 17) = CH 2 (10)
^{(Wherein, R 17} is as defined ^above, R ^{18, R 19} together carbanion C ^- a is an electron withdrawing group stabilizing or one of the other hydrogen or a 1 to 10 carbon atoms in the electron-withdrawing group Represents an alkyl group or a phenyl group, R ²⁰ represents a direct bond or a divalent organic group having 1 to 10 carbon atoms, and may contain one or more ether bonds, M ⁺ represents an alkali metal ion, Or a quaternary ammonium ion)
As the electron withdrawing group for R ¹⁸ and R ¹⁹ , those having a structure of —CO ₂ R, —C (O) R and —CN are particularly preferable.

(Ae) An enolate anion is prepared by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with, for example, a single metal such as zinc or an organometallic compound. A method of reacting with an electrophilic compound having an alkenyl group, such as an alkenyl group-containing compound having a leaving group such as an acetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, an acid halide having an alkenyl group .

(Af) For example, an oxyanion or carboxylate anion having an alkenyl group represented by the general formula (11) or (12) is added to a vinyl polymer having at least one carbon-halogen bond having high reactivity. A method of replacing halogen by reaction.
_{^{H 2 C = C (R 17}} ) -R 21 -O - M + (11)
(Wherein R ¹⁷ and M ⁺ are the same as above. R ²¹ is a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds)
_{^{H 2 C = C (R 17}} ) -R 22 -C (O) O - M + (12)
(In the formula, R ¹⁷ and M ⁺ are the same as above. R ²² is a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds.)
Etc.
The above-described method for synthesizing a vinyl polymer having at least one carbon-halogen bond having high reactivity is an atom transfer radical polymerization method using an organic halide as described above as an initiator and a transition metal complex as a catalyst. For example, but not limited to.

Further, the vinyl polymer having at least one alkenyl group can be obtained from a vinyl polymer having at least one hydroxyl group, and the methods exemplified below can be used, but are not limited thereto.
In the hydroxyl group of a vinyl polymer having at least one hydroxyl group,
(Ag) A method of reacting a base such as sodium methoxide with an alkenyl group-containing halide such as allyl chloride.
(Ah) A method of reacting an alkenyl group-containing isocyanate compound such as allyl isocyanate.
(Ai) A method in which an alkenyl group-containing acid halide such as (meth) acrylic acid chloride is reacted in the presence of a base such as pyridine.
(Aj) A method of reacting an alkenyl group-containing carboxylic acid such as acrylic acid in the presence of an acid catalyst, and the like.

In the present invention, when halogen is not directly involved in the method of introducing an alkenyl group such as (Aa) and (Ab), it is preferable to synthesize a vinyl polymer using a living radical polymerization method. . The method (Ab) is more preferable in terms of easier control.
When introducing an alkenyl group by converting the halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halide having at least one highly reactive carbon-halogen bond, or A vinyl heavy polymer having at least one highly reactive carbon-halogen bond at the terminal, obtained by radical polymerization of a vinyl monomer using a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst (atom transfer radical polymerization method). It is preferable to use coalescence. The method (Af) is more preferable in terms of easier control.

Moreover, there is no restriction | limiting in particular as a hydrosilane compound which has a crosslinkable silyl group, When a typical thing is shown, the compound shown by General formula (13) will be illustrated.
^{_{H- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (13)
{Wherein R ¹ and R ² are the same or different and are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) _3. A triorganosiloxy group represented by SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). When two or more R ¹ or R ² are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. }

Among these hydrosilane compounds, in particular, the general formula (14)
_{^{H-Si (R 2) 3}} -a (Y) a (14)
(Wherein R ² , Y and a are the same as above)
The compound which has a crosslinkable group shown by is preferable from a point with easy acquisition.

When the hydrosilane compound having a crosslinkable silyl group is added to an alkenyl group, a transition metal catalyst is usually used. Examples of the transition metal catalyst include platinum simple substance, alumina, silica, carbon black and the like in which a platinum solid is dispersed, chloroplatinic acid, a complex of chloroplatinic acid and alcohol, aldehyde, ketone, etc., platinum-olefin. Complex, platinum (0) -divinyltetramethyldisiloxane complex is mentioned. Examples of the catalyst other than platinum _{compounds, RhCl (PPh 3) 3,} RhCl 3, RuCl 3, IrCl 3, FeCl 3, AlCl 3, PdCl 2 · H 2 O, NiCl 2, TiCl 4 , and the like.

Examples of the method for producing a vinyl polymer having at least one hydroxyl group used in the methods (B) and (Ag) to (Aj) include the following methods, but are limited to these methods. It is not something.
(Ba) When synthesizing a vinyl polymer by radical polymerization, for example, a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule as shown in the following general formula (15) is used as the second monomer. How to react as.
_{^{H 2 C = C (R 14}} ) -R 15 -R 16 -OH (15)
(Wherein R ¹⁴ , R ¹⁵ and R ¹⁶ are the same as above)
There is no limitation on the timing of reacting the compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule. However, particularly in the case of living radical polymerization, when the rubber-like properties are expected, the end of the polymerization reaction or a predetermined monomer. After completion of the reaction, it is preferable to react as the second monomer.

(Bb) When a vinyl polymer is synthesized by living radical polymerization, an alkenyl alcohol such as 10-undecenol, 5-hexenol or allyl alcohol is reacted at the end of the polymerization reaction or after the completion of the reaction of a predetermined monomer. How to make.
(Bc) A method in which a vinyl monomer is radically polymerized using a large amount of a hydroxyl group-containing chain transfer agent such as a hydroxyl group-containing polysulfide disclosed in JP-A-5-262808.
(Bd) A method of radical polymerization of a vinyl monomer using hydrogen peroxide or a hydroxyl group-containing initiator as disclosed in, for example, JP-A-6-239912 and JP-A-8-283310.
(Be) A method of radical polymerization of a vinyl monomer by using an excessive amount of alcohol as disclosed in JP-A-6-116312, for example.
(Bf) For example, a halogen of a vinyl polymer having at least one carbon-halogen bond having high reactivity is hydrolyzed or reacted with a hydroxyl group-containing compound by a method as disclosed in JP-A-4-132706. To introduce a hydroxyl group into the terminal.

(Bg) A method in which a vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having a hydroxyl group as listed in the general formula (16) to substitute a halogen.
^{M + C - (R 18)} (R 19) -R 20 -OH (16)
(Wherein R ¹⁸ , R ¹⁹ , R ²⁰ and M ⁺ are the same as above)
As the electron withdrawing group for R ¹⁸ and R ¹⁹ , those having a structure of —CO ₂ R, —C (O) R and —CN are particularly preferable.

(Bh) An enolate anion is prepared by allowing a metal polymer such as zinc or an organometallic compound to act on a vinyl polymer having at least one highly reactive carbon-halogen bond, and then aldehydes. Or a method of reacting ketones.
(Bi) A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with, for example, an oxyanion or carboxylate anion having a hydroxyl group as shown in the general formula (17) or (18). To replace the halogen.
HO—R ²¹ —O ^— M ⁺ (17)
(Wherein R ²¹ and M ⁺ are the same as above)
HO—R ²² —C (O) O ⁻ M ⁺ (18)
(Wherein R ²² and M ⁺ are the same as above)

(Bj) When synthesizing a vinyl polymer by living radical polymerization, as the second monomer after the end of the polymerization reaction or after the completion of the reaction of the predetermined monomer, an alkenyl group and a hydroxyl group having low polymerizability in one molecule A method of reacting a compound having
Although it does not specifically limit as such a compound, The compound etc. which are shown by General formula (19) are mentioned.
_{^{H 2 C = C (R 14}} ) -R 21 -OH (19)
(In the formula, R ¹⁴ and R ²¹ are the same as those described above.)
The compound represented by the general formula (19) is not particularly limited, but alkenyl alcohols such as 10-undecenol, 5-hexenol and allyl alcohol are preferable because they are easily available.

In the present invention, when halogen is not directly involved in the method of introducing a hydroxyl group such as (Ba) to (Be) and (Bj), a vinyl polymer is obtained by using a living radical polymerization method. It is preferable to synthesize. The method (Bb) is more preferable in terms of easier control.
When introducing a hydroxyl group by converting the halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halide or a sulfonyl halide compound is used as an initiator, and a transition metal complex is used as a catalyst. It is preferable to use a vinyl polymer having at least one highly reactive carbon-halogen bond at the terminal obtained by radical polymerization of a vinyl monomer (atom transfer radical polymerization method). The method (Bi) is more preferable from the viewpoint of easier control.

Examples of the compound having a crosslinkable silyl group and a group capable of reacting with a hydroxyl group such as an isocyanate group in one molecule include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and γ-isocyanate. Examples thereof include natopropyltriethoxysilane, and a generally known catalyst for urethanization reaction can be used if necessary.

As a compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule used in the method (C), for example, trimethoxysilylpropyl (meth) acrylate, methyldimethoxysilylpropyl (meth) acrylate, etc., What is shown by the following general formula (20) is mentioned.
_{^{H 2 C = C (R 14}} ) -R 15 -R 23 - [Si (R 1) 2-b (Y) b O] m -Si (R 2) 3-a (Y) a (20)
(Wherein R ¹ , R ² , R ¹⁴ , R ¹⁵ , Y, a, b, m are the same as above. R ²³ is a direct bond or one divalent organic group having 1 to 20 carbon atoms. (The above ether bond may be included, provided that a + mb ≧ 1 is satisfied.)

There is no particular limitation on the timing of reacting the compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule. However, particularly in the case of living radical polymerization, when a rubber-like property is expected, the end of the polymerization reaction or a predetermined value is determined. It is preferable to make it react as a 2nd monomer after completion | finish of reaction of this monomer.

Examples of the chain transfer agent having a crosslinkable silyl group used in the chain transfer agent method of (D) include mercaptans having a crosslinkable silyl group and crosslinkable silyl as shown in, for example, Japanese Patent Publication Nos. 3-14068 and 4-55444. And hydrosilane having a group.

The method for synthesizing a vinyl polymer having at least one highly reactive carbon-halogen bond, which is used in the method (E), uses an organic halide as described above as an initiator, and a transition metal complex. Examples thereof include, but are not limited to, an atom transfer radical polymerization method using a catalyst. Examples of the compound having both a crosslinkable silyl group and a stabilized carbanion in one molecule include those represented by the general formula (21).
^{M + C - (R 18)} (R 19) -R 24 -C (H) (R 25) -CH 2 - [Si (R 1) 2-b (Y) b O] m -Si (R 2) _3-a (Y) _a (21)
(Wherein R ¹ , R ² , R ¹⁸ , R ¹⁹ , Y, a, b, m are the same as above. R ²⁴ is a direct bond or one divalent organic group having 1 to 10 carbon atoms. R ²⁵ which may contain the above ether bond, represents hydrogen, 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, provided that a + mb ≧ Satisfied to be 1.)
As the electron withdrawing group for R ¹⁸ and R ¹⁹ , those having a structure of —CO ₂ R, —C (O) R and —CN are particularly preferable.

<Use of multiple vinyl polymers>
Only one kind of the above-mentioned vinyl polymers can be used, or two or more kinds of vinyl polymers can be used in combination.
When only one kind is used, it is preferable to use a vinyl polymer having a molecular weight of 5,000 to 50,000 and a number of crosslinkable silyl groups of 1.2 to 3.5.
When two or more vinyl polymers are combined, the first polymer is a vinyl polymer having a molecular weight of 5,000 to 50,000 and a number of crosslinkable silyl groups of 1.2 to 3.5. When the second polymer is a polymer having a small number of crosslinkable silyl groups, a cured product having high elongation at break, low bleeding property, low surface contamination, and excellent paint adhesion can be obtained. . Moreover, the viscosity of a composition can be reduced by setting the molecular weight of a 2nd polymer smaller. The preferred molecular weight of the polymer to be the low molecular weight component is less than 10,000, more preferably less than 5,000, and the preferred number of crosslinkable silyl groups is less than 1.2, further 1 or less. Further, since the viscosity can be further reduced, the molecular weight distribution is preferably less than 1.8. When a vinyl polymer having a crosslinkable functional group and a molecular weight distribution of 1.8 or more and a vinyl polymer having a crosslinkable silyl group at one end are added, the effect of reducing the viscosity is remarkable.

As a polymer having such a low molecular weight and a small number of crosslinkable silyl groups, it is definitely possible to use a vinyl polymer having a crosslinkable silyl group at one end obtained by the following production method. It is preferable because it can be introduced.
A vinyl polymer having a crosslinkable silyl group at one end has approximately one crosslinkable silyl group per molecule at the end of the polymer. Use of the above-mentioned living radical polymerization method, particularly the atom transfer radical polymerization method, has a high proportion of crosslinkable silyl groups at the molecular chain ends, a molecular weight distribution of less than 1.8, a narrow molecular weight distribution, and a low viscosity. Since a vinyl polymer is obtained, it is preferable.

About the method of introduce | transducing a crosslinkable silyl group into one terminal, the method shown below can be used, for example. In the method of introducing a crosslinkable silyl group, an alkenyl group, and a hydroxyl group by terminal functional group conversion, these functional groups can be precursors to each other, and therefore, are described in the order starting from the method of introducing the crosslinkable silyl group.
(1) A method of adding a hydrosilane compound having a crosslinkable silyl group to a polymer having one alkenyl group per molecule at the molecular chain end in the presence of a hydrosilylation catalyst,
(2) A method of reacting a polymer having one hydroxyl group per molecular chain end with a compound having both a crosslinkable silyl group and a group capable of reacting with a hydroxyl group such as an isocyanate group in one molecule,
(3) A method in which a polymer having one highly reactive carbon-halogen bond per molecule per molecule is reacted with a compound having a crosslinkable silyl group and a stable carbanion in one molecule.
Etc.

Polymers having one alkenyl group per molecule chain end in the method (1) can be obtained by various methods. Although a manufacturing method is illustrated below, it is not necessarily limited to these.
(1-1) Various polymers having an alkenyl group such as organotin, such as allyltributyltin and allyltrioctyltin, in a polymer having one highly reactive carbon-halogen bond per molecule chain end A method of replacing halogen by reacting an organometallic compound.
(1-2) A polymer having one highly reactive carbon-halogen bond per molecule per molecule is reacted with a stabilized carbanion having an alkenyl group as shown in the general formula (10) to form a halogen. How to replace
^{M + C - (R 18)} (R 19) -R 20 -C (R 17) = CH 2 (10)
(Wherein, R ^18, R ¹⁹ together carbanion C ^- or an electron withdrawing group stabilizing, or one of the other hydrogen or an alkyl group having 1 to 10 carbon atoms in the electron-withdrawing group, or a phenyl group R ²⁰ represents a direct bond or a divalent organic group having 1 to 10 carbon atoms, and may include one or more ether bonds, and R ¹⁷ represents hydrogen or an alkyl group having 1 to 20 carbon atoms. Represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and M ⁺ represents an alkali metal ion or a quaternary ammonium ion.
As the electron withdrawing group for R ¹⁸ and R ¹⁹ , those having a structure of —CO ₂ R, —C (O) R and —CN are particularly preferable.

(1-3) An enolate anion is prepared by reacting a polymer having one highly reactive carbon-halogen bond per molecule chain molecule with a single metal such as zinc or an organometallic compound, for example, Thereafter, an electrophilic compound having an alkenyl group, such as an alkenyl group-containing compound having a leaving group such as a halogen or an acetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, an acid halide having an alkenyl group, etc. How to react with.

(1-4) A polymer having one highly reactive carbon-halogen bond per molecule per molecule, for example, an oxyanion having an alkenyl group as shown in the general formula (11) or (12) A method of replacing halogen by reacting with a carboxylate anion.
_{^{H 2 C = C (R 17}} ) -R 21 -O - M + (11)
(Wherein R ¹⁷ and M ⁺ are the same as above. R ²¹ is a divalent organic group having 1 to 20 carbon atoms, and may contain one or more ether bonds)
_{^{H 2 C = C (R 17}} ) -R 22 -C (O) O - M + (12)
(In the formula, R ¹⁷ and M ⁺ are the same as above. R ²² is a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds.)
Etc.

The above-described method for synthesizing a polymer having one highly reactive carbon-halogen bond per molecule at the end of a molecule chain is an atom transfer using an organic halide as described above as an initiator and a transition metal complex as a catalyst. Examples include, but are not limited to, radical polymerization methods.
Further, a polymer having one alkenyl group per molecule at the molecular chain end can be obtained from a polymer having at least one hydroxyl group at the molecular chain end, and the methods exemplified below can be used, but are not limited thereto. It is not done.

In the polymer hydroxyl group having at least one hydroxyl group at the molecular chain end,
(1-5) A method of reacting a base such as sodium methoxide with an alkenyl group-containing halide such as allyl chloride,
(1-6) a method of reacting an alkenyl group-containing isocyanate compound such as allyl isocyanate,
(1-7) a method of reacting an alkenyl group-containing acid halide such as (meth) acrylic acid chloride in the presence of a base such as pyridine,
(1-8) a method of reacting an alkenyl group-containing carboxylic acid such as acrylic acid in the presence of an acid catalyst,
Etc.

When an alkenyl group is introduced by converting a halogen of a polymer having one highly reactive carbon-halogen bond per molecule at the end of the molecule chain, one highly reactive carbon-halogen bond per molecule A highly reactive carbon-halogen bond is formed at the terminal obtained by radical polymerization (atom transfer radical polymerization) of a vinyl monomer using an organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst. It is preferable to use a polymer having one molecule per molecule chain end.

Moreover, there is no restriction | limiting in particular as a hydrosilane compound which has a crosslinkable silyl group, When a typical thing is shown, the compound shown by General formula (13) will be illustrated.
^{_{H- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (13)
(In the formula, R ¹ , R ² , Y, a, b and m are the same as described above. When two or more R ¹ or R ² are present, they may be the same or different. However, it shall be satisfied that a + mb ≧ 1.)
Among these hydrosilane compounds, in particular, the general formula (14)
_{^{H-Si (R 2) 3}} -a (Y) a (14)
(Wherein R ² , Y and a are the same as above)
The compound which has a crosslinkable silyl group shown by is preferable from a point with easy acquisition.

When the hydrosilane compound having a crosslinkable silyl group is added to an alkenyl group, a transition metal catalyst is usually used. Examples of the transition metal catalyst include platinum simple substance, alumina, silica, carbon black and the like in which a platinum solid is dispersed, chloroplatinic acid, a complex of chloroplatinic acid and alcohol, aldehyde, ketone, etc., platinum-olefin. Complex, platinum (0) -divinyltetramethyldisiloxane complex is mentioned. Examples of the catalyst other than platinum _{compounds, RhCl (PPh 3) 3,} RhCl 3, RuCl 3, IrCl 3, FeCl 3, AlCl 3, PdCl 2 · H 2 O, NiCl 2, TiCl 4 , and the like.

The amount of vinyl polymer having a crosslinkable silyl group at one end, preferably a polymer having a molecular weight distribution of less than 1.8, is 5 in terms of modulus and elongation with respect to 100 parts by weight of the vinyl polymer. It is preferable that it is -400 weight part.

As a second embodiment in which two or more kinds of vinyl polymers are used in combination, a vinyl polymer having a molecular weight distribution of 1.8 or more and a vinyl polymer having a molecular weight distribution of less than 1.8 are used in combination. You can also. A vinyl polymer having a molecular weight distribution of 1.8 or more may or may not have a crosslinkable silicon group, but having a crosslinkable silicon group is preferable because weather resistance, adhesive strength, and strength at break are further improved. . Moreover, the improvement of the tear strength of the hardened | cured material of a composition can be anticipated. As the main chain of the vinyl polymer having a molecular weight distribution of less than 1.8, used as the first polymer, the vinyl polymer having a molecular weight distribution of 1.8 or more, or the second polymer, Polymers derived from the vinyl monomers mentioned can be used, and both polymers are preferably acrylate polymers.

A vinyl polymer having a molecular weight distribution of 1.8 or more 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, radical initiator, chain transfer agent and the like and reacting at 50 to 150 ° C. In this case, generally a molecular weight distribution of 1.8 or more is obtained.

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 nonreactive solvents such as ethers, hydrocarbons, and esters.

Examples of the method for introducing a crosslinkable silyl group include a method of copolymerizing a compound having both a polymerizable unsaturated bond and a crosslinkable silyl group with a (meth) acrylate monomer unit.
As a compound having both a polymerizable unsaturated bond and a crosslinkable silyl group, the general formula (26):
_{^{CH 2 = C (R 28)}} COOR 30 - [Si (R 1) 2-b (Y) b O] m Si (R 2) 3-a (Y) a (26)
(In the formula, R ²⁸ is the same as above. R ³⁰ is a divalent alkylene group having 1 to 6 carbon atoms. R ¹ , R ² , Y, a, b and m are the same as above.)
Or general formula (27):
_{^{CH 2 = C (R 28)}} - [Si (R 1) 2-b (Y) b O] m Si (R 2) 3-a (Y) a (27)
^{(Wherein, R 28, R 1, R} 2, Y, a, b, m are as defined 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.

Further, when a compound having both a mercapto group and a crosslinkable silyl group is used as a chain transfer agent, the crosslinkable silyl group can be introduced into the polymer terminal. Examples of such chain transfer agents include mercaptans such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldiethoxysilane. .

A vinyl polymer having a crosslinkable functional group and having a molecular weight distribution of 1.8 or more preferably has a number average molecular weight of 500 to 100,000 in terms of polystyrene as measured by GPC. Furthermore, the thing of 1,500-30,000 is more preferable from the weather resistance of a hardened | cured material, and workability | operativity being favorable.

<< Epoxy resin (II) >>
The epoxy resin (II) used in the curable composition of the present invention includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type. Rubber-modified epoxy containing epoxy resin, novolac type epoxy resin, glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, hydrogenated bisphenol A type (hydrogenated bisphenol A type) epoxy resin, fluorinated epoxy resin, polybutadiene or NBR Resin, Flame retardant epoxy resin such as glycidyl ether of tetrabromobisphenol A, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy Fatty, diaminodiphenylmethane epoxy resin, urethane-modified epoxy resin having urethane bond, various alicyclic epoxy resins, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol Examples include glycidyl ethers of polyhydric alcohols such as diglycidyl ether and glycerin, epoxidized products of unsaturated polymers such as hydantoin type epoxy resins, petroleum resins, etc., but are not limited to these and generally The used epoxy resin can be used. These epoxy resins may be used alone or in combination of two or more.

Among these epoxy resins, those having at least two epoxy groups in one molecule are preferable from the viewpoint of high reactivity and easy formation of a three-dimensional network upon curing.
In addition, since the cured product when the curable composition containing the vinyl polymer of the present invention and the epoxy resin is cured is transparent, the epoxy resin may be compatible with the vinyl polymer. preferable. For example, hydrogenated bisphenol A type epoxy resins and glycidyl ester type epoxy resins are easily compatible with various vinyl polymers and easily obtain a transparent cured product. Among these, hydrogenated bisphenol A type epoxy resins are more preferable from the viewpoint of compatibility and the like.

A curable composition having a combination of good compatibility between the vinyl polymer and the epoxy resin is likely to have a modulation structure when cured, and as a result, a transparent cured product is easily obtained. Furthermore, the mechanical properties may be remarkably improved.
As a preferable combination of the vinyl polymer and the epoxy resin, for example, a vinyl polymer or vinyl copolymer having a main chain having a higher polarity than the butyl acrylate homopolymer and an epoxy resin having an aromatic ring. Examples thereof include combinations and combinations of vinyl polymers or vinyl copolymers and epoxy resins having no aromatic ring.
Although it does not specifically limit as an example of the epoxy resin which does not have an aromatic ring, An alicyclic epoxy resin is preferable and the epoxy resin in which a glycidyl group is not directly attached to an alicyclic ring is more preferable.
In addition, the epoxy resin which does not have an aromatic ring tends to be excellent in weather resistance and difficult to be colored. Moreover, the epoxy resin which does not contain an ester bond in the main chain tends to be excellent in heat resistance.

The main chain is not particularly limited as the vinyl polymer or vinyl copolymer having a higher polarity than the butyl acrylate homopolymer, but, as described above, represented by the general formula (i). Preferred are polymers or copolymers having a repeating unit structure.
_{- [CH 2 -CR (COOR '} )] - (i)
(In the formula, R is hydrogen or a methyl group, and R ′ is the same or different and is an alkoxyalkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 3 carbon atoms.)

As a combination of a vinyl polymer and an epoxy resin, specifically, a copolymer weight of ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate (molar ratio: 40 to 50/20 to 30/30 to 20) A combination of a polymer and a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a hydrogenated bisphenol A type epoxy resin; butyl acrylate homopolymer, a hydrogenated bisphenol A type epoxy resin or hexahydrophthalic acid diglycidyl ester A combination of these is preferred, but is not limited thereto.
In addition, by adding a filler such as calcium carbonate or carbon black to this curable composition, the cured product becomes opaque, but the modulation structure is not essentially destroyed.

<< Mixing ratio of vinyl polymer (I) and epoxy resin (II) >>
In the curable composition of the present invention, the mixing ratio [(I) / (II)] of the vinyl polymer (I) having at least one crosslinkable silyl group and the epoxy resin (II) is 100 / weight ratio. The range of 1 to 1/100 is preferable, the range of 100/5 to 5/100 is more preferable, and the range of 100/10 to 10/100 is still more preferable, but the mixing ratio is not limited, and each application Can be set according to the purpose.
Due to its characteristics, this curable composition can be used as an elastic adhesive for bonding materials with different linear expansion coefficients or for members that are repeatedly displaced by a heat cycle. Taking advantage of its properties, it can be used as a coating agent in applications where the substrate can be seen. For example, in this elastic adhesive application, if the mixing ratio of the epoxy resin is too large, the cured product becomes hard and the peel strength tends to decrease, and if it is too small, the adhesive strength and water resistance tend to decrease. The amount of (II) used is usually preferably about 10 to 150 parts by weight and more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the vinyl polymer (I).

<< Room-temperature curable latent curing agent (III) >>
The room temperature curable latent curing agent (III) used in the curable composition of the present invention is not particularly limited, and examples thereof include ketimine; oxazolidine; silamine obtained by dehydrochlorination condensation of an amine compound and trimethylchlorosilane. It is done. Of these, ketimine is preferred from the balance between curability and storage stability.

The ketimine is a compound having a functional group represented by the following general formula (001).
R ⁴⁰ R ⁴¹ C═N— (001)
(In the formula, R ⁴⁰ and R ⁴¹ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.)

Ketimine is stably present in the absence of moisture, and is decomposed into primary amines and ketones by moisture, and the resulting primary amine becomes a room temperature curable curing agent for the epoxy resin.
Examples of such ketimines include compounds represented by the following general formula (002).
(R ⁴⁰ R ⁴¹ C = N) _l -Z (002)
(In the formula, R ⁴⁰ and R ⁴¹ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, Z represents an organic group, and l represents 1, 2 or 3. )

The ketimine can be obtained by a condensation reaction between an amine compound and a carbonyl compound. A known amine compound or carbonyl compound may be used for the synthesis of ketimine.
Examples of amine compounds include ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane, 2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, and p-phenylene. Diamines such as diamine and p, p'-biphenylenediamine; polyvalent amines such as 1,2,3-triaminopropane, triaminobenzene, tris (2-aminoethyl) amine and tetra (aminomethyl) methane; diethylenetriamine, Polyalkylene polyamines such as triethylenetriamine and tetraethylenepentamine; polyoxyalkylene polyamines; γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- ( -Aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- ( 2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyl Diethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane , - aminosilane such as vinylbenzyl -γ- aminopropyltriethoxysilane can be used.
Examples of the carbonyl compound include aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, diethylacetaldehyde, glyoxal, and benzaldehyde; cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone, and trimethylcyclohexanone; Aliphatic ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone; acetylacetone, methyl acetoacetate, ethyl acetoacetate, malonic acid Β-dicarbonyl such as dimethyl, diethyl malonate, methyl ethyl malonate, dibenzoylylmethane Compounds and the like can be used.
Examples of commercially available ketimines include ADEKA HARDNER EH-235R, EH-235R-2, EH-235R-2S (above, manufactured by Asahi Denka), EpiCure H-30 (manufactured by Japan Epoxy Resin), and the like.

Further, ketiminated aminosilanes can also be used, and examples include trade name Silaace S340 (N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, manufactured by Chisso). In addition to the action as a room temperature curing type latent curing agent, the ketiminized aminosilane also has effects such as a curing catalyst, improvement of mechanical properties of a cured product, and imparting adhesiveness.
When an imino group is present in the ketimine, the imino group may be reacted with styrene oxide; glycidyl ether such as butyl glycidyl ether or allyl glycidyl ether; glycidyl ester or the like.
These ketimines may be used alone or in combination of two or more.

Oxazolidine is a compound having a saturated 5-membered heterocyclic ring containing oxygen and nitrogen and having an oxazolidine ring that opens in the presence of moisture. For example, it is synthesized from N-methylethanolamine, and N-methylethanolamine is regenerated by moisture in the air.
Examples of the oxazolidine include N-hydroxyalkyl oxazolidine and its polyisocyanate adduct, oxazolidine silyl ether, carbonate oxazolidine, ester oxazolidine, and alkyl oxazolidine. Specific examples include the following.

(In the formula, R ⁵¹ is an alkylene group having 2 to 6 carbon atoms, R ⁵² and R ⁵³ are each independently a hydrogen atom, an alkyl group having 1 or more carbon atoms, an alicyclic alkyl group having 5 to 7 carbon atoms, or An aryl group having 6 to 10 carbon atoms, R ⁵⁴ represents an alkylene group having 2 to 6 carbon atoms, an aryl group, an alkylene group having 2 to 6 carbon atoms including a urethane bond, or an aryl group including a urethane bond ^. Is an aliphatic hydrocarbon group having 5 or more carbon atoms, R ⁵⁶ is a residue obtained by removing an isocyanate group from an organic polyisocyanate, m is an integer of 1 to 6, and n is an integer of 0 to 4.)

Here, R ⁵¹ is an alkylene group having 2 to 6 carbon atoms, preferably 2 to 3 carbon atoms, and more preferably 2 carbon atoms.
R ⁵² and R ⁵³ are each independently a hydrogen atom, an alkyl group having 1 or more carbon atoms, an alicyclic alkyl group having 5 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
R ⁵⁴ is an alkylene group having 2 to 6 carbon atoms, an aryl group, an alkylene group having 2 to 6 carbon atoms including a urethane bond, or an aryl group including a urethane bond, and alkylene having 2 to 5 carbon atoms having a urethane bond. It is preferably a group or an aryl group.
R ⁵⁵ is an aliphatic hydrocarbon group having 5 or more carbon atoms, preferably 5 to 15 carbon atoms, such as n-pentyl, 2-methylpentyl, 3-methylpentyl, 3,5,5-trimethylpentyl, Examples include n-heptyl, n-octyl, n-nonyl, n-decanyl, n-undecanyl, n-dodecanyl, n-tridecanyl, n-tetradecanyl and the like. Especially, a C5-C10 thing is preferable.
R ⁵⁶ is a residue obtained by removing an isocyanate group from an organic polyisocyanate, and may be any of aliphatic, alicyclic, and aromatic. For example, aromatic groups such as tolylene, diphenylmethane, phenylene, polymethylene polyphenylene, aliphatic groups such as hexamethylene, alicyclic hydrocarbon groups such as isophorone, aromatic aliphatic groups such as xylene, and carbodiimide modification A group or an isocyanurate-modified group, and the like, and one or a combination of two or more thereof is used.
m is an integer of 1 to 6, and 2 to 3 is particularly preferable in terms of curability and physical properties of the cured product.
n is an integer of 0 to 4, and 0 to 2 is particularly preferable from the viewpoint of curability.

N-hydroxyalkyloxazolidine can be prepared, for example, by a dehydration condensation reaction between an alkanolamine and a ketone or aldehyde. Oxazolidine silyl ether includes the above-mentioned N-hydroxyalkyl oxazolidine, trimethoxysilane, tetramethoxysilane, triethoxysilane, dimethoxydimethylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, It can be obtained by reaction with an alkoxysilane such as γ-glycidoxypropyltriethoxysilane. The carbonate oxazolidine can be obtained, for example, by reacting the above-mentioned N-hydroxyalkyl oxazolidine with a carbonate such as diallyl carbonate, dimethyl carbonate, or dipropylene carbonate using a polyhydric alcohol such as diethylene glycol or glycerin. The ester oxazolidine can be obtained, for example, by reacting the above-mentioned N-hydroxyalkyl oxazolidine with a lower alkyl ether of dicarboxylic acid or polycarboxylic acid. Moreover, you may use the oxazolidine compound which has a 3 or more oxazolidine ring in 1 molecule, This compound can be obtained by making N-hydroxyalkyl oxazolidine and a polyisocyanate compound react.

Silamine is obtained by dehydrochlorination condensation of various amines and trimethylchlorosilane, and is easily hydrolyzed by moisture in the air to regenerate the amine. The amine as a raw material is preferably a secondary amine or an aromatic amine from the viewpoint of storage stability. For example, m-xylenediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetra Examples include oxaspiro [5,5] undecane (ATU), piperidine and the like.

In addition, a curing agent such as an aromatic diazonium salt compound, a diallyl iodonium salt compound, a triallyl sulfonium salt, or a selenium salt compound activated by light irradiation may be used as the room temperature curing type latent curing agent (III). it can.

The use amount of the room temperature curable latent curing agent (III) is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin (II). Unlikely, it is preferably calculated based on the active hydrogen equivalent and the epoxy equivalent of amine produced by decomposition by moisture, preferably 0.4 to 1.2 times the active hydrogen equivalent of the epoxy equivalent. 0.5 to 1.0 times is more preferable, and 0.6 to 0.7 times is more preferable. When the amount of the room temperature curable latent curing agent is too large, when the epoxy resin is bundled, the epoxy resin starts to react, and the storage stability may be lowered. In addition, when a reactive diluent (M-1230: Kyoeisha Chemical Co., Ltd.) is added, this storage stability may be improved. In addition, the storage stability may be improved by a dehydrating agent such as vinyltrimethoxysilane.

<< Reactive silicon group-containing silane compound (IV) >>
In the curable composition of the present invention, a reactive silicon group-containing silane compound (IV) can be further added.
The reactive silicon group-containing silane compound (IV) is a generic term for low molecular weight silicon compounds having a hydrolyzable functional group that reacts in the presence of moisture, and usually has a molecular weight of 500 or less.
Examples of the hydrolyzable functional group include an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an aminooxy group, an amide group, and an alkenyloxy group. Examples of the substituent include an epoxy-containing group, an amino-containing group, an acrylic-containing group, and a mercapto-containing group.

Specific examples of such reactive silicon group-containing silane compounds (IV) include Si (OC ₂ H ₅ ) ₄ , CH ₂ = CHSi (OAc) ₃ , CH ₃ -Si [ON = C (CH ₃ ). (C ₂ H ₅ )] ₃ , CH ₃ Si [N (CH ₃ ) ₂ ] ₃ , CH ₃ Si [N (CH ₃ ) (C ₂ H ₅ )] ₃ , CH ₃ Si [N (CH ₃ ) Ac ] ₃ , CH ₃ Si [OC (C ₂ H ₅ ) = CH ₂ ] ₃ , CH ₂ (O) CHCH ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₂ = CH ₂ Si (OCH ₃ ) ₃ , CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , HS (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH _{3) 3, H 2 N (} CH 2) 2 NH (CH 2) 3 Si (CH 3) (OCH 3) 2, (C 2 H 5 O) 3 Si (CH 2) 3 NH (CH 2) 2 NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃
(In the formula, Ac represents an acetyl group) and the like.

These silane compounds (IV) may be used alone or in combination of two or more.
The amount of these silane compounds (IV) used is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the total amount of the vinyl polymer (I) and the epoxy resin (II). If it is less than 0.01 part by weight, the expected adhesiveness is hardly exhibited, and if it exceeds 20 parts by weight, the physical properties of the rubber after curing tend to decrease.

Although not particularly limited, among the reactive silicon group-containing silane compound (IV), a compound such as aminosilane having both a group that reacts with a glycidyl group and a group that reacts with a crosslinkable silyl group is present in the present curable composition. This is more preferable because it significantly improves the adhesive properties of the product and the mechanical properties of the cured product obtained by curing the product.

<< Polyether polymer (V) >>
In the curable composition of the present invention, it is also possible to use a polyether polymer (V).

<Polyether polymer having a crosslinkable functional group>
Main chain The main chain of the polyether polymer is not particularly limited, and examples thereof include polyethylene oxide, polypropylene oxide, polybutylene oxide, and polyphenylene oxide. Of these, it is preferably essentially polyoxyalkylene, more preferably essentially polypropylene oxide, which may contain ethylene oxide, butylene oxide, phenylene oxide and the like in addition to propylene oxide. The polyether polymer may or may not contain a urethane bond in the main chain.
Here, “the main chain is essentially polypropylene oxide” means that propylene oxide units occupy 50% or more of the repeating units constituting the main chain, preferably 70% or more, more preferably 90%. % Or more.
The lower the viscosity, the better the handleability, so that the molecular weight distribution (Mw / Mn) of the polypropylene oxide polymer is more preferably 1.5 or less.

Crosslinkable functional group The crosslinkable functional group in the polyether polymer is not particularly limited, but is preferably a crosslinkable silyl group, alkenyl group, hydroxyl group, amino group, polymerizable carbon-carbon dioxygen. Examples include a group having a heavy bond and an epoxy group. In particular, a crosslinkable silyl group is preferable.
The number of crosslinkable functional groups possessed by the polyether polymer is preferably at least one on average in the molecule, but may be less than one. From the viewpoint of curability of the composition, it is preferably more than 1, more preferably 1.1 to 4.0 on average, and even more preferably 1.5 to 2.5 on average. Moreover, it is preferable from a viewpoint of rubber elasticity of hardened | cured material that a crosslinkable functional group exists in the terminal of a polyether-type polymer. More preferably, there are functional groups at both ends of the polymer.

Molecular weight The polyether polymer having at least one crosslinkable functional group preferably has a number average molecular weight of 7500 or more, but may be less than 7500. In particular, it is more preferable to use an organic polymer having a number average molecular weight of 7500 to 25000. When the number average molecular weight of the polyether polymer is less than 7500, the cured product is hard and the elongation tends to be low, and when the number average molecular weight exceeds 25000, there is no problem in the flexibility and elongation of the cured product. There is a tendency that the adhesiveness of the coalescence itself is lowered and the practicality is lowered. However, even if the molecular weight is low, flexibility and elongation may be improved if the number of crosslinkable functional groups is small, and adhesion is improved if the number of crosslinkable functional groups is large even if the molecular weight is high. There are things to do. The number average molecular weight is particularly preferably 8000 to 20000 from the viewpoint of viscosity, but it may be less than 8000 or may exceed 20000.

Use amount of the polyether polymer (V) The use amount of the polyether polymer (V) may be any amount, but a vinyl polymer having at least one crosslinkable silyl group ( The weight ratio [(V) / ((I) + (II))] is preferably in the range of 100/1 to 1/100 with respect to the total of I) and the epoxy resin (II), and 100/5 to 5/100. Is more preferable, and the range of 100/10 to 10/100 is still more preferable. The addition amount can be set according to each application and purpose. However, if the addition amount is too large, the excellent heat resistance and weather resistance, which are one of the effects of the present invention, may be lowered.

In the above polyether polymer, (meth) acrylic polymer produced by a general radical polymerization method, or high-temperature continuous bulk polymer (for example, SGO oligomer manufactured by Toa Gosei Co., Ltd.) or silylated product thereof Those previously mixed with may be used for mixing with the vinyl polymer.

<Polyether polymer having a crosslinkable silyl group>
The polyether polymer having a crosslinkable silyl group will be described below.
Main chain The main chain structure of the polyether polymer having a crosslinkable silyl group is the same as described above. The main chain may be linear or branched, or a mixture thereof. Of these, a main chain derived from polyoxypropylene diol, polyoxypropylene triol or a mixture thereof is particularly preferable. Further, other monomer units and the like may be contained, but the repeating unit constituting the main chain of the polyether polymer is 50% by weight or more, preferably 80% by weight or more in the polymer. Preferably it is present.
The main chain may or may not contain a urethane bond or urea bond.

The molecular structure of the polyether-based polymer varies depending on the intended use and intended characteristics, and those described in JP-A-63-112642 can be used. Such polyoxyalkylenes can be prepared by conventional polymerization methods (anionic polymerization methods using caustic), cesium metal catalysts, JP-A 61-197631, JP-A 61-215622, and JP-A 61-215623. And a porphyrin / aluminum complex catalyst exemplified in JP-A-61-218632 and the like, a double metal cyanide complex catalyst exemplified in JP-B-46-27250 and JP-B-59-15336, etc., and JP-A-10-273512 It can be obtained by a method using a catalyst composed of the exemplified polyphosphazene salt.

In a method using a porphyrin / aluminum complex catalyst, a double metal cyanide complex catalyst or a catalyst comprising a polyphosphazene salt, the molecular weight distribution (Mw / Mn) is 1.6 or less, and further a small value such as 1.5 or less. An oxyalkylene polymer can be obtained. When the molecular weight distribution is small, there is an advantage that the viscosity of the composition can be reduced while maintaining the low modulus and high elongation of the cured product.

Crosslinkable silyl group As the crosslinkable silyl group, a group represented by the above general formula (1) can be used as in the vinyl polymer (I). The group represented is preferred. The explanation about the group represented by the general formula (1) or the general formula (6) is similarly applied to the polyether polymer having a crosslinkable silyl group. The crosslinkable silyl group in the polyether polymer may have the same structure as the crosslinkable silyl group in the vinyl polymer having a crosslinkable silyl group, or may have a different structure.
Since the bond between the crosslinkable silyl group and the polyether moiety is resistant to hydrolysis, it appears that there are at least three carbon atoms between the silicon atom of the silyl group and the ether oxygen atom of the polyether moiety. In addition, an alkylene group such as trimethylene and tetramethylene is preferable.

Number and position of crosslinkable silyl groups The average number of crosslinkable silyl groups in the polyether polymer (V) is at least one in the molecule from the viewpoint of curability of the composition. Preferably, it is more preferably at least 1.2, more preferably more than 1.2 and 4.0 or less, and particularly preferably 1.5 or more and 2.5 or less. Moreover, it is preferable that the crosslinkable silyl group of a polyether-type polymer exists in the terminal of a molecular chain from a viewpoint of rubber elasticity of hardened | cured material, More preferably, it exists in the both terminal of a polymer.

Further, a polyether polymer having 1.2 or less crosslinkable silyl groups on average can be used. In this case, a cured product having high elongation at break, low bleeding, low surface contamination, and excellent paint adhesion can be obtained. Moreover, the viscosity of a composition can be reduced by setting the molecular weight of this polymer smaller. The lower limit of the number of crosslinkable silyl groups is preferably at least 0.1, more preferably 0.3 or more, and even more preferably 0.5 or more. The crosslinkable silyl group is preferably at the end of the molecular chain. Further, the crosslinkable silyl group of this polyether polymer is preferably only at one end in the main chain and not at the other end, but if it is 1.2 or less on average It is not particularly limited. In the case of reducing the viscosity by using a polyether polymer having 1.2 or less crosslinkable silyl groups on average, the preferable molecular weight is less than 10,000, more preferably less than 5,000.

Method for introducing crosslinkable silyl group The introduction of the crosslinkable silyl group may be carried out by a known method. For example, the following method etc. are mentioned. For example, in the case of an oxyalkylene polymer obtained using a double metal cyanide complex catalyst, JP-A-3-72527, and in the case of an oxyalkylene polymer obtained using a polyphosphazene salt and active hydrogen as a catalyst, 60723.

(1) An oxyalkylene polymer having a functional group such as a hydroxyl group at the terminal is reacted with an organic compound having an active group and an unsaturated group which are reactive with the functional group, or an unsaturated group-containing epoxy compound To obtain an unsaturated group-containing oxyalkylene polymer. Next, hydrosilylation is performed by allowing hydrosilane having a crosslinkable silyl group to act on the obtained reaction product.
(2) An unsaturated group-containing oxyalkylene polymer obtained in the same manner as in the method (1) is reacted with a compound having a mercapto group and a crosslinkable silyl group.
(3) A functional group (hereinafter referred to as Y ′) having reactivity with this Y functional group to an oxyalkylene polymer having a hydroxyl group, a functional group such as an epoxy group or an isocyanate group (hereinafter referred to as Y functional group) at the terminal. And a compound having a crosslinkable silyl group).

Examples of the silicon compound having a Y ′ functional group include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, 3- Amino-2-methylpropyltrimethoxysilane, N-ethyl-3-amino-2-methylpropyltrimethoxysilane, 4-amino-3-methylpropyltrimethoxysilane, 4-amino-3-methylpropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and amino group-containing silanes such as partial Michael addition reaction products of various amino group-containing silanes with maleic esters and acrylate compounds; γ-mercaptopropyltrimethoxysilane Γ-mercaptopropylmethyldi Mercapto group-containing silanes such as methoxysilane; epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; vinyltriethoxysilane, γ -Vinyl type unsaturated group-containing silanes such as methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, etc .; Chlorine atom-containing silanes such as γ-chloropropyltrimethoxysilane; γ-isocyanatopropyl Isocyanate-containing silanes such as triethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropyltrimethoxysilane, etc .; methyldimethoxysilane, trimethoxysilane, methyldiethoxysilane, tri Specific examples include hydrosilanes such as ethoxysilane, but are not limited thereto.

In addition, when producing a polymer having an average number of crosslinkable silyl groups of 1.2 or less, a polyether polymer having only one functional group in the molecule when introducing the crosslinkable silyl group. And a method for obtaining a polyether polymer having an average of 1.2 or less crosslinkable silyl groups by reacting the functional group with a compound having a crosslinkable silyl group in an equivalent amount or a smaller amount. By using a polyether polymer having an average of one or more functional groups in the molecule and reacting a compound having a crosslinkable silyl group that is less than the functional group, There is a method for obtaining a polyether polymer having an average of 1.2 or less.

Use amount of the polyether polymer having a crosslinkable silyl group The use amount of the polyether polymer (V) having a crosslinkable silyl group may be any amount. The total of the vinyl polymer (I) and the epoxy resin (II) having at least one has a weight ratio [(V) / ((I) + (II))] of 100/1 to 1/100. Preferably, the range of 100/5 to 5/100 is more preferable, and the range of 100/10 to 10/100 is still more preferable. The addition amount can be set according to each application and purpose. However, if the addition amount is too large, the excellent heat resistance and weather resistance, which are one of the effects of the present invention, may be lowered.
When a polyether polymer having 1.2 or less crosslinkable silyl groups on average is used, the amount used is 1 to 200 parts by weight with respect to 100 parts by weight of the vinyl polymer (I). Part or less, preferably 3 parts by weight or more and 100 parts by weight or less, more preferably 5 parts by weight or more and 80 parts by weight or less. If it is less than 1 part by weight, the effect of addition is difficult to obtain, and if it exceeds 200 parts by weight, the physical properties of the cured product tend to become unstable.

As an embodiment to be used as a mixture, (i) a vinyl polymer having a crosslinkable silyl group represented by the general formula (1) is added to a polyether polymer having a crosslinkable silyl group and an average of 1.2. Add the following polyether polymer having a crosslinkable silyl group, (ii) Add a polyether polymer having a crosslinkable silyl group and a vinyl polymer having a crosslinkable silyl group at one end (Iii) When adding a polyether polymer having a crosslinkable silyl group and a vinyl polymer having a crosslinkable functional group and a molecular weight distribution of 1.8 or more, an average of 1.2 Adding a polyether polymer having the following crosslinkable silyl group and a vinyl polymer having a crosslinkable silyl group at one end; (iv) an average of 1.2 or less crosslinkable silyl groups; Polyer with The molecular weight has a Le-based polymer and a crosslinkable functional group distribution and the like by adding 1.8 or more vinyl polymers, and the like.

<< Arbitrary Polymer Components Having Various Crosslinkable Functional Groups >>
In the curable composition of the present invention, polymers having various crosslinkable functional groups may be added as optional components. Examples of the polymer having a crosslinkable functional group include (1) a polyisobutylene polymer having a crosslinkable functional group, particularly a polyisobutylene polymer having a crosslinkable silyl group, and (2) polysiloxane. . These polymers can be added using 1 type (s) or 2 or more types.

When these polymer optional components are added to the vinyl polymer having a crosslinkable silyl group of the present invention, the polymer has a hydrolyzable silicon group formed by bonding two hydrolyzable groups per silicon atom. A vinyl polymer and a polymer arbitrary component formed by bonding three hydrolyzable groups per crosslinkable functional group may be combined. Conversely, three hydrolyzable groups per silicon atom are combined. You may combine the vinyl polymer which has a hydrolysable silicon group formed by combining, and the polymer arbitrary component formed by combining two hydrolyzable groups per crosslinkable functional group. Also, any polymer may be a combination having a crosslinkable functional group formed by bonding three hydrolyzable groups, or a combination having a crosslinkable functional group formed by bonding two hydrolyzable groups. . Furthermore, one to three things may be mixed.

<< Curable composition >>
In the curable composition of the present invention, a curing catalyst or a curing agent is often added. Moreover, you may add various compounding agents according to the target physical property.

<Curing catalyst and curing agent>
Curing catalyst / curing agent for vinyl polymer (I) having at least one crosslinkable silyl group The vinyl polymer (I) having a crosslinkable silyl group is prepared in the presence of various conventionally known condensation catalysts. Alternatively, it is crosslinked and cured by forming a siloxane bond in the absence. The properties of the cured product can be broadly created from rubbery to resinous depending on the molecular weight and main chain skeleton of the polymer.

Examples of such condensation catalysts include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutylmalate, dibutyltin Diisooctylmalate, dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, dioctyltin diisooctylmalate Dialkyltin dicarboxylates such as dibutyltin dimethoxide, dialkyltin alkoxides such as dibutyltin diphenoxide, such as dibutyltin diacetylacetonate, dibutyltin Intramolecular coordination derivatives of dialkyl tin such as ethyl acetoacetate, for example, reaction products of dialkyl tin oxide such as dibutyl tin oxide and dioctyl tin oxide and ester compounds such as dioctyl phthalate, diisodecyl phthalate and methyl maleate For example, a reaction product of a dialkyltin oxide and a silicate compound such as dibutyltin bistriethoxysilicate and dioctyltin bistriethoxysilicate, and a tetravalent tin compound such as an oxy derivative (stannoxane compound) of these dialkyltin compounds; Divalent tin compounds such as tin octylate, tin naphthenate, tin stearate, and tin ferzatic acid, or a reaction product and mixture of these with an amine compound such as laurylamine described later; Monoalkyltins such as monobutyltin compounds and monooctyltin compounds such as ate and monobutyltin triisopropoxide; for example, tetrabutyltitanate, tetrapropyltitanate, tetra (2-ethylhexyl) titanate, isopropoxytitanium bis (ethylacetoacetate) ), Etc .; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; bismuth carboxylate, iron carboxylate, titanium carboxylate, lead carboxylate, Vanadium carboxylate, zirconium carboxylate, calcium carboxylate, potassium carboxylate, barium carboxylate, manganese carboxylate, cerium carboxylate, carboxyl Metal salts such as nickel acid, cobalt carboxylate, zinc carboxylate, and aluminum carboxylate (2-ethylhexanoic acid, neodecanoic acid, versatic acid, oleic acid, naphthenic acid, etc.) metal salts, and these and laurylamine described later Reaction products and mixtures with amine compounds; chelating compounds such as zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, dibutoxyzirconium diacetylacetonate, zirconium acetylacetonate bis (ethylacetoacetate, titanium tetraacetylacetonate, etc. Methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decyl Aliphatic primary amines such as amine, laurylamine, pentadecylamine, cetylamine, stearylamine, cyclohexylamine; dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dioctylamine, di (2-ethylhexyl) ) Aliphatic secondary amines such as amine, didecylamine, dilaurylamine, dicetylamine, distearylamine, methylstearylamine, ethylstearylamine, butylstearylamine; aliphatic such as triamylamine, trihexylamine, trioctylamine Tertiary amines; Aliphatic unsaturated amines such as triallylamine and oleylamine; Aromatic amines such as laurylaniline, stearylaniline and triphenylamine; and others As amines, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, ethylenediamine, hexamethylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) undecene-7 (DBU), etc. Amine compounds, or salts of these amine compounds with carboxylic acids, etc .; and amine tin compounds such as laurylamine and tin octylate reactants or mixtures Reaction product and mixture with compound; low molecular weight polyamide resin obtained from excess polyamine and polybasic acid; reaction product of excess polyamine and epoxy compound; γ-aminopropyltrimethoxysilane, γ-aminopropyltri Ethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl) aminopropyltrimethoxysilane, N- (β-aminoethyl) ) Aminopropylmethyldimethoxysilane, N- (β-aminoethyl) aminopropyltriethoxysilane, N- (β-aminoethyl) aminopropylmethyldiethoxysilane, N- (β-aminoethyl) aminopropyltriisopropoxysilane Γ-ureidopropyltrimeth Examples include xylsilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, and N-vinylbenzyl-γ-aminopropyltriethoxysilane. Silanol condensation catalysts such as silane coupling agents having amino groups such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, etc., are derivatives obtained by modifying these. Furthermore, known silanol condensation catalysts such as other acidic catalysts such as fatty acids such as ferrous acid and organic acidic phosphoric acid ester compounds, basic catalysts and the like can be exemplified.

Examples of the organic acidic phosphoric acid ester compound for the acidic catalyst include (CH ₃ O) ₂ —P (═O) (— OH), (CH ₃ O) —P (═O) (— OH) ₂ , (C ₂ H _{5 O) 2 -P (= O} ) (- OH), (C 2 H 5 O) -P (= O) (- OH) 2, (C 3 H 7 O) 2 -P (= O) (- _{OH), (C 3 H 7} O) -P (= O) (- OH) 2, (C 4 H 9 O) 2 -P (= O) (- OH), (C 4 H 9 O) -P _{(= O) (- OH)} 2, (C 8 H 17 O) 2 -P (= O) (- OH), (C 8 H 17 O) -P (= O) (- OH) 2, (C _{10 H 21 O) 2 -P (} = O) (- OH), (C 10 H 21 O) -P (= O) (- OH) 2, (C 13 H 27 O) 2 -P (= O) _{(-OH), (C 13 H} 27 O) -P (= O) (- _{H) 2, (C 16 H} 33 O) 2 -P (= O) (- OH), (C 16 H 33 O) -P (= O) (- OH) 2, (HO-C 6 H 12 O _{) 2 -P (= O) (} - OH), (HO-C 6 H 12 O) -P (= O) (- OH) 2, (HO-C 8 H 16 O) -P (= O) ( _{-OH), (HO-C 8} H 16 O) -P (= O) (- OH) 2, [(CH 2 OH) (CHOH) O] 2 -P (= O) (- OH), [( _{CH 2 OH) (CHOH) O} ] -P (= O) (- OH) 2, [(CH 2 OH) (CHOH) C 2 H 4 O] 2 -P (= O) (- OH), [( CH ₂ OH) (CHOH) C ₂ H ₄ O] —P (═O) (— OH) _{2 and the} like can be mentioned, but are not limited to the exemplified substances.

The combined system of these organic acids and amines is more preferable from the viewpoint of reducing the amount of use because the catalytic activity is increased. Among organic acid and amine combined systems, acidic phosphate ester and amine, organic carboxylic acid and amine, especially organic acidic phosphate ester and amine, and aliphatic carboxylic acid and amine combined system have higher catalytic activity and faster speed. It is preferable from the viewpoint of curability.
These catalysts may be used alone or in combination of two or more.

The amount of the condensation catalyst is preferably about 0.01 to 20 parts, more preferably 0.5 to 5 parts, relative to 100 parts (parts by weight, hereinafter the same) of the polymer having a crosslinkable silyl group. When the amount of the silanol condensation catalyst is below this range, the curing rate may be slow, and the curing reaction may not proceed sufficiently. On the other hand, if the blending amount of the silanol condensation catalyst exceeds this range, local heat generation and foaming occur during curing, and it becomes difficult to obtain a good cured product, and the pot life tends to be shortened and workability tends to be reduced. .
The 100 parts by weight of the polymer having a crosslinkable silyl group means 100 parts by weight of the vinyl polymer (I) having a crosslinkable silyl group, but also includes a polyether polymer having a crosslinkable silyl group. In this case, the total amount of the vinyl polymer (I) having a crosslinkable silyl group and the polyether polymer having a crosslinkable silyl group is 100 parts by weight (the same applies hereinafter).

In addition, although it does not specifically limit, a tin-type curing catalyst gives a favorable result at the point which is easy to control sclerosis | hardenability.
Although not particularly limited, in the case of a one-component composition as described later, tetravalent tin is preferable in the case of a tin-based curing catalyst from the viewpoint of curing speed, storage stability of the composition, and the like. Combinations of valent tin and organic amines and non-tin compounds can also be used.
In addition, although not particularly limited, when used for applications such as a sealing agent for siding board, it is easy to relieve the stress of the cured product, regardless of whether it is a one-component or two-component system. Tetravalent tin is preferable from the standpoint that there is no peeling at the adhesive interface.
In recent years, environmental issues have been focused on and tin catalysts may be disliked. In such cases, other non-tin catalysts such as bismuth carboxylate and titanium carboxylate may be selected.

Further, in the curable composition of the present invention, in order to further enhance the activity of the condensation catalyst, it is also possible to use the above-mentioned silane coupling agent having an amino group as a cocatalyst in the same manner as the amine compound. . The amino group-containing silane coupling agent is a compound having a silicon atom to which a hydrolyzable group is bonded (hereinafter referred to as a hydrolyzable silyl group) and an amino group, and the groups already exemplified as the hydrolyzable group. A methoxy group, an ethoxy group, and the like are preferable from the viewpoint of hydrolysis rate. The number of hydrolyzable groups is preferably 2 or more, particularly 3 or more.

The compounding amount of these amine compounds is preferably about 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polymer having a crosslinkable silyl group. If the compounding amount of the amine compound is less than 0.01 parts by weight, the curing rate may be slow, and the curing reaction may not proceed sufficiently. On the other hand, when the compounding amount of the amine compound exceeds 30 parts by weight, the pot life may be shortened and workability tends to be lowered.
These amine compounds may be used alone or in combination of two or more.

Furthermore, a silicon compound having no amino group or silanol group may be added as a promoter. These silicon compounds are not limited, but phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, triphenylmethoxysilane and the like are preferable. In particular, diphenyldimethoxysilane and diphenyldiethoxysilane are most preferable because of low cost and easy availability.
The amount of the silicon compound is preferably about 0.01 to 20 parts, more preferably 0.1 to 10 parts, based on 100 parts of the polymer having a crosslinkable silyl 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.

In addition, it is possible to control the sclerosis | hardenability of this invention, a mechanical physical property, etc. according to the objective and a use by changing the kind and addition amount of a curing catalyst and a hardening | curing agent. Also, depending on the reactivity of the silyl group of the polymer having a crosslinkable silyl group, it is possible to change the type and amount of the curing catalyst / curing agent, and if the reactivity is high, 0.01 to 1 part It can be cured sufficiently in a small amount.
The type and addition amount of the curing catalyst / curing agent can be selected depending on the type of Y and the number of a in the vinyl polymer (I) of the present invention, and the curability of the present invention depends on the purpose and application. And mechanical properties can be controlled. When Y is an alkoxy group, the lower the number of carbon atoms, the higher the reactivity, and the higher the number a, the higher the reactivity, so that it can be sufficiently cured in a small amount.

Curing catalyst / curing agent for epoxy resin (II) The curable composition of the present invention contains a curing agent for epoxy resin to the extent that it does not interfere with the effect of the room temperature curing type latent curing agent (III). Can do.
A conventionally well-known thing can be widely used as a hardening | curing agent for epoxy resins. For example, aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, methylpentamethylenediamine, trimethylhexamethylenediamine, guanidine, tetramethylguanidine, oleylamine; , Isophorone diamine, norbornane diamine, piperidine, N, N′-dimethylpiperazine, N-aminoethylpiperazine, BASF Ramilon C-260, CIBA Araldit HY-964, Rohm and Haas Mensendiamine, 1, 2-diaminocyclohexane, diaminodicyclohexylmethane, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclo Xylyl) methane, polycyclohexylpolyamine, alicyclic amines such as 1,8-diazabicyclo [5,4,0] undecene-7 (DBU); m-xylylenediamine, m-phenylenediamine, 4, 4′- Aromatic amines such as diaminodiphenylmethane and 4,4′-diaminodiphenylsulfone; (CH ₃ ) ₂ N (CH ₂ ) _n N (CH ₃ ) ₂ (where n is an integer of 1 to 10) Linear tertiary amine represented by a chain diamine, (CH ₃ ) ₂ —N (CH ₂ ) _n —CH ₃ (where n is an integer of 0 to 10), N {(CH ₂ ) _n CH ₃ } ₃ alkyl tertiary monoamines (wherein n where integer of 1 to 10) represented by; benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol Aliphatic aromatic amines such as 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane (ATU), morpholine, N-methylmorpholine, poly Amines having an ether bond such as oxypropylene diamine, polyoxypropylene triamine, and polyoxyethylene diamine; hydroxyl-containing amines such as diethanol amine and triethanol amine; triethylene diamine, pyridine, picoline, diazabicycloundecene, phthalic anhydride, Acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, dodecyl succinic anhydride; dimer acid To Polyamides obtained by reacting polyamines such as tylenetriamine and triethylenetetramine, polyamide resins such as polyamide resins, polyamides using polycarboxylic acids other than dimer acid, and various imidazoles such as 2-ethyl-4-methylimidazole Dicyandiamide and derivatives thereof; polyoxypropylene amines such as polyoxypropylene diamines and polyoxypropylene triamines; phenols; epoxy-modified amines obtained by reacting the above amines with epoxy compounds; Modified amines such as Mannich-modified amine and Michael addition-modified amine obtained by reacting formalin and phenols; amine salts such as 2-ethylhexanoate of 2,4,6-tris (dimethylaminomethyl) phenol; N − ( Examples thereof include compounds having an amino group and a hydrolyzable silyl group in one molecule such as β-aminoethyl) -γ-aminopropyltrimethoxysilane.
These curing agents may be used alone or in combination of two or more. Although not particularly limited, among these curing agents for epoxy resins, 2,4,6-tris (dimethylaminomethyl) phenol and polyoxypropylene-based diamine are preferable from the viewpoint of curability and physical property balance.

Such a curing agent for epoxy resins is usually in the range of about 1 to 60 parts by weight, preferably 2 to 50 parts by weight, based on 100 parts by weight of the polymer having a crosslinkable silyl group, although it depends on the amount of the epoxy resin. It is good to be used within a range. If it is less than 1 part by weight, the epoxy resin is not sufficiently cured and the adhesive strength tends to be lowered. On the other hand, if it exceeds 60 parts by weight, bleeding to the interface occurs and the adhesiveness tends to decrease.
If a compound having a group capable of reacting with both the crosslinkable silyl group of the vinyl polymer (I) and the epoxy group of the epoxy resin (II) is added to the curable resin composition, the strength is further improved. preferable. Specific examples thereof include N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane. Etc.

<Dehydrating agent>
The curable composition increases in viscosity and gelation during storage due to moisture at the time of production, causing difficulty in workability during use, and also increases in viscosity and gelation. By using the advanced curable composition, the physical properties of the cured product after curing may be deteriorated, resulting in a problem that the original sealing property and the like are impaired. That is, the storage stability of the curable composition may be a problem.

In order to improve the storage stability of the curable composition, there is a method of reducing the moisture content of the curable composition by azeotropic dehydration. For example, about 0.1 to 10 parts by weight of a volatile organic compound having a minimum azeotropic point with respect to water is added and mixed uniformly, and then heated to about 50 to 90 ° C. The method of taking out the azeotropic composition of an organic compound out of the system is mentioned.
Volatile organic compounds having a minimum azeotropic point with respect to water include halides such as methylene chloride, chloroform, carbon tetrachloride, and trichloroethylene; alcohols such as ethanol, allyl alcohol, 1-propanol, and butanol; ethyl acetate, propion Examples thereof include esters such as methyl acid; ketones such as methyl ethyl ketone and 3-methyl-2-butanone; ethers such as ethyl ether and isopropyl ether; hydrocarbons such as benzene, toluene, xylene and hexane. However, since this method requires a devolatilization operation, it is necessary to devise other volatile compounding agents, or it is necessary to treat and recover the volatile organic compound to be azeotroped. For this reason, it may be preferable to add the following dehydrating agents.

As described above, a dehydrating agent for removing water in the composition can be added to the curable composition of the present invention for the purpose of improving storage stability.
Examples of the dehydrating agent include inorganic solids such as phosphorus pentoxide, sodium hydrogen carbonate, sodium sulfate (anhydrous bow glass), and molecular sieves.
These solid dehydrating agents may be used, but the liquidity after addition tends to be acidic or basic, conversely tends to condense, resulting in poor storage stability, and poor workability such as removing the solid later. In some cases, the liquid hydrolyzable ester compound described below is preferable.
Examples of hydrolyzable ester compounds include trialkyl orthoformate, triethyl orthoformate, tripropyl orthoformate, tributyl orthoformate, trialkyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoacetate. And trialkyl orthoacetate such as tributyl orthoacetate, and those selected from the group consisting of these compounds.

Other hydrolyzable ester compounds may further include the formula R _4-n SiY _n (wherein Y is a hydrolyzable group, R is an organic group and may or may not contain a functional group). n is an integer of 1 to 4, preferably 3 or 4, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, and methyltrimethoxy. Silane, methyltriethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, methyltriacetoxysilane, tetramethyl orthosilicate (tetramethoxysilane or methyl silicate), tetraethyl orthosilicate (tetraethoxysilane or ethyl silicate), tetra orthosilicate Sila such as propyl, tetrabutyl orthosilicate Compounds or partial hydrolysis condensates thereof, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-acryloxy Propyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, etc. Examples thereof include silane coupling agents or partial hydrolysis condensates thereof. One or more of these can be used in combination.

The dehydrating agent not only prevents hydrolysis of the vinyl polymer during storage and forms a three-dimensional network structure by silanol condensation reaction, but also decomposes the ketimine with water and reacts with the epoxy resin to cure. Therefore, it is more preferable as a storage stability improver.
The amount of the storage stability improver used is 0.1 to 30 parts by weight, preferably 0.3 to 20 parts by weight, more preferably 0.5 to 10 parts by weight based on 100 parts by weight of the vinyl polymer (I). Parts by weight.
In addition, when adding these storage stability improving agents, it is preferable to carry out after making a curable composition anhydrous, but you may add in the state containing moisture.

<Adhesive agent>
A silane coupling agent or an adhesion-imparting agent other than the silane coupling agent can be added to the composition of the present invention. When the adhesion-imparting agent is added, the joint width and the like fluctuate due to an external force, thereby further reducing the risk of the sealing material peeling from the adherend such as a siding board. Further, in some cases, it is not necessary to use a primer used for improving adhesion, and simplification of construction work is expected.

Specific examples of the silane coupling agent include silane coupling agents having functional groups such as amino group, mercapto group, epoxy group, carboxyl group, vinyl group, isocyanate group, isocyanurate, and halogen. Specific examples thereof include isocyanate group-containing silanes such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatopropylmethyldimethoxysilane; γ-aminopropyl. Trimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxy Silane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldie Xysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N Amino group-containing silanes such as vinylbenzyl-γ-aminopropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxy Mercapto group-containing silanes such as silane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexane) E) Epoxy group-containing silanes such as ethyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane Carboxysilanes such as N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropyl Vinyl-type unsaturated group-containing silanes such as methyltriethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate, bis (3-tri Butoxy silyl propyl) can be given polysulfane such as tetrasulfane like. In addition, a reaction product of the amino group-containing silane and the epoxy group-containing silane, a reaction product of an amino group-containing silane and an acroyloxy group-containing silane, an amino group-containing silane and an isocyanate group-containing silane These reactants can also be used. In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, blocked isocyanate silanes, silylated polyesters, etc., which are derivatives of these, are also used as silane coupling agents. Can be used.

The silane coupling agent used for this invention is normally used in 0.1-20 parts with respect to 100 parts of polymers which have a crosslinkable silyl group. In particular, it is preferably used in the range of 0.5 to 10 parts. The effects of the silane coupling agent added to the curable composition of the present invention are various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, mortar, vinyl chloride, acrylic, polyester, When used for organic base materials such as polyethylene, polypropylene, polycarbonate, etc., it exhibits a remarkable adhesive improvement effect under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving adhesion to various adherends is particularly remarkable. Moreover, if the usage-amount is about 1 part with respect to 100 parts of polymers which have a crosslinkable silyl group, it will hardly affect transparency of hardened | cured material.

Specific examples other than the silane coupling agent are not particularly limited. For example, epoxy resin, phenol resin, polystyrene-polybutadiene-polystyrene, polystyrene-polyisoprene-polystyrene, polystyrene-polyisoprene / butadiene copolymer-polystyrene, polystyrene. -Polyethylene / propylene copolymer-Polystyrene, polystyrene-Polyethylene / butylene copolymer-Linear or branched block copolymer such as polystyrene, polystyrene-polyisobutene-polystyrene, alkyl sulfonate, sulfur, alkyl titanates And aromatic polyisocyanate. The epoxy resin can be used by reacting with the above amino group-containing silanes.

The adhesiveness-imparting agent may be used alone or in combination of two or more. By adding these adhesion-imparting agents, the adhesion to the adherend can be improved. Although not particularly limited, 0.1-20 parts by weight of a silane coupling agent is used in combination with the above-mentioned adhesion-imparting agent in order to improve adhesion, particularly adhesion to a metal-coated surface such as an oil pan. Is preferred.
The type and amount of the adhesion-imparting agent can be selected according to the type of Y and the number of a in the vinyl polymer of the present invention, and the curability and mechanical properties of the present invention depending on the purpose and application. Can be controlled. In particular, care must be taken when selecting because it affects curability and elongation.

<Plasticizer>
You may use various plasticizers for the curable composition of this invention as needed. When a plasticizer is used in combination with a filler to be described later, it becomes more advantageous because the elongation of the cured product can be increased or a large amount of filler can be mixed, but it is not necessarily added.
Although it does not specifically limit as a plasticizer, For purposes, such as adjustment of a physical property and adjustment of properties, phthalic acid esters, such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, etc. Non-aromatic dibasic esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate; aliphatic esters such as butyl oleate and methyl acetyl ricinoleate; diethylene glycol dibenzoate, triethylene glycol di Polyalkylene glycol esters such as benzoate and pentaerythritol ester; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Polystyrenes such as re-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; polyethylene Polyether polyols such as glycol, polypropylene glycol, ethylene oxide-propylene oxide copolymer, polytetramethylene glycol, etc., converting one end or both ends or all ends of hydroxyl groups of these polyether polyols to alkyl ester groups or alkyl ether groups Polyethers such as alkyl derivatives; epoxy group-containing plasticizers such as epoxidized soybean oil, epoxy benzyl stearate, E-PS; sebacic acid, adipic acid, azelaic acid, Polyester plasticizers obtained from dibasic acids such as phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; various vinyl monomers including acrylic plasticizers And vinyl polymers obtained by polymerization according to the above method.

Among them, a polymer plasticizer which is a polymer having a number average molecular weight of 500 to 15,000 is added, whereby the viscosity and slump property of the curable composition and the tensile strength of the cured product obtained by curing the composition are obtained. Mechanical properties such as strength and elongation can be adjusted, and the initial physical properties can be maintained over a long period of time compared to the case of using a low molecular plasticizer that is a plasticizer that does not contain a polymer component in the molecule. It is possible to improve the drying property (also referred to as paintability) when an alkyd paint is applied. Although not limited, the polymer plasticizer may or may not have a functional group.

Although the number average molecular weight of the polymer plasticizer was described as 500 to 15,000 above, it is preferably 800 to 10,000, and more preferably 1,000 to 8,000. If the molecular weight is too low, the plasticizer flows out over time due to heat or rain, and the initial physical properties cannot be maintained over a long period of time, and the alkyd paintability may not be improved. Moreover, when molecular weight is too high, a viscosity will become high and workability | operativity may worsen.

Among these polymer plasticizers, polyether plasticizers and (meth) acrylic polymer plasticizers are preferable from the viewpoint of high elongation characteristics or high weather resistance. Examples of the synthesis method of the acrylic polymer include those obtained by conventional solution polymerization and solvent-free acrylic polymers. The latter acrylic plasticizer is prepared by a high-temperature continuous polymerization method (USP 4414370, JP 59-6207, JP-B-5-58005, JP 1-313522, USP 5010166) without using a solvent or a chain transfer agent. More preferred for the purposes of the present invention. Examples thereof include, but are not particularly limited to, for example, ARUFON UP series (UP-1000, UP-1110, UP-2000, UP-2130) (referred to as SGO) of Toagosei Co., Ltd. (waterproof journal, June 2002) Issue). Of course, the living radical polymerization method can also be mentioned as another synthesis method. According to this method, the molecular weight distribution of the polymer is narrow and the viscosity can be lowered, and the atom transfer radical polymerization method is more preferable, but it is not limited thereto.

The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow from the viewpoint of viscosity, and preferably less than 1.8. 1.7 or less is more preferable, 1.6 or less is more preferable, 1.5 or less is further preferable, 1.4 or less is particularly preferable, and 1.3 or less is most preferable.
From the viewpoint of viscosity, it is preferable to have a branched structure in the main chain because the viscosity becomes lower at the same molecular weight. The high temperature continuous polymerization method mentioned above is mentioned as this example.
The plasticizer containing the above-mentioned polymer plasticizer may be used alone or in combination of two or more, but is not necessarily required. If necessary, a high molecular plasticizer may be used, and a low molecular plasticizer may be further used in combination as long as the physical properties are not adversely affected. Further, for example, in the case of a composition in which the vinyl polymer (I) of the present invention and a polyether polymer (V) which is one of optional components having a crosslinkable functional group are mixed, Of these, phthalates and acrylic polymers are particularly preferable.

These plasticizers can also be blended at the time of polymer production.
The amount of the plasticizer used is not limited, but it is 5 to 150 parts by weight, preferably 10 to 120 parts by weight, more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the polymer having a crosslinkable silyl group. It is. If the amount is less than 5 parts by weight, the effect as a plasticizer is hardly exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product tends to be insufficient.

<Filler>
You may use various fillers for the curable composition of this invention as needed.
The filler is not particularly limited, but wood powder, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, rice husk powder, graphite, diatomaceous earth, white clay, silica (fumed silica, sedimentation) Silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, amorphous spherical silica, etc.), reinforcing filler such as carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, Diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, zinc dust, zinc carbonate and shirasu balloon, glass microballoon, Organic microballoons, PVC powder, PMMA powder of phenol resin and vinylidene chloride resin Fillers like resin powders and the like; asbestos, glass fibers and glass filaments, carbon fibers, Kevlar fibers, fibrous fillers such as polyethylene fiber and the like.

Of these fillers, precipitated silica, fumed silica, crystalline silica, fused silica, dolomite, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable.
In particular, when it is desired to obtain a cured product with high transparency or strength with these fillers, fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, crystallinity A filler selected from silica, fused silica, calcined clay, clay and activated zinc white can be added. These are suitable for transparent architectural sealants, transparent DIY adhesives and the like. Among them, the specific surface area (according to BET adsorption method) of ^{10 m} 2 / g or more, usually 50 to 400 m ² / g, is preferably 100 to 300 m ² / g approximately ultrafine powdery silica preferred. Further, silica whose surface is previously hydrophobically treated with an organosilicon compound such as organosilane, organosilazane, diorganocyclopolysiloxane or the like is more preferable.

More specific examples of silica-based fillers having high reinforcing properties are not particularly limited. However, Nippon Aerosil Co., Ltd., which is one of fumed silica, and Nippon Silica Co., Ltd., which is one of precipitated silicas. Nipsil and the like. Silica having an average particle diameter of 1 nm to 30 μm can be used. Particularly for fumed silica, it is more preferable to use fumed silica having an average primary particle size of 1 nm to 50 nm because the reinforcing effect is particularly high. In addition, the average particle diameter in this invention is based on the sieving method. Specifically, the powder is classified with various sieves (such as micro sieves), and the value corresponding to the sieve openings through which 50% by weight of the total weight of the powder used for measurement has passed (weight average) Particle size). A composition reinforced with a filler is excellent in quick fixability and suitable for automobile glass glazing adhesion.
Transparency can also be obtained by using a resin powder such as PMMA powder as a filler.

Moreover, when it is desired to obtain a cured product having low strength and large elongation, a filler selected mainly from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like can be added. In general, when calcium carbonate has a small specific surface area, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product may not be sufficient. The larger the specific surface area value, the greater the effect of improving the strength at break, elongation at break, adhesion and weather resistance of the cured product. As the shape of calcium carbonate, various shapes such as a cubic non-cubic shape and an irregular shape can be used.

Furthermore, it is more preferable that the calcium carbonate is subjected to a surface treatment using a surface treatment agent. When the surface-treated calcium carbonate is used, the workability of the composition of the present invention is improved as compared with the case where calcium carbonate that is not surface-treated is used, and the adhesiveness and weather resistance of the curable composition are improved. The improvement effect is considered to be further improved. As the surface treatment agent, organic substances such as fatty acids, fatty acid soaps and fatty acid esters, various surfactants, and various coupling agents such as silane coupling agents and titanate coupling agents are used. Specific examples include, but are not limited to, fatty acids such as caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc. And salts of these fatty acids such as sodium and potassium, and alkyl esters of these fatty acids. Specific examples of the surfactants include polyoxyethylene alkyl ether sulfates and long chain alcohol sulfates, sulfate anion surfactants such as sodium salts and potassium salts thereof, alkylbenzene sulfonic acids, and alkylnaphthalenes. Examples thereof include sulfonic acid, paraffin sulfonic acid, α-olefin sulfonic acid, alkylsulfosuccinic acid and the like, and sulfonic acid type anionic surfactants such as sodium salt and potassium salt thereof. The treatment amount of the surface treatment agent is preferably in the range of 0.1 to 20% by weight and more preferably in the range of 1 to 5% by weight with respect to calcium carbonate. When the treatment amount is less than 0.1% by weight, the workability, adhesiveness and weatherability may not be sufficiently improved. When the treatment amount exceeds 20% by weight, the storage stability of the curable composition may be reduced. May decrease.

Although there is no particular limitation, when calcium carbonate is used, colloidal calcium carbonate is used when particularly improving effects such as thixotropy of the compound, breaking strength of the cured product, elongation at break, adhesion and weather resistance are expected. Is preferred.
On the other hand, heavy calcium carbonate may be added for the purpose of lowering the viscosity of the compound, increasing the amount, reducing costs, etc. When using this heavy calcium carbonate, use the following as necessary. be able to.

Heavy calcium carbonate is obtained by mechanically pulverizing and processing natural chalk (chalk), marble, limestone, and the like. There are dry and wet methods for the pulverization method, but wet pulverized products are often not preferred because they often deteriorate the storage stability of the curable composition of the present invention. Heavy calcium carbonate becomes products having various average particle sizes by classification. Although not particularly limited, when the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product is expected, the specific surface area has a value of 1.5 m ² / g or more and 50 m ² / g or less. more preferably from ^2m 2 / g or more ^{50 m} 2 / g or less, more preferably 2.4 m ² / g or more ^{50 m} 2 / g or less, ^3m 2 / g or more ^{50 m} 2 / g or less is particularly preferred. When the specific surface area is less than 1.5 m ² / g, the improvement effect may not be sufficient. Of course, this is not the case when the viscosity is simply lowered or only for the purpose of increasing the viscosity.

In addition, the value of a specific surface area means the measured value by the air permeation method (method which calculates | requires a specific surface area from the permeability | transmittance of the air with respect to a powder filling layer) performed according to JISK5101 as a measuring method. As a measuring instrument, it is preferable to use a specific surface area meter SS-100 manufactured by Shimadzu Corporation.

These fillers may be used alone or in combination of two or more according to the purpose and necessity. Although there is no particular limitation, for example, when heavy calcium carbonate and colloidal calcium carbonate having a specific surface area of 1.5 m ² / g or more are combined as needed, the increase in viscosity of the compound is moderately suppressed and cured. The effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the product can be greatly expected.

When the filler is used, the addition amount is preferably 5 to 1,000 parts by weight with respect to 100 parts by weight of the polymer having a crosslinkable silyl group, and preferably 20 to 500 parts by weight. More preferably, it is used in a range of 40 to 300 parts by weight. When the blending amount is less than 5 parts by weight, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product may not be sufficient, and when it exceeds 1,000 parts by weight, the curable composition Workability may be reduced.
It should be noted that dolomite, carbon black, calcium carbonate, titanium oxide, talc, and the like may be added in large amounts, thereby hindering the transparency of the present invention and resulting in an opaque cured product.

<Micro hollow particles>
Furthermore, for the purpose of reducing the weight and cost without causing a significant decrease in physical properties, fine hollow particles may be used in combination with these reinforcing fillers.
Such fine hollow particles (hereinafter referred to as “balloons”) are not particularly limited, but as described in “the latest technology of functional filler” (CMC), the diameter is 1 mm or less, preferably 500 μm or less, and more preferably Is a hollow body made of an inorganic or organic material of 200 μm or less. In particular, it is preferable to use a micro hollow body having a true specific gravity of 1.0 g / cm ³ or less, and more preferably to use a micro hollow body having a specific gravity of 0.5 g / cm ³ or less.

Examples of the inorganic balloon include a silicate balloon and a non-silicate balloon. Examples of the silicate balloon include shirasu balloon, pearlite, glass (silica) balloon, fly ash balloon, and the like. Non-silicate balloon includes alumina. Examples include balloons, zirconia balloons, and carbon balloons. As specific examples of these inorganic balloons, Shirasu balloons made by Idichi Kasei Co., Ltd., Sankilite made by Sanki Kogyo Co., Ltd., Fuji Silicia Chemicals Fuji Balloon made by glass (silica) balloons, Nippon Sheet Glass Kaloon, Sumitomo 3M Cellstar Z-28, EMERSON & CUMING made by MICRO BALLON, PITTSBURGE CORNING made by CELAMIC GLASSMMODULES, 3M made by GLAST BUBBLES, Asahi Glass Q-CEL, Taiheiyo Cement made by E-SPHERE, P FILLITE U. S. FILLITE manufactured by A, BW manufactured by Showa Denko as an alumina balloon, HOLLOW ZIRCONIUM SPHEES manufactured by ZIRCOA as a zirconia balloon, and Kureha sphere made by Kureha Chemical, and a carbo sphere manufactured by GENERAL TECHNOLOGIES as a carbon balloon.

Examples of the organic balloon include a thermosetting resin balloon and a thermoplastic resin balloon. The thermosetting balloon includes a phenol balloon, an epoxy balloon, and a urea balloon. The thermoplastic balloon includes a saran balloon, a polystyrene balloon, Examples thereof include polymethacrylate balloons, polyvinyl alcohol balloons, and styrene-acrylic balloons. A crosslinked thermoplastic balloon can also be used. The balloon here may be a balloon after foaming, or a balloon containing a foaming agent may be foamed after blending.

Specific examples of these organic balloons include UCAR and PHENOLIC MICROBALLONONS made by Union Carbide as phenolic balloons, ECCOSPHERES made by EMERSON & CUMING as epoxy balloons, ECCOSPHERES VF-O made by EMERSON & CUMING, and DOWEMIC PHALS made by Saran Balloon by Saran Balloon. EXPANSEL manufactured by Nippon Filament, Matsumoto Microsphere manufactured by Matsumoto Yushi Seiyaku, DYLITE EXPANDABLE POLYSTYRENE manufactured by ARCO POLYMERS as polystyrene balloon, EXPANDABLE POLYSTYRENE BEADS manufactured by BASF WYANDOTE, Bridge-type styrene - acrylic acid balloons, JSR made SX863 (P) are commercially available.

The balloons may be used alone or in combination of two or more. Furthermore, to improve the dispersibility and workability of the compound with the fatty acid, fatty acid ester, rosin, rosin acid lignin, silane coupling agent, titanium coupling agent, aluminum coupling agent, polypropylene glycol, etc. on the surface of these balloons. The processed one can also be used. These balloons are designed to improve workability such as cutting properties before curing the composition, reduce costs by reducing weight without losing flexibility and elongation / strength after curing, and further design such as surface matting and sputtering. Used for imparting sex.

Although content of a balloon is not specifically limited, Preferably it is 0.1-50 parts with respect to 100 weight part of polymers which have a crosslinkable silyl group, More preferably, it can use in 0.1-30 parts. If this amount is less than 0.1 part, the effect of weight reduction is small, and if it exceeds 50 parts, a decrease in tensile strength may be observed among the mechanical properties when this compound is cured. Moreover, when the specific gravity of a balloon is 0.1 or more, 3 to 50 parts are preferable, and 5 to 30 parts are more preferable.

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

<Silanol-containing compound>
You may add a silanol containing compound to the curable composition of this invention as needed, such as changing the physical property of hardened | cured material. The silanol-containing compound refers to a compound having one silanol group in the molecule and / or a compound capable of producing a compound having one silanol group in the molecule by reacting with moisture. Only one of these may be used, or both compounds may be used simultaneously.

The compound having one silanol group in the molecule which is one of the silanol-containing compounds is not particularly limited, and the compounds shown below,
(CH ₃ ) ₃ SiOH, (CH ₃ CH ₂ ) ₃ SiOH, (CH ₃ CH ₂ CH ₂ ) ₃ SiOH, (n-Bu) ₃ SiOH, (sec-Bu) ₃ SiOH, (t-Bu) ₃ SiOH , (T-Bu) Si (CH ₃ ) ₂ OH, (C ₅ H ₁₁ ) ₃ SiOH, (C ₆ H ₁₃ ) ₃ SiOH, (C ₆ H ₅ ) ₃ SiOH, (C ₆ H ₅ ) ₂ Si ( _{CH 3) OH, (C 6} H 5) Si (CH 3) 2 OH, (C 6 H 5) 2 Si (C 2 H 5) OH, C 6 H 5 Si (C 2 H 5) 2 OH, C _{6 H 5 CH 2 Si (C} 2 H 5) 2 OH, C 10 H 7 Si (CH 3) 2 OH
(However, in the above formula, C ₆ H ₅ represents a phenyl group, and C ₁₀ H ₇ represents a naphthyl group.)
A compound that can be represented by (R ″) ₃ SiOH, where R ″ is the same or different substituted or unsubstituted alkyl group or aryl group,

Cyclic polysiloxane compounds containing silanol groups, such as

(In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 1 to 20)
A chain polysiloxane compound containing a silanol group such as

(In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 1 to 20)
A compound in which the main chain is composed of silicon, carbon, and the like, and a silanol group is bonded to the polymer end,

(In the formula, n represents an integer of 1 to 20)
A compound having a silanol group bonded to the polysilane main chain terminal, such as

(In the formula, m represents an integer of 1 to 20, and n represents an integer of 1 to 20)
Examples thereof include a compound in which a main chain is composed of silicon, carbon, oxygen and a silanol group bonded to a polymer terminal. Among these, (CH ₃ ) ₃ SiOH, which is easy to obtain and has a low molecular weight, is preferable from the viewpoint of effects.
The compound having one silanol group in the molecule reacts with a crosslinkable silyl group of a polymer having a crosslinkable silyl group or a siloxane bond formed by crosslinking, thereby reducing the number of crosslinking points, and a cured product. Gives a composition with excellent surface tack and dust adhesion.

Moreover, the compound which can produce | generate the compound which has one silanol group in a molecule | numerator by reacting with a water | moisture content is although it does not specifically limit, N, O-bis (trimethylsilyl) acetamide, N- (trimethylsilyl) acetamide, bis ( Trimethylsilyl) trifluoroacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, bistrimethylsilylurea, N- (t-butyldimethylsilyl) N-methyltrifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (N , N-diethylamino) trimethylsilane, hexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, N- (trimethylsilyl) imidazole, trimethylsilyl trifluoromethanesulfonate, trimethylsilylphenoxide Trimethylsilylated product of n-octanol, trimethylsilylated product of 2-ethylhexanol, tris (trimethylsilyl) ated product of glycerin, tris (trimethylsilylated) product of trimethylolpropane, tris (trimethylsilylated) product of pentaerythritol, tetra (trimethylsilylated) product of pentaerythritol , (CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ , (CH ₃ ) ₃ SiNSi (CH ₃ ) ₂ , allyloxytrimethylsilane, N, O-bis (trimethylsilyl) acetamide, N- (trimethylsilyl) acetamide, bis (trimethylsilyl) ) Trifluoroacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, bistrimethylsilylurea, N- (t-butyldimethylsilyl) N-methyl Trifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (N, N-diethylamino) trimethylsilane, hexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, N- (trimethylsilyl) imidazole, Trimethylsilyl trifluoromethanesulfonate, trimethylsilylphenoxide, trimethylsilylated product of n-octanol, trimethylsilylated product of 2-ethylhexanol, tris (trimethylsilyl) ated product of glycerin, tris (trimethylsilyl) ated product of trimethylolpropane, tris (trimethylsilyl) of pentaerythritol product, tetra (trimethylsilyl) ated product of _{pentaerythritol, (CH 3) 3 SiNHSi (} CH 3) 3, (CH 3) 3 SiNSi (CH ) _2,

Etc. can be used suitably. (CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ is particularly preferred from the amount of silanol groups contained in the hydrolysis product.
Furthermore, the compound which can produce | generate the compound which has one silanol group in a molecule | numerator by reacting with a water | moisture content is although it does not specifically limit, The compound represented by following General formula (46) other than the said compound is preferable.
((R ⁵⁸ ) ₃ SiO) _n R ⁵⁹ (46)
(In the formula, R ⁵⁸ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. A plurality of R ⁵⁸ may be the same or different. N is a positive number, and R ⁵⁹ is an active hydrogen.) Indicates a group obtained by removing some or all active hydrogen from the contained compound.)
^R58 is preferably a methyl group, an ethyl group, a vinyl group, a t-butyl group, or a phenyl group, and more preferably a methyl group.
The (R ⁵⁸ ) ₃ Si group is particularly preferably a trimethylsilyl group in which all three R ⁵⁸ are methyl groups. N is preferably 1 to 5.

The active hydrogen-containing compound from which ^R59 is derived is not particularly limited, and examples thereof include methanol, ethanol, n-butanol, i-butanol, t-butanol, n-octanol, 2-ethylhexanol, benzyl alcohol, and ethylene glycol. , Alcohols such as diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propanediol, tetramethylene glycol, polytetramethylene glycol, glycerin, trimethylolpropane, pentaerythritol; phenol, cresol, bisphenol A, hydroquinone, etc. Phenols: formic acid, acetic acid, propionic acid, lauric acid, palmitic acid, stearic acid, behenic acid, acrylic acid, methacrylic Carboxylic acids such as acid, oleic acid, linoleic acid, linolenic acid, sorbic acid, oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid, benzoic acid, phthalic acid, terephthalic acid, trimellitic acid; ammonia; methylamine Amines such as dimethylamine, ethylamine, diethylamine, n-butylamine and imidazole; acid amides such as acetamide and benzamide; ureas such as urea and N, N′-diphenylurea; acetone, acetylacetone and 2,4-heptadione And ketones.

A compound capable of generating a compound having one silanol group in the molecule by reacting with the water represented by the general formula (46) is, for example, trimethylsilyl chloride or dimethyl (t It can be obtained by reacting a compound having a group capable of reacting with an active hydrogen such as a halogen group together with a (R ⁵⁸ ) ₃ Si group, which is also called a silylating agent such as -butyl) chloride, but is not limited thereto. (However, R ⁵⁸ is the same as described above.)

Specific examples of the compound represented by the general formula (46) include allyloxytrimethylsilane, N, O-bis (trimethylsilyl) acetamide, N- (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, N- Methyl-N-trimethylsilyltrifluoroacetamide, bistrimethylsilylurea, N- (t-butyldimethylsilyl) N-methyltrifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (N, N-diethylamino) trimethylsilane, Hexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, N- (trimethylsilyl) imidazole, trimethylsilyltrifluoromethanesulfonate, trimethylsilylphenoxide, n-octanol trimethyl Silylated product, Trimethylsilylated product of 2-ethylhexanol, Tris (trimethylsilyl) product of glycerin, Tris (trimethylsilyl) product of trimethylolpropane, Tris (trimethylsilyl) product of pentaerythritol, Tetra (trimethylsilyl) product of pentaerythritol, Polypropylene glycol Examples include, but are not limited to, trimethylsilylated products, trimethylsilylated products of polyether polyols such as trimethylsilylated products of polypropylenetriol, trimethylsilylated products of polypropylenetetraol, and trimethylsilylated products of acrylic polyols. These may be used alone or in combination of two or more.

Further, a compound that can be represented by the general formula (((R ⁶⁰ ) ₃ SiO) (R ⁶¹ O) _s ) _t Z, CH ₃ O (CH ₂ CH (CH ₃ ) O) ₅ Si (CH ₃ ) ₃ ,
_{CH 2 = CHCH 2 (CH 2} CH (CH 3) O) 5 Si (CH 3) 3,
(CH ₃ ) ₃ SiO (CH ₂ CH (CH ₃ ) O) ₅ Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO (CH ₂ CH (CH ₃ ) O) ₇ Si (CH ₃ ) ₃
(Wherein R ⁶⁰ is the same or different substituted or unsubstituted monovalent hydrocarbon group or hydrogen atom, R ⁶¹ is a divalent hydrocarbon group having 1 to 8 carbon atoms, and s and t are positive integers. , S is 1 to 6, s × t is 5 or more, Z is a 1 to 6-valent organic group)
Etc. can also be used suitably. These may be used alone or in combination of two or more.

Among the compounds that can produce a compound having one silanol group in the molecule by reacting with moisture, the active hydrogen compound produced after hydrolysis is not adversely affecting storage stability, weather resistance, etc. Phenols, acid amides and alcohols are preferable, and phenols and alcohols whose active hydrogen compounds are hydroxyl groups are more preferable.

Among the above compounds, N, O-bis (trimethylsilyl) acetamide, N- (trimethylsilyl) acetamide, trimethylsilylphenoxide, trimethylsilylated product of n-octanol, trimethylsilylated product of 2-ethylhexanol, tris (trimethylsilyl) ated product of glycerin, A tris (trimethylsilyl) product of trimethylolpropane, a tris (trimethylsilyl) product of pentaerythritol, a tetra (trimethylsilyl) product of pentaerythritol and the like are preferable.

A compound that can generate a compound having one silanol group in the molecule by reacting with moisture has one silanol group in the molecule by reacting with moisture during storage, curing or after curing. A compound is produced. The compound having one silanol group in the molecule thus produced reacts with the crosslinkable silyl group of the vinyl polymer (I) or the siloxane bond formed by the crosslinking as described above, thereby forming a crosslinking point. It is presumed that the number of the above is reduced, and the cured product is given flexibility.

The structure of the silanol-containing compound can be selected depending on the type of Y and the number of a in the vinyl polymer (I) of the present invention, and the curability, mechanical properties, etc. of the present invention depending on the purpose and application. Can be controlled.
The silanol-containing compound may be used in combination with an air oxidation curable material described later, and by using it together, the modulus of the cured product is kept low, and the curability and dust adhesion of the alkyd paint coated on the surface are improved. Therefore, it is preferable.

The addition amount of the silanol-containing compound can be appropriately adjusted according to the expected physical properties of the cured product. The silanol-containing compound can be added in an amount of 0.1 to 50 parts by weight, preferably 0.3 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the polymer having a crosslinkable silyl group. If it is less than 0.1 part by weight, the effect of addition hardly appears, and if it exceeds 50 parts by weight, the crosslinking becomes insufficient, and the strength and gel fraction of the cured product tend to decrease.
Moreover, the time which adds a silanol containing compound is not specifically limited, You may add at the time of manufacture of a polymer, and you may add at the time of preparation of a curable composition.

<Thixotropic agent (anti-sagging agent)>
A thixotropic agent (anti-sagging agent) may be added to the curable composition of the present invention as necessary to prevent sagging and improve workability.
A thixotropic agent (anti-sagging agent) is also called a thixotropic agent. Thixotropy imparts fluidity when a strong force is applied, such as when extruding from a cartridge into a bead, applying with a spatula, or spraying with a spray, etc., until it hardens after application or construction. It imparts the property of not flowing down.
The thixotropy imparting agent (anti-sagging agent) is not particularly limited, and examples thereof include amide waxes, hydrogenated castor oil, hydrogenated castor oil derivatives, fatty acid derivatives, stears represented by Disparon (manufactured by Enomoto Kasei). Metal soap such as calcium phosphate, aluminum stearate, barium stearate, organic compounds such as 1,3,5-tris (trialkoxysilylalkyl) isocyanurate, calcium carbonate and fine powder surface-treated with fatty acids and resin acids Examples thereof include inorganic compounds such as silica and carbon black.

Fine powder silica means a natural or artificial inorganic filler mainly composed of silicon dioxide. Specific examples include kaolin, clay, activated clay, silica sand, silica stone, diatomaceous earth, anhydrous aluminum silicate, hydrous magnesium silicate, talc, perlite, white carbon, mica fine powder, bentonite, and organic bentonite. it can.
Among these, ultrafine anhydrous silica or organic bentonite produced by reacting a volatile compound containing silicon in the gas phase is preferable. At least ^{50 m} 2 / g, and more preferably it has a specific surface area of 50 to 400 m ² / g. Either hydrophilic silica or hydrophobic silica can be used. Hydrophobic silica whose surface is hydrophobically treated with silazane, chlorosilane, alkoxysilane, or polysiloxane having only a methyl group as an organic substituent bonded to a silicon atom is preferable. .

Specific examples of the surface treatment agent include silazanes such as hexamethyldisilazane; halogenated silanes such as trimethylchlorosilane, dimethyldichlorosilane, and methyltrichlorosilane; trimethylalkoxysilane and dimethyldialkoxysilane. Alkoxysilanes such as methyltrialkoxysilane (wherein alkoxy groups include methoxy, ethoxy, propoxy, butoxy, etc.); cyclic or linear polydimethylsiloxane, etc. Examples thereof include siloxanes, and these may be used alone or in combination of two or more. Among these, hydrophobic fine powder silica subjected to a surface treatment with siloxanes (dimethylsilicone oil) is preferable from the viewpoint of thixotropic effect.

Moreover, thixotropy is increased when a polyether compound such as diethylene glycol, triethylene glycol, or polyethylene glycol, a reaction product of a polyether compound and a functional silane, or a nonionic surfactant having an ethylene oxide chain is used in combination with fine powder silica. . These nonionic surfactants may be used alone or in combination of two or more.

Specific examples of the fine powder silica include, for example, trade names Aerosil R974, R972, R972V, R972CF, R805, R812, R812S, RY200, RX200, RY200S, # 130, # 200, # 300, R202, etc., manufactured by Nippon Aerosil. And trade names Nippon Sil SS series made by Nippon Silica, trade names Rheorosil MT-10, MT-30, QS-102, QS-103 made by Tokuyama Soda, trade names Cabosil TS-720, MS-5, MS made by Cabot -7, commercial products such as Sven and Organite manufactured by Toyoshiro Yoko.

The organic bentonite is a powdery substance obtained by finely pulverizing montmorillonite ore, which is surface-treated with various organic substances. As the organic compound, aliphatic primary amines, aliphatic quaternary amines (all of which preferably have 20 or less carbon atoms) are used. Specific examples of the organic bentonite include, for example, trade names Orven D, New D Orven, manufactured by Shiraishi Kogyo, trade name Hard Sil, manufactured by Kaolin Tsuchiya, clay # 30 manufactured by Bergess Pigment, Southern Cray # 33, manufactured by National Lead, USA. “Bentone 34” (dimethyloctadecyl ammonium bentonite) and the like.

The thixotropic index means a ratio of apparent viscosity at a low rotation speed (for example, 0.5 to 12 rpm) and a high speed (for example, 2.5 to 60 rpm) in viscosity measurement using a rotational viscometer (however, The ratio of the speed of high speed rotation to the speed of low speed rotation is preferably at least 5 and more preferably in the range of 5-10.
These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more.
The addition amount of the thixotropic agent is preferably 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the polymer having a crosslinkable silyl group.

<Photo-curing substance>
You may add a photocurable substance to the curable composition of this invention as needed. A photo-curing substance is a substance in which the molecular structure undergoes a chemical change in a short time by the action of light, resulting in a change in physical properties such as curing. By adding this photocurable substance, the tackiness (also referred to as residual tack) of the cured product surface when the curable composition is cured can be reduced. This photo-curing substance is a substance that can be cured by exposure to light, but a typical photo-curing substance should be allowed to stand at room temperature for one day, for example, in a room where the sun is exposed (near the window). It is a substance that can be cured by. Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as this type of compound, and the type thereof is not particularly limited. For example, unsaturated acrylic compounds, polycinnamic acid Examples thereof include vinyls or azide resins, epoxy compounds, vinyl ether compounds and the like.

Specific examples of unsaturated acrylic compounds include (meth) acrylic acid esters (oligoester acrylates) of low molecular weight alcohols such as ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, and neopentyl alcohol; bisphenol A (Meth) acrylic acid esters of alcohols obtained by modifying acids such as isocyanuric acid or the above-mentioned low molecular weight alcohols with ethylene oxide or propylene oxide; polyether polyols whose main chain is a polyether and having a hydroxyl group at the terminal; Polymer polyols obtained by radical polymerization of vinyl monomers in polyols that are ethers, polyester polyols with a main chain of polyester and a hydroxyl group at the terminal, and main chains of vinyl or (meth) acrylic (Meth) acrylic acid esters such as polyols with hydroxyl groups in the main chain; the main chain is a vinyl or (meth) acrylic polymer and a polyfunctional acrylate is copolymerized in the main chain (Meth) acrylic esters obtained by reacting epoxy resins such as bisphenol A type and novolak type with (meth) acrylic acid; polyol, polyisocyanate and hydroxyl group-containing (meta ) Urethane acrylate oligomers having a urethane bond and a (meth) acryl group in the molecular chain obtained by reacting acrylate or the like.

Polyvinyl cinnamate is a photosensitive resin having a cinnamoyl group as a photosensitive group, and includes many polyvinyl cinnamate derivatives other than those obtained by esterifying polyvinyl alcohol with cinnamic acid.
Azide resin is known as a photosensitive resin having an azide group as a photosensitive group. In general, in addition to a rubber photosensitive solution in which an azide compound is added as a photosensitive agent, “photosensitive resin” (published March 17, 1972). , Published by the Printing Society Press, page 93 to page 106 to page 117), these are detailed examples, and these can be used alone or in combination, and a sensitizer can be added if necessary.
Examples of the epoxy compound and vinyl ether compound include epoxy group-terminated or vinyl ether group-terminated polyisobutylene.

Among the above-mentioned photocurable materials, unsaturated acrylic compounds are preferable because they are easy to handle.
The photocurable material is preferably added in an amount of 0.01 to 20 parts by weight with respect to 100 parts by weight of the polymer having a crosslinkable silyl group. If the amount is less than 0.01 parts by weight, the effect is small. If the amount exceeds 20 parts by weight, the physical properties may be adversely affected. Note that the addition of a sensitizer such as ketones or nitro compounds or an accelerator such as amines may enhance the effect.

<Air oxidation curable substance>
If necessary, an air oxidation curable material may be added to the curable composition of the present invention. The air oxidation curable substance is a compound having an unsaturated group that can be crosslinked and cured by oxygen in the air. By adding this air oxidation curable substance, the tackiness (also referred to as residual tack) of the cured product surface when the curable composition is cured can be reduced. The air oxidation curable substance in the present invention is a substance that can be cured by contact with air, and more specifically, has a property of curing by reacting with oxygen in the air. A typical air oxidation curable substance can be cured by, for example, standing in air indoors for 1 day.

Examples of air oxidative curable substances include drying oils such as tung oil and linseed oil; various alkyd resins obtained by modifying these drying oils; acrylic polymers modified with drying oil, epoxy resins, silicone resins, Urethane resin: 1,2-polybutadiene, 1,4-polybutadiene, C5 to C8 diene polymers and copolymers, and various modified products of the polymers and copolymers (maleinized modified products, boil oil modified products) And the like. Of these, paulownia oil, diene polymer liquid (liquid diene polymer) and modified products thereof are particularly preferred.

Specific examples of the liquid diene polymer include a liquid polymer obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene, and copolymerizable with these diene compounds. Polymers such as NBR and SBR obtained by copolymerizing monomers such as acrylonitrile and styrene having a main component with a diene compound, and various modified products thereof (maleinized modified products, boiled oils) Modified products etc.). These may be used alone or in combination of two or more. Of these liquid diene compounds, liquid polybutadiene is preferred.

The air oxidation curable substance may be used alone or in combination of two or more. In addition, the effect may be enhanced if a catalyst that promotes the oxidative curing reaction or a metal dryer is used together with the air oxidative curable substance. Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, and zirconium octylate, amine compounds, and the like.

The air oxidation curable substance may be used in combination with the above-described photocurable substance, and further, the above-mentioned silanol-containing compound may be used in combination. Combined use of these two components or combination of the three components further demonstrates its effect, especially when exposed to long-term use, and in a severely polluted area with a lot of dust and fine earth and sand. This is particularly preferable.
The air oxidation curable substance is preferably added in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the polymer having a crosslinkable silyl group. If the amount is less than 0.01 parts by weight, the effect is small. If the amount exceeds 20 parts by weight, the physical properties may be adversely affected.

<Antioxidant>
You may add antioxidant to the curable composition of this invention as needed. Various types of antioxidants are known, and are described in, for example, “Antioxidant Handbook” published by Taiseisha, “Degradation and Stabilization of Polymer Materials” (235-242), issued by CM Chemical Co., Ltd. Although various things are mentioned, it is not necessarily limited to these.

Examples of the antioxidant include thioether-based antioxidants such as MARK PEP-36 and MARK AO-23 (all manufactured by Asahi Denka Kogyo Co., Ltd.); Irgafos 38, Irgafos 168, Irgafos P-EPQ (all of these are Ciba Specialty Chemicals) And phosphorous antioxidants such as hindered phenolic compounds. Of these, hindered phenol compounds as shown below are preferred.

Specific examples of the hindered phenol compound include the following. 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, mono (or di- or tri) (α-methylbenzyl) phenol, 2,2′- Methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4 , 4′-thiobis (3-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, triethylene glycol-bis- [3- (3 -T-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [ -(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino)- 1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5- Di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-to Limethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl) calcium, tris -(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4-2,4-bis [(octylthio) methyl] o-cresol, N, N'-bis [3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, tris (2,4-di-t-butylphenyl) phosphite, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2 -[2-Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyl Enyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5 -Chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) -benzotriazole, methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-condensate with polyethylene glycol (molecular weight about 300), hydroxyphenylbenzotriazole derivative, 2- (3 5-Di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6- Ntamechiru 4-piperidyl), 2,4-di -t- butyl-3,5-di -t- butyl-4-hydroxybenzoate, and the like.

In terms of trade names, Nocrack 200, Nocrack M-17, Nocrack SP, Nocrack SP-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack 300, Nocrack NS-7, Nocrack DAH (all above Manufactured by Ouchi Shinsei Chemical Industry), MARK AO-30, MARK AO-40, MARK AO-50, MARK AO-60, MARK AO-616, MARK AO-635, MARK AO-658, MARK AO-80, MARK AO-15, MARK AO-18, MARK 328, MARK AO-37 (all manufactured by Asahi Denka Kogyo), IRGANOX-245, IRGANOX-259, IRGANOX-565, IRGANOX-1010, IRGANOX-1024, IRGANOX 1035, IRGANOX-1076, IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330, IRGANOX-1425WL (all of these are manufactured by Ciba Specialty Chemicals), Sumizer GM, Sumilizer GA-80 (all of which are manufactured by Sumitomo Chemical) However, the present invention is not limited to these examples.

Antioxidants may be used in combination with the light stabilizers described later, and are particularly preferred because they can further exert their effects and improve heat resistance in particular. Tinuvin C353, Tinuvin B75 (both manufactured by Ciba Specialty Chemicals) or the like in which an antioxidant and a light stabilizer are mixed in advance may be used.
It is preferable that the usage-amount of antioxidant is the range of 0.1-10 weight part with respect to 100 weight part of polymers which have a crosslinkable silyl group. If the amount is less than 0.1 parts by weight, the effect of improving the weather resistance is small, and if it exceeds 5 parts by weight, the effect is not greatly different, which is economically disadvantageous.

<Light resistance stabilizer>
You may add a light-resistant stabilizer to the curable composition of this invention as needed. Various types of light-resistant stabilizers are known and described in, for example, “Antioxidant Handbook” published by Taiseisha, “Degradation and Stabilization of Polymer Materials” (235-242), issued by CMC Chemical, and the like. There are various types. Although it is not necessarily limited to these, in a light-resistant stabilizer, a ultraviolet absorber and a hindered amine light stabilizer compound are preferable.

Specific examples of ultraviolet absorbers include benzotriazole compounds such as Tinuvin P, Tinuvin 234, Tinuvin 320, Tinuvin 326, Tinuvin 327, Tinuvin 329, Tinuvin 213 (all of which are manufactured by Ciba Specialty Chemicals). A triazine compound such as Tinuvin 1577; a benzophenone compound such as CHIMASSORB 81; and a benzoate compound such as Tinuvin 120 (manufactured by Ciba Specialty Chemicals).

Hindered amine compounds are also preferred, and such compounds are described below.
Dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate of succinate, poly [{6- (1,1,3,3-tetramethylbutyl) Amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino}], N, N′-bis (3aminopropyl) ethylenediamine- 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate, succinic acid-bis (2,2,6,6-tetramethyl-4-piperidinyl) ester and the like.

In terms of product names, Tinuvin 622LD, Tinuvin 144, CHIMASSORB 944LD, CHIMASSORB 119FL, Irgafos 168 (all of which are manufactured by Ciba Specialty Chemicals), MARK LA-52, MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-63, MARK LA-68, MARK LA-82, MARK LA-87 (all manufactured by Asahi Denka Kogyo), Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Examples include, but are not limited to, Sanol LS-1114, Sanol LS-744, Sanol LS-440 (all of which are manufactured by Sankyo).

The light-resistant stabilizer may be used in combination with the above-mentioned antioxidant, and is particularly preferable because the effect is further exhibited by using it together, and the weather resistance may be improved. The combination is not particularly limited, but the combination of the above-mentioned hindered phenol antioxidant and, for example, a benzotriazole ultraviolet absorber, or the combination of the above-mentioned hindered phenol antioxidant and a hindered amine light stabilizer compound may be used. preferable. Or the combination of the above-mentioned hindered phenolic antioxidant, for example, a benzotriazole type ultraviolet absorber and a hindered amine light stabilizer compound is preferable. Tinuvin C353, Tinuvin B75 (both manufactured by Ciba Specialty Chemicals) or the like in which a light stabilizer and an antioxidant are mixed in advance may be used.

The hindered amine light stabilizer may be used in combination with the above-mentioned photo-curing substance, and it is particularly preferable because the hindered amine light stabilizer further exerts its effect and particularly the weather resistance may be improved. The combination is not particularly limited, but in this case, a hindered amine light stabilizer containing a tertiary amine is preferable because the increase in viscosity during storage is small and the storage stability is good.
It is preferable that the usage-amount of a light stabilizer is the range of 0.1-10 weight part with respect to 100 weight part of polymers which have a crosslinkable silyl group. If it is less than 0.1 parts by weight, the effect of improving the weather resistance is small, and if it exceeds 5 parts by weight, there is no great difference in the effect, which is economically disadvantageous.

<Compatibilizer>
A compatibilizing agent can be added to the curable composition of the present invention. As a specific example of such a compatibilizing agent, for example, a copolymer of a plurality of vinyl monomers described in the specification of JP-A-2001-329025 can be used.
The addition amount of the compatibilizing agent is preferably 1 to 200 parts by weight, more preferably 5 to 100 parts by weight with respect to 100 parts by weight of the polymer having a crosslinkable silyl group.

<Compound having an α, β diol structure or an α, γ diol structure in the molecule>
A compound having an α, β diol structure or an α, γ diol structure in the molecule may be added to the curable composition of the present invention. As the compound having an α, β diol structure or an α, γ diol structure, generally well-known compounds can be used. In the present specification, the α, β diol structure represents a structure having two hydroxyl groups at adjacent carbon atoms, and the α, γ diol structure has two hydroxyl groups at adjacent carbon atoms. In addition, as represented by glycerin and the like, both α and β diol structures and α and γ diol structures, or polyols such as triols and tetraols containing either structure are also included.

The compound having an α, β diol structure or an α, γ diol structure in the molecule is not particularly limited. For example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3 Diols such as butanediol, 2,3-butanediol, pinacol, 2,2-dimethyl-1,3-propanediol, 2-methyl-2-hydroxymethyl-1,3-propanediol; glycerin, 1, Triols such as 2,6-hexanetriol, 1,1,1-tris (hydroxymethyl) propane, 2,2-bis (hydroxymethyl) butanol; pentaerythritol, D-sorbitol, D-mannitol, diglycerin, poly Tetravalent or higher polyols such as glycerin;
Glycerol monostearate, glycerol monoisostearate, glycerol monooleate, glycerol monolaurate, glycerol monopalmitate, glycerol monocaprylate, glycerol monoacetate, glycerol monocarboxylic acid esters such as glycerol monobehenate; diglycerol Monostearate, diglycerol monooleate, diglycerol monolaurate, tetraglycerol monostearate, tetraglycerol monooleate, tetraglycerol monolaurate, tetraglycerol distearate, tetraglycerol dioleate, tetraglycerol dilaurate, Decaglycerin monostearate, decaglycerin monooleate, decaglycerin monolaurate, decaglycerin distearate, decaglyce Polyglycerol carboxylic acid esters such as dioleolate and decaglycerin dilaurate; pentaerythritol monocarboxylic acid esters such as pentaerythritol monostearate, pentaerythritol monoisostearate, pentaerythritol monooleate and pentaerythritol monolaurate; pentaerythritol Pentaerythritol dicarboxylic acid esters such as distearate, pentaerythritol dioleate, pentaerythritol dilaurate; sorbitan monoesters such as sorbitan monostearate, sorbitan monooleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monobehenate Carboxylic acid esters; sorbitan distearate, sorbitan dioleate, sorbitan Laurate, sorbitan distearate palmitate, sorbitan distearate acids SL such as sorbitan dibehenate;
Glycerin monoalkyl ethers such as glycerol monostearyl ether, glycerol monooleyl ether, glycerol monolauryl ether, glycerol mono-2-ethylhexyl ether; diglycerol monostearyl ether, diglycerol monooleyl ether, diglycerol monolauryl ether, tetraglycerol Monostearyl ether, tetraglycerin monooleyl ether, tetraglycerin monolauryl ether, tetraglycerin distearyl ether, tetraglycerin dioleyl ether, tetraglycerin dilauryl ether, decaglycerin monostearyl ether, decaglycerin monooleyl ether, decaglycerin monolauryl Ether, decaglycerin distearyl ether, decaglycerin Polyglycerol alkyl ethers such as dioleyl ether and decaglycerol dilauryl ether; Pentaerythritol monoalkyl ethers such as pentaerythritol monostearyl ether, pentaerythritol monooleyl ether and pentaerythritol monolauryl ether; pentaerythritol distearyl ether, penta Pentaerythritol dialkyl ethers such as erythritol dioleyl ether and pentaerythritol dilauryl ether; sorbitan monoalkyl ethers such as sorbitan monostearyl ether, sorbitan monooleyl ether and sorbitan monolauryl ether; sorbitan distearyl ether, sorbitan dioleyl ether, Sorbi such as sorbitan dilauryl ether Down dialkyl ether, and the like can be mentioned.

Many of the above-mentioned compounds are easily used as emulsifiers, surfactants, dispersants, antifoaming agents, antifogging agents, solubilizers, thickeners, and lubricants.
The above compounds may be used alone or in combination of two or more. The amount of the compound used is preferably 0.01 to 100 parts by weight with respect to 100 parts by weight of the vinyl polymer (I). If it is less than 0.01 part by weight, the intended effect cannot be obtained, and if it exceeds 100 parts by weight, the mechanical strength of the cured product tends to be insufficient. More preferably, it is 0.1-20 weight part.

<Other additives>
Various additives may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include flame retardants, curability modifiers, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, and the like. These various additives may be used alone or in combination of two or more.
Specific examples of such additives are described in, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, and the like. .

<Preparation of curable composition>
As described above, the curable composition of the present invention comprises a vinyl polymer (I) having an average of at least one crosslinkable silyl group, an epoxy resin (II), and a room temperature curable latent curing agent (III ). The curable composition can further contain a reactive silicon group-containing silane compound (IV) and a polyether polymer (V). Furthermore, the said curable composition can also contain the said various additives.

The curable composition of the present invention can be used substantially without a solvent. Although a solvent may be used from the viewpoint of workability and the like, it is desirable not to use it because of environmental influences.
The curable composition of the present invention may be prepared as a one-component type in which all compounding components are preliminarily blended and stored and cured by moisture in the air after construction. The vinyl polymer (I) and epoxy resin ( II) Separate each curing agent / curing catalyst, separately blend components such as filler, plasticizer, water, etc., and mix the blending material containing each polymer composition before use. You may adjust as a 2 component type.
For example, although it is not limited, as the A agent, an amine as a curing agent for the vinyl polymer (I) and the epoxy resin (II), an aminosilane as an adhesion-imparting agent, and the like are prepared, and an epoxy is used as the B agent. It is also possible to prepare a tin compound as a curing catalyst for the resin (II) and the vinyl polymer (I), water, etc., and mix and use the above-mentioned A agent and B agent immediately before construction. .
When the two-component type is used, a colorant can be added when the two components are mixed. For example, when providing a sealing material that matches the color of the siding board, an abundant color alignment is possible with a limited stock. This makes it possible to easily cope with the increase in the number of colors required by the market, and is preferable for low-rise buildings. In addition, for the same reason as the two-component type, a colorant may be added when using the one-component curable composition. In particular, the one-component curable composition in a can container can easily cope with multicolorization. Become. When using and adjusting what was adjusted as a 1 component type, after taking out from a container, you may make it harden by adding water, mixing, etc.
The colorant is easy to work if, for example, a pigment and a plasticizer, and in some cases, a paste prepared by mixing a filler is used. Further, by adding a retarder during mixing of the two components, the curing rate can be finely adjusted at the work site.

<< Usage >>
The curable composition of the present invention includes, but is not limited to, an elastic sealant for buildings, a sealant for siding boards, a sealant for double glazing, a sealant for vehicles, and the like, and a sealing agent for construction and industry, solar cell Electrical and electronic component materials such as backside sealants, electrical insulation materials such as insulation coating materials for electric wires and cables, adhesives, adhesives, elastic adhesives, contact adhesives, tile adhesives, reactive hot melt adhesives Coating materials, powder coating materials, coating materials, foams, sealing materials for can lids, potting agents for electrical and electronic use, films, gaskets, casting materials, various molding materials, artificial marble, and meshed glass and laminated glass end faces Rust prevention / waterproof sealing materials for (cutting parts), vibration-proof / vibration-proof / sound-proof / isolation materials used in automobiles, ships, home appliances, etc., automotive parts, electrical parts, various machine parts, etc. Liquid sealing agent used, are available in a variety of applications such as waterproofing agents.

Furthermore, the molded product showing rubber elasticity obtained from the curable composition of the present invention can be widely used mainly for gaskets and packings. For example, in the automobile field, it can be used as a body part as a sealing material for maintaining airtightness, an anti-vibration material for glass, an anti-vibration material for vehicle body parts, particularly a wind seal gasket and a door glass gasket. As chassis parts, it can be used for vibration-proof and sound-proof engines and suspension rubbers, especially engine mount rubbers. Engine parts can be used for hoses for cooling, fuel supply, exhaust control, etc., sealing materials for engine oil, and the like. It can also be used for exhaust gas cleaning device parts and brake parts. In the home appliance field, it can be used for packing, O-rings, belts and the like. Specifically, decorations for lighting fixtures, waterproof packings, anti-vibration rubbers, insect-proof packings, anti-vibration / sound absorption and air sealing materials for cleaners, drip-proof covers for electric water heaters, waterproof packings, heater parts Packing, electrode packing, safety valve diaphragm, hose for sake cans, waterproof packing, solenoid valve, waterproof packing for steam microwave oven and jar rice cooker, water tank packing, water absorption valve, water receiving packing, connection hose, belt, heat insulation Oil packing for combustion equipment such as heater packing, steam outlet seal, etc., O-ring, drain packing, pressure tube, blower tube, feed / intake packing, anti-vibration rubber, oil filler packing, oil meter packing, oil feed tube, Speaker gaskets, speaker edges, turntable systems for acoustic equipment such as diaphragm valves and air pipes Door, belts, pulleys, and the like. In the construction field, it can be used for structural gaskets (zipper gaskets), air membrane roof materials, waterproof materials, fixed sealing materials, vibration-proof materials, sound-proof materials, setting blocks, sliding materials, and the like. In the sports field, it can be used for all-weather pavement materials, gymnasium floors, etc. as sports floors, shoe sole materials, midsole materials, etc. as sports shoes, golf balls etc. as ball for ball games. In the field of anti-vibration rubber, it can be used as anti-vibration rubber for automobiles, anti-vibration rubber for railway vehicles, anti-vibration rubber for aircraft, anti-vibration materials, and the like. In the marine and civil engineering fields, structural materials include rubber expansion joints, bearings, waterstops, waterproof sheets, rubber dams, elastic pavements, anti-vibration pads, protective bodies, etc., rubber molds, rubber packers, rubber skirts as construction secondary materials , Sponge mats, mortar hoses, mortar strainers, etc., rubber sheets, air hoses, etc. as construction auxiliary materials, rubber buoys, wave-absorbing materials, etc. as safety measures products, oil fences, silt fences, antifouling materials, marine hoses, etc. Can be used for draging hoses, oil skimmers, etc. In addition, it can be used for sheet rubber, mats, foam boards and the like.

Among these, the curable composition of the present invention is particularly useful as a sealing material and an adhesive, and is particularly useful for applications that require weather resistance and heat resistance and for applications that require transparency. Moreover, since the curable composition of this invention is excellent in a weather resistance and adhesiveness, it can be used for the construction method of an outer wall tile adhesion | attachment without joint filling. Furthermore, it can be used for adhesion of materials with different linear expansion coefficients, application of elastic adhesives for adhesion of members that are repeatedly displaced by heat cycle, and coating agents for applications where the base can be seen by taking advantage of transparency. It is also useful for applications such as adhesives used for bonding transparent materials such as glass, polycarbonate and methacrylic resin.

The curable composition of the present invention is excellent in storage stability as a curable composition and has a low viscosity, but the cured product when cured is given a wide elastic body from hard to soft, and weather resistance In addition, it has excellent heat resistance, improves the hard and brittle nature of epoxy resin, has rubber elasticity, and has high adhesive strength.

Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples.
In the following synthesis examples, examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.
Synthesis examples of the polymer in the present invention are shown below.
In the following synthesis examples, “number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column packed with polystyrene cross-linked gel (shodex GPC K-804; manufactured by Showa Denko) and chloroform as a GPC solvent were used.

(Synthesis example 1) Synthesis example of poly (acrylic acid-n-butyl) polymer having a crosslinkable silyl group CuBr (1.09 kg), acetonitrile (11.4 kg) in a 250 L reactor under nitrogen atmosphere , -N-butyl acrylate (26.0 kg) and diethyl 2,5-dibromoadipate (2.28 kg) were added, and the mixture was stirred at 70 to 80 ° C. for about 30 minutes. To this was added pentamethyldiethylenetriamine to initiate the reaction. Over 30 minutes after the start of the reaction, acrylic acid-n-butyl (104 kg) was continuously added over 2 hours. During the reaction, pentamethyldiethylenetriamine was appropriately added so that the internal temperature became 70 ° C to 90 ° C. The total amount of pentamethyldiethylenetriamine used so far was 220 g. Four hours after the start of the reaction, volatile components were removed by heating and stirring at 80 ° C. under reduced pressure. Acetonitrile (45.7 kg), 1,7-octadiene (14.0 kg) and pentamethyldiethylenetriamine (439 g) were added thereto, and stirring was continued for 8 hours. The mixture was heated and stirred at 80 ° C. under reduced pressure to remove volatile components.
Toluene is added to this concentrate to dissolve the polymer, diatomaceous earth is added as a filter aid, aluminum silicate and hydrotalcite are added as adsorbents, and an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6%) is set to an internal temperature of 100. The mixture was heated and stirred at ° C. The solid content in the mixed solution was removed by filtration, and the filtrate was heated and stirred at an internal temperature of 100 ° C. under reduced pressure to remove volatile components.
Furthermore, aluminum silicate, hydrotalcite, and a heat deterioration inhibitor were added as adsorbents to the concentrate, and the mixture was heated and stirred under reduced pressure (average temperature of about 175 ° C., reduced pressure of 10 Torr or less).
Furthermore, aluminum silicate and hydrotalcite were added as adsorbents, an antioxidant was added, and the mixture was heated and stirred at an internal temperature of 150 ° C. in an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6%).
Toluene was added to this concentrate to dissolve the polymer, and then the solid content in the mixed solution was removed by filtration. The filtrate was heated and stirred under reduced pressure to remove volatile matter, and the polymer having an alkenyl group was removed. Obtained.

Polymer having this alkenyl group, dimethoxymethylsilane (2.0 molar equivalents relative to alkenyl group), methyl orthoformate (1.0 molar equivalents relative to alkenyl group), bis (1,3-divinyl as platinum catalyst) A xylene solution of -1,1,3,3-tetramethyldisiloxane) platinum complex catalyst (10 mg as platinum relative to 1 kg of polymer) was mixed and heated and stirred at 100 ° C. in a nitrogen atmosphere. After confirming disappearance of the alkenyl group, the reaction mixture was concentrated to obtain a poly (acrylic acid-n-butyl) polymer [P1] having a dimethoxysilyl group at the terminal. The number average molecular weight of the obtained polymer was about 26000, and the molecular weight distribution was 1.3. When the average number of silyl groups introduced per molecule of the polymer was determined by ¹ H NMR analysis, it was about 1.8.

(Synthesis example 2) Synthesis example of poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate) copolymer having a crosslinkable silyl group CuBr was added to a 250 L reactor in a nitrogen atmosphere. (1.21 kg), acetonitrile (10.8 kg), acrylate-n-butyl (7.19 kg), ethyl acrylate (10.3 kg), 2-methoxyethyl acrylate (8.47 kg) and 2,5- Diethyl dibromoadipate (3.37 kg) was added, and the mixture was stirred at 70-80 ° C. for about 30 minutes. To this was added pentamethyldiethylenetriamine to initiate the reaction. A mixture of n-butyl acrylate (28.8 kg), ethyl acrylate (41.3 kg) and 2-methoxyethyl acrylate (33.9 kg) was continuously added over 2 hours after 30 minutes from the start of the reaction. did. During the reaction, pentamethyldiethylenetriamine was appropriately added so that the internal temperature became 70 ° C to 90 ° C. The total amount of pentamethyldiethylenetriamine used so far was 243 g. Four hours after the start of the reaction, volatile components were removed by heating and stirring at 80 ° C. under reduced pressure. Acetonitrile (32.5 kg), 1,7-octadiene (30.9 kg) and pentamethyldiethylenetriamine (486 g) were added thereto, and stirring was continued for 4 hours. The mixture was heated and stirred at 80 ° C. under reduced pressure to remove volatile components.
Toluene was added to this concentrate to dissolve the polymer, diatomaceous earth was added as a filter aid, aluminum silicate and hydrotalcite were added as adsorbents, and the mixture was heated and stirred in an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6%). . The solid content in the mixed solution was removed by filtration, and the filtrate was heated and stirred at an internal temperature of 100 ° C. under reduced pressure to remove volatile components.
Furthermore, aluminum silicate, hydrotalcite, and a heat deterioration inhibitor were added as adsorbents to the concentrate, and the mixture was heated and stirred under reduced pressure (average temperature of about 175 ° C., reduced pressure of 10 Torr or less).
Furthermore, aluminum silicate and hydrotalcite were added as adsorbents, an antioxidant was added, and the mixture was heated and stirred in an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6%).
Toluene was added to this concentrate to dissolve the polymer, and then the solid content in the mixed solution was removed by filtration. The filtrate was heated and stirred under reduced pressure to remove volatile matter, and the polymer having an alkenyl group was removed. Obtained.

Polymer having this alkenyl group, dimethoxymethylsilane (2.0 molar equivalents relative to alkenyl group), methyl orthoformate (1.0 molar equivalents relative to alkenyl group), bis (1,3-divinyl as platinum catalyst) A xylene solution of -1,1,3,3-tetramethyldisiloxane) platinum complex catalyst (10 mg as platinum relative to 1 kg of polymer) was mixed and heated and stirred at 100 ° C. in a nitrogen atmosphere. After confirming the disappearance of the alkenyl group, the reaction mixture was concentrated to obtain a poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate) copolymer [P2] having a dimethoxysilyl group at the terminal. Obtained. The number average molecular weight of the obtained copolymer was about 18,000 and the molecular weight distribution was 1.2. When the average number of silyl groups introduced per molecule of the copolymer was determined by ¹ H NMR analysis, it was about 1.9.

(Example 1)
70 parts of the polymer [Polymer P1] obtained in Synthesis Example 1, 30 parts of hydrogenated bisphenol A type epoxy resin Epolite 4000 (manufactured by Kyoeisha), 2 parts of vinyltrimethoxysilane A-171 (manufactured by Nihon Unicar) , 3 parts A-187 (manufactured by Nihon Unicar) of γ-glycidoxypropyltrimethoxysilane, 15 parts of epicure H-30 (ketimine type, made by Japan Epoxy Resin) of room temperature curable latent curing agent for epoxy resin, dibutyl A tin compound # 918 (polymer catalyst having a crosslinkable silyl group: manufactured by Sansha Co., Ltd.), 0.7 parts by hand, well stirred, mixed and stored as a one-part curable composition It was adjusted.
This curable composition was stored at 50 ° C. for 1 week, and then taken out and applied to a degreased aluminum adherend in the form of a bead having a diameter of about 5 mm, and left at room temperature for 3 days, and further at 50 ° C. After leaving still for 4 days to cure and curing, peeling by hand was attempted. As a result, it showed sufficient workability and adhesive strength to such an extent that it would not peel off even when pulled lightly.

The physical properties in the following examples and comparative examples were measured as follows.
(viscosity)
The viscosity of the obtained curable composition was measured using an E-type viscometer (measurement temperature 23 ° C.).
(Breaking strength and breaking elongation)
The obtained curable composition was applied to a sheet having a thickness of about 2 mm while heating and reducing the pressure, and the sheet-like construction was allowed to stand at room temperature for 3 days, and further allowed to stand at 50 ° C. for 4 days to cure. Cured. A 2 (1/3) type dumbbell-shaped test piece shown in JIS K 7113 is punched out from the cured product after curing and cured, and a tensile test (using an autograph manufactured by Shimadzu, measurement temperature: 23 ° C., tensile speed: 200 mm / min) ).

(Tensile shear strength)
In accordance with JIS K 6850, the obtained curable composition was applied to a 2 mm-thick degreased aluminum adherend at a thickness of about 100 μm to prepare a sample for tensile shearing and left at room temperature for 3 days. Further, after standing still at 50 ° C. for 4 days to cure and curing, a tensile test (using Shimadzu autograph, measuring temperature: 23 ° C., tensile speed: 50 mm / min) was performed.
(T-type peel strength)
In accordance with JIS K 6854, the obtained curable composition was applied to a 0.1 mm thick degreased aluminum adherend at a thickness of about 100 μm to prepare a T-shaped release sample, and at room temperature for 3 days. After standing still and further curing at 50 ° C. for 4 days, a tensile test (using Shimadzu autograph, measuring temperature: 23 ° C., tensile speed: 200 mm / min) was performed.

(Examples 2-7, Comparative Examples 1-2)
A blend obtained by adding the polymer [Polymer P2] obtained in Synthesis Example 2 above, an epoxy resin, and various blending agents in the blending amounts shown in Table 1 below is thoroughly stirred and mixed by hand, and the mixture is put into a sealed container. It preserve | saved and adjusted as 1 liquid type curable composition.
Using the obtained curable composition, the viscosity, breaking strength, and breaking elongation before storage were measured as described above.
Next, the curable composition preserve | saved at said airtight container was stored at 50 degreeC for 1 week. Using the curable composition after storage, the viscosity, breaking strength, and breaking elongation after storage were measured as described above. Moreover, the viscosity increase rate was calculated and workability | operativity was evaluated.
These results are shown in Table 1. In Comparative Examples 1 and 2, thickening was observed and the viscosity was measured quickly, but gelled in about 30 to 100 minutes.

(Example 8)
A curable composition was obtained in the same manner as in Example 1 except that instead of [Polymer P1] in Example 1, the polymer [Polymer P2] obtained in Synthesis Example 2 was used. When the tensile shear strength was measured as described above using the curable composition, it was 534 (N / cm ² ), and the T-shaped peel strength was 8.9 (N / 25 mm). Sufficient adhesive properties were exhibited.

Example 9
Using the same raw materials as in Example 8, [Polymer P2] from 70 parts to 50 parts, epoxy resin from 30 parts to 50 parts, epicure H-30 from 15 parts to 25 parts, and # 918 to 0.7 parts A curable composition was obtained in the same manner as in Example 8 except that the amount was changed from 0.5 part to 0.5 part. When the tensile shear strength was measured as described above using the curable composition, it was 690 (N / cm ² ), and the T-shaped peel strength was 11.2 (N / 25 mm). Sufficient adhesive properties were exhibited.

In addition, the following were used for the epoxy resin and various compounding agents which were used for each Example and the comparative example.
Epolite 4000: Hydrogenated bisphenol A type epoxy resin (manufactured by Kyoeisha)
# 918: No. 918 (dibutyltin compound, polymer catalyst having a crosslinkable silyl group; manufactured by Sansha Co., Ltd.)
EpiCure H-30: Room temperature curing type latent curing agent (ketimine type, epoxy resin curing agent; manufactured by Japan Epoxy Resin)
Adeka Hardener EH-235R-2S: Room temperature curing type latent curing agent (ketimine type, epoxy resin curing agent; manufactured by Asahi Denka)
Adeka Hardener EH-235R-2: Room temperature curing type latent curing agent (ketimine type, epoxy resin curing agent; manufactured by Asahi Denka)
Ancamine K54: 2,4,6-tris-dimethylaminomethyl-phenol (epoxy resin curing agent; manufactured by Air Products Japan)
A-171: Vinyltrimethoxysilane (Nihon Unicar)
A-187: γ-glycidoxypropyltrimethoxysilane (manufactured by Nihon Unicar)
A-1122: N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane (Nihon Unicar)

The cured product obtained by curing any of the curable compositions of any of the examples improves the hard and brittle nature of the epoxy resin, has sufficient rubber elasticity, and is as high as the conventional two-component system. It had strength and maintained good workability and physical properties even after storage at 50 ° C. for 1 week.

The curable composition of the present invention is excellent in storage stability as a curable composition and has a low viscosity, but the cured product when cured is given a wide elastic body from hard to soft, and weather resistance In addition, it has excellent heat resistance, improves the hard and brittle nature of epoxy resin, has rubber elasticity, and has high adhesive strength.

Claims (22)

A curable composition comprising a vinyl polymer (I) having at least one crosslinkable silyl group on average, an epoxy resin (II), and a room temperature curable latent curing agent (III). 2. The curable composition according to claim 1, which is prepared as a one-component type in which all compounding components are preliminarily blended and stored and cured by moisture in the air after construction. The curable composition according to claim 1 or 2, comprising a vinyl polymer (I) having a molecular weight distribution of less than 1.8. The crosslinkable silyl group in the vinyl polymer (I) has the general formula (1)
^{_{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
(In the formula, R ¹ and R ² are the same or different and each represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO. (Wherein R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. A plurality of R ′ may be the same or different.) When two or more R ¹ or R ² are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and two or more Y are present. , They may be the same or different, a represents 0, 1, 2, or 3. b represents 0, 1, or 2. m represents an integer of 0 to 19, provided that A + mb ≧ 1).
It is represented by these, The curable composition in any one of Claims 1-3 characterized by the above-mentioned. The main chain of the vinyl polymer (I) is at least one selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and silicon-containing vinyl monomers. The curable composition according to any one of claims 1 to 4, wherein the curable composition is produced mainly by polymerizing monomers. The curable composition according to claim 5, wherein the main chain of the vinyl polymer (I) is a (meth) acrylic polymer. The curable composition according to claim 6, wherein the main chain of the vinyl polymer (I) is an acrylic polymer. The curable composition according to claim 7, wherein the main chain of the vinyl polymer (I) is an acrylate polymer. The curable composition according to any one of claims 1 to 8, wherein the main chain of the vinyl polymer (I) is produced by a living radical polymerization method. The curable composition according to claim 9, wherein the main chain of the vinyl polymer (I) is produced by an atom transfer radical polymerization method. The curable composition according to any one of claims 1 to 10, wherein the crosslinkable silyl group of the vinyl polymer (I) is at a molecular chain terminal. The curable composition according to any one of claims 1 to 11, wherein the epoxy resin (II) is an epoxy resin having no aromatic ring. The curable composition according to claim 12, wherein the epoxy resin (II) is an alicyclic epoxy resin. The curable composition according to claim 13, which is an epoxy resin in which the glycidyl group of the epoxy resin (II) is not directly attached to the alicyclic ring. The curable composition according to claim 14, wherein the epoxy resin (II) is at least one selected from the group of hydrogenated bisphenol A type epoxy resins and glycidyl ester type epoxy resins. The curable composition according to any one of claims 1 to 15, wherein the room temperature curable latent curing agent (III) is ketimine. The curable composition according to any one of claims 1 to 15, wherein the room temperature curable latent curing agent (III) is oxazolidine. 16. The curable composition according to claim 1, wherein the room temperature curable latent curing agent (III) is a silamine obtained by dehydrochlorination condensation of an amine compound and trimethylchlorosilane. The curable composition according to any one of claims 1 to 18, further comprising a reactive silicon group-containing silane compound (IV). Furthermore, polyether type polymer (V) is contained, The curable composition in any one of Claims 1-19 characterized by the above-mentioned. 21. The curable composition according to claim 20, wherein the main chain of the polyether polymer (V) is essentially polypropylene oxide. The curable composition according to claim 21, wherein the polyether polymer (V) is a polymer having an average of at least one crosslinkable silyl group.