JP2010077442A - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition low in viscosity of a curable composition, having good workability, suppressing bleeding of a plasticizer on the surface of a cured material prepared by curing the curable composition thereby reducing the contamination of the cured material (including coating contamination), further low in modulus and high in elongation of the cured material, also retaining the mechanical properties for a long period of time, and furthermore having good adhesive properties and a high gel fraction. <P>SOLUTION: The curable composition which comprises a vinyl polymer having at least one crosslinkable silyl group and a polyether polymer having 1.2 or less crosslinkable silyl group on average, is used. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a curing containing a vinyl polymer (I) having at least one crosslinkable silyl group and a polyether polymer (II) having an average of 1.2 or less crosslinkable silyl groups. It relates to a sex composition.

  Among polymers obtained by ionic polymerization or condensation polymerization, vinyl polymers obtained by radical polymerization and having a functional group, particularly a functional group at the terminal, have hardly been put into practical use. Among vinyl polymers, (meth) acrylic polymers have characteristics that cannot be obtained with polyether polymers, hydrocarbon polymers, or polyester polymers, such as high weather resistance and transparency. In addition, those having an alkenyl group or a crosslinkable silyl group in the side chain are used for highly weather-resistant paints. On the other hand, the polymerization control of the acrylic polymer is not easy because of the side reaction, and it is very difficult to introduce a functional group at the terminal.

  If a vinyl polymer having an alkenyl group at the molecular chain terminal can be obtained by a simple method, a cured product having excellent cured product properties can be obtained as compared with those having a crosslinkable group in the side chain. Therefore, many researchers have studied the production method so far, but it is not easy to produce them industrially. For example, Patent Documents 1 and 2 disclose a method for synthesizing a (meth) acrylic polymer having an alkenyl group at the terminal, using an alkenyl group-containing disulfide as a chain transfer agent.

  In Patent Document 3, a vinyl polymer having hydroxyl groups at both ends is synthesized using a disulfide having a hydroxyl group, and further, an alkenyl group is provided at the end using the reactivity of the hydroxyl group (meth). A method for synthesizing acrylic polymers is disclosed.

  In Patent Document 4, a vinyl polymer having hydroxyl groups at both ends is synthesized using a polysulfide having hydroxyl groups, and further, a hydroxyl group is used to have a silyl group at the terminal (meth). A method for synthesizing acrylic polymers is disclosed.

  In these methods, it is difficult to reliably introduce functional groups at both ends, and a cured product having satisfactory characteristics cannot be obtained. In order to reliably introduce functional groups at both ends, a large amount of chain transfer agent must be used, which is a problem in the production process. In these methods, since ordinary radical polymerization is used, it is difficult to control the molecular weight and molecular weight distribution (ratio of number average molecular weight to number average molecular weight) of the obtained polymer.

  In contrast to such conventional techniques, the inventors have so far made numerous inventions regarding vinyl polymers having various crosslinkable functional groups at their terminals, their production methods, curable compositions, and applications. (See Patent Documents 5 to 16).

  For example, a silicon-containing group having a hydroxyl group or hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond with moisture or the like even at room temperature (hereinafter also referred to as “crosslinkable silyl group”) The vinyl polymer having a cured product obtained from the composition or the composition thereof is excellent in heat resistance or weather resistance, and is not particularly limited. However, the sealing material such as an elastic sealing material sealant for buildings and a sealing material for multi-layer glass, solar Electrical and electronic component materials such as battery backside sealing materials, electrical insulation materials such as insulation coating materials for electric wires and cables, adhesives, adhesives, elastic adhesives, paints, powder paints, coating materials, foams, electrical and electronic products Potting agents, films, gaskets, casting materials, various molding materials, and anti-rust / waterproof sealing materials for meshed glass and laminated glass end faces (cut parts) Automotive parts and electrical parts, are available in a variety of applications of the seal such as various machine parts.

  Among the above-mentioned uses, sealing materials, particularly general architectural sealants, are generally used for the purpose of filling the joints and gaps between various members to provide watertightness and airtightness. Therefore, since followability to the site of use over a long period of time is extremely important, the physical properties of the cured product are required to have a low modulus, high elongation, high strength, and long-term maintenance of those properties. On the other hand, low viscosity is required as a curable composition (compound) in consideration of workability in these constructions.

  When the vinyl polymer is made high in molecular weight, the cured product of the curable composition using it as a raw material can have a low modulus, high elongation, and high strength, but the viscosity of the compound increases, Workability becomes worse. On the contrary, if the viscosity of the vinyl polymer is lowered, the workability is improved, but the mechanical properties of the cured product are lowered (high modulus, low elongation, low strength). In order to solve this problem, phthalic acid plasticizers such as phthalic acid esters having no functional group, polyether plasticizers, and the like are usually used.

JP-A-1-247403 Japanese Patent Laid-Open No. 5-255415 JP-A-5-262808 Japanese Patent Application Laid-Open No. 5-21922 JP-A-11-080249 Japanese Patent Laid-Open No. 11-080250 JP-A-11-005815 JP-A-11-116617 JP-A-11-116606 Japanese Patent Laid-Open No. 11-080571 JP-A-11-080570 JP-A-11-130931 Japanese Patent Laid-Open No. 11-100433 Japanese Patent Laid-Open No. 11-116763 JP-A-9-272714 Japanese Patent Laid-Open No. 9-272715

  However, when a large amount of such a plasticizer is blended, in the cured product obtained by curing the blend, the plasticizer bleeds on the surface of the cured product over time (also referred to as migration or oil bleed), causing problems such as stickiness. . Furthermore, this causes problems such as contamination of the periphery of the cured product (sealant and the like), surface contamination after coating, a decrease in adhesion, a decrease in hardness, elongation, and the like of the cured product.

  In addition, such a vinyl polymer having a crosslinkable silyl group often used a polymer having a hydrolyzable silicon group formed by bonding two hydrolyzable groups per silicon atom. There are also, especially when very fast curing speed is required, such as when using adhesives or at low temperatures, the curing speed is not sufficient, and if you want to give flexibility after curing, There is a problem in that the crosslink density needs to be lowered, and therefore the crosslink density is not sufficient, resulting in stickiness (surface tack).

  Therefore, the present invention provides a curable composition mainly comprising a vinyl polymer having at least one crosslinkable silyl group and a polyether polymer having 1.2 or less crosslinkable silyl groups on average. It has a low viscosity and good workability, and suppresses bleeding of the plasticizer on the surface of the cured product obtained by curing the curable composition, thereby contaminating the cured product (including paint contamination). The cured product has a low modulus and high elongation, maintains its mechanical properties for a long period of time, and further exhibits good adhesion, good alkyd paintability, and high gel fraction. Is to provide.

  As a result of diligent studies to solve such problems, the present inventors have found that a vinyl polymer having at least one crosslinkable silyl group and an average of 1.2 or less crosslinkable silyl groups. The present inventors have found that the above problems can be solved by using a curable composition containing as a main component a polyether-based polymer, and have completed the present invention.

  That is, the present invention includes a vinyl polymer (I) having at least one crosslinkable silyl group and a polyether polymer (II) having an average of 1.2 or less crosslinkable silyl groups. It relates to a curable composition.

  The vinyl polymer (I) is not particularly limited, but the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) measured by gel permeation chromatography is less than 1.8. Preferably there is.

  Further, the main chain of the vinyl polymer (I) is not particularly limited, but the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and silicon-containing vinyl monomers. It is preferably produced mainly by polymerizing a monomer selected from: (meth) acrylic monomers, more preferably acrylic monomers, more preferably acrylic ester monomers, for general architectural use, etc. In particular, it is most preferable to polymerize by using a butyl acrylate monomer 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, it is preferably produced by polymerization using an ethyl acrylate monomer in applications around automobile engines and machinery that require oil resistance, heat resistance, high strength, etc. It is more preferable to produce an ethyl acrylate monomer by copolymerization mainly using a 2-methoxyethyl acrylate monomer and a butyl acrylate monomer in view of properties. In consideration of physical properties such as oil resistance and low temperature characteristics, it is possible to change the ratio of monomers to be copolymerized.

  The main chain of the vinyl polymer (I) is not limited, but is preferably produced by living radical polymerization, more preferably atom transfer radical polymerization. Further, the atom transfer radical polymerization is not limited, but a catalyst selected from a transition metal complex having a central metal of a group 7, 8, 9, 10, or 11 element of the periodic table is used as a catalyst. More preferred is a complex selected from the group consisting of copper, nickel, ruthenium, or iron complexes, and particularly preferred is a copper complex.

  The position of the crosslinkable silyl group of the vinyl polymer (I) is not limited, but the terminal is preferable. In addition, although it may have the same functional group inside the main chain, it is preferable to have a functional group only at the terminal when, for example, rubber elasticity is required for the crosslinked cured product.

  The number of crosslinkable functional groups of the vinyl polymer (I) is not particularly limited, but in order to obtain a cured product having higher crosslinkability, it is preferable to have one or more on average, more preferably 1. 1 or more and 4.0 or less, more preferably 1.2 or more and 3.5 or less.

  The polyether polymer (II) having 1.2 or less crosslinkable silyl groups on average is not particularly limited, but the crosslinkable silyl group is preferably at the end of the main chain. Further, the crosslinkable silyl group of the polyether polymer (II) is preferably only at one terminal in the main chain and not at the other terminal, but is 1.2 or less on average. If it is, it will not specifically limit.

On the other hand, the vinyl polymer (I) is a crosslinkable silyl group in which a is 3 among the crosslinkable silyl groups represented by the general formula (1) in order to increase the curing rate and crosslink density of the blend. It is preferable to contain a vinyl polymer.
-SiY _a R _3-a (1)
(In the formula, R is 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— (R ′ is 1 carbon atom). A monovalent hydrocarbon group of -20, wherein three R's may be the same or different), and when there are two or more R And Y may be the same or different, and Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they may be the same or different. a represents 1, 2, or 3)
As described above, the position of the crosslinkable silyl group represented by the formula (1) is not limited, but the main chain terminal of the vinyl polymer (I) is preferable.

  The present invention comprises a curable composition comprising a vinyl polymer having at least one crosslinkable silyl group and a polyether polymer having an average of 1.2 or less crosslinkable silyl groups. Contamination of the cured product (including paint contamination) by suppressing the bleeding of the plasticizer on the surface of the cured product obtained by curing the curable composition. In addition, the cured product has a low modulus and high elongation, maintains its mechanical properties for a long period of time, and further has a good alkyd paintability and a high gel fraction.

  The present invention relates to a curable composition. More specifically, the following two components: a vinyl polymer (I) having at least one crosslinkable functional group, and a polyether polymer having an average of 1.2 or less crosslinkable silyl groups (II) ) Containing the curable composition. Below, the curable composition of this invention is explained in full detail.

<< About vinyl polymer >>
<Main chain>
The inventors of the present invention have made numerous inventions with respect to vinyl polymers having various crosslinkable functional groups at the end of the polymer, methods for producing the same, curable compositions, and uses (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, JP-A-11-116763, JP-A-9-272714, JP-A-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 decyl, (meth) acrylic acid dodecyl, (meth) Phenyl acrylate, tolyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (Meth) acrylic acid-3-methoxybutyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, stearyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic 2-aminoethyl acid, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, Perfluoroethyl methyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, perfluoroethyl perfluorobutyl methyl (meth) acrylate, 2-perfluoroethyl-2-perfluoro (meth) acrylate Butylethyl, (meth) acrylic acid perful Oroethyl, perfluoromethyl (meth) acrylate, diperfluoromethyl methyl (meth) acrylate, 2,2-diperfluoromethyl ethyl (meth) acrylate, perfluoromethyl perfluoroethyl methyl (meth) acrylate, (Meth) acrylic acid 2-perfluoromethyl-2-perfluoroethylethyl, (meth) acrylic acid 2-perfluorohexylmethyl, (meth) acrylic acid 2-perfluorohexylethyl, (meth) acrylic acid 2-per (Meth) acrylic monomers such as fluorodecylmethyl, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylmethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate; Styrene, vinyl toluene, α-methyl styrene, Aromatic vinyl monomers such as styrene, styrene sulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene and vinylidene fluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane Monomers; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octyl Maleimide monomers such as maleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; acrylonitrile, methacrylonitrile Amyl group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; Alkenes such as ethylene and propylene Conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be used alone or a plurality of these may be copolymerized.

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

  Of these, a styrene monomer and a (meth) acrylic acid monomer are preferable from the physical properties of the product. More preferred are acrylic ester monomers and methacrylic ester monomers, and particularly preferred are acrylic ester monomers. In applications such as general construction, a butyl acrylate monomer is more preferred 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, its good oil resistance is impaired. Therefore, for applications requiring oil resistance, the ratio is preferably 40% or less, and more preferably 30% or less. More preferably. 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 40% or less. 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 balance of physical properties such as oil resistance, heat resistance, and low temperature characteristics include ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate (40-50 / 20 by weight) 30/30 to 20).

  In the present invention, these preferable monomers may be copolymerized with other monomers, and further block copolymerized, and in this case, it is preferable that these preferable monomers are contained in a weight ratio of 40%. 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 number average molecular weight (Mn) measured by gel permeation chromatography is not particularly limited, but preferably Is less than 1.8, more preferably not more than 1.7, still more preferably not more than 1.6, still more preferably not more than 1.5, particularly preferably not more than 1.4, most preferably Is 1.3 or less. In the GPC measurement in the present invention, chloroform is usually used as the mobile phase, the measurement is performed with a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene.

  The number average molecular weight of the vinyl polymer in the present invention is not particularly limited, but when measured by gel permeation chromatography, a range of 500 to 1,000,000 is preferable, and 1,000 to 100,000 is more preferable. 5,000 to 50,000 are more preferable.

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

Controlled radical polymerization The radical polymerization method is a “general radical polymerization method” in which a monomer having a specific functional group and a vinyl monomer are simply copolymerized using an azo compound or a peroxide as a polymerization initiator. Can be classified into “controlled radical polymerization methods” 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 “living radical polymerization method” in which a polymer having a molecular weight almost as designed can be 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 scavenger such as a nitroxide compound, and “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 scavenger 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 radical initiator is appropriate for 1 mol of 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 shown in the above figure, 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 scavenger 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, a more preferred atom transfer radical polymerization method 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 1 -C (H) (X}} ) -CO 2 R 2, R 1 -C (CH 3) (X) -CO 2 R 2, R 1 -C (H) (X) -C (O) R 2 _{^{, R 1 -C (CH 3)}} (X) -C (O) R 2,
(Wherein R ¹ and R ² 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 ¹ —C ₆ H ₄ —SO ₂ X
(Wherein R ¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and X is chlorine, bromine, or iodine).

  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 4 R 5 C (X)} -R 6 -R 7 -C (R 3) = CH 2 (2)
(Wherein R ³ is hydrogen or a methyl group, R ⁴ and R ⁵ 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. R ⁶ is —C (O) O— (ester group), —C (O) — (keto group), or o-, m-, p-phenylene group, R ⁷ is a direct bond, or carbon number 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 ⁴ and R ⁵ include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, pentyl group, hexyl group and the like. R ⁴ and R ⁵ 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 each of 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 each of 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 each of 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 3}} ) -R 7 -C (R 4) (X) -R 8 -R 5 (3)
(Wherein R ³ , R ⁴ , R ⁵ , R ⁷ and X are the same as above, R ⁸ is a direct bond, —C (O) O— (ester group), —C (O) — (keto group) Or an o-, m-, p-phenylene group)
R ⁷ is a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds), and 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 or a phenylene group as R ⁸ , and a direct bond may be used. When R ⁷ is not a direct bond, R ⁸ 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).

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 4 R 5 C (X)} -R 6 -R 7 -C (H) (R 3) CH 2 - [Si (R 9) 2-b (Y) b O] m -Si (R 10) 3- _a (Y) _a (4)
(In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and X are the same as above, and R ⁹ and R ¹⁰ are all alkyl groups, aryl groups, aralkyl groups having 1 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 or different). Represents an organosiloxy group, and when two or more R ⁹ or R ¹⁰ are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and Y represents two or more When present, 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 from 0 to 19. (Provided that a + mb ≧ 1)
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, n is an integer of 0-20)
_{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 10) 3-a (}} Y) a Si- [OSi (R 9) 2-b (Y) b] m -CH 2 -C (H) (R 3) -R 7 -C (R 4) ( X) -R < ⁸ > -R < ⁵ > (5)
(Wherein R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , 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)
(In the formula, 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 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)
(In the formula, 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 epoxy group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.

(In the formula, 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. More preferable examples include a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. is there. When a copper compound is used, 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity A ligand such as a polyamine is added. A preferred ligand is a nitrogen-containing compound, a more preferred ligand is a chelate-type nitrogen-containing compound, and a more preferred ligand is N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine. It is. A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. 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, and these can be used alone or in admixture of two or more.

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

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

<Functional group>
Number of crosslinkable silyl groups The number of crosslinkable silyl groups in the vinyl polymer is not particularly limited, but from the viewpoint of the curability of the composition and the physical properties of the cured product, it is preferable to have one or more on average. More preferably, they are 1.1 or more and 4.0 or less, More preferably, they are 1.2 or more and 3.5 or less.

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

  A method for producing a vinyl polymer having at least one crosslinkable silyl group at its molecular terminal, in particular, a (meth) acrylic polymer is disclosed in Japanese Patent Publication No. 3-14068, Japanese Patent Publication No. 4-55444, No. 6-211922 and the like. However, since these methods are free radical polymerization methods using the above-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. It is preferable.

These functional groups will be described below.
The crosslinking silyl group of the crosslinkable silyl group present invention, the general formula (6);
^{_{- [Si (R 9) 2}} -b (Y) b O] m -Si (R 10) 3-a (Y) a (6)
{In the formula, R ⁹ and R ¹⁰ are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups 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's may be the same or different, and represents a triorganosiloxy group represented by R ⁹ or When two or more R ¹⁰ 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. } Is represented.

  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 fewer 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 (7)
-Si (R ¹⁰ ) _3-a (Y) _a (7)
A crosslinkable silyl group represented by the formula (wherein R ¹⁰ , Y and a are the same as described above) is preferable because it is easily available.

  Although not particularly limited, a is preferably 2 or more in view 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 three (for example, a trimethoxy functional group).

  In addition, those having 3 a (for example, trimethoxy functional group) are faster in curing than those having 2 (for example, dimethoxy functional group), but those having 2 in terms of storage stability and mechanical properties (elongation, etc.). May be better. In order to balance curability and physical properties, two (for example, a dimethoxy functional group) and three (for example, a 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.

The following method of introducing the crosslinkable silyl group, will be described method of introducing the crosslinkable silyl group into the vinyl polymer of the present invention, 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 A method of reacting; and the like.

  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)
(In the formula, R ¹⁴ represents hydrogen or a methyl group, R ¹⁵ represents —C (O) O—, or o-, m-, p-phenylene group, R ¹⁶ represents a direct bond, 20 represents a divalent organic group having 20 and may contain one or more ether bonds, and 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 in which halogen is substituted 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 is 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). .

  The method for synthesizing a vinyl polymer having at least one highly reactive carbon-halogen bond 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 in which an alkenyl group-containing carboxylic acid such as acrylic acid is reacted in the presence of an acid catalyst;
In the present invention, when a halogen is not directly involved in a method for introducing an alkenyl group such as (Aa) and (Ab), it is preferable to synthesize a vinyl polymer using a living radical polymerization method. In view of easier control, the method (Ab) is more preferable.

  When an alkenyl group is introduced 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. In view of easier control, the method (Af) is more preferable.

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 9) 2}} -b (Y) b O] m -Si (R 10) 3-a (Y) a (13)
{In the formula, R ⁹ and R ¹⁰ are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups 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's may be the same or different, and represents a triorganosiloxy group represented by R ⁹ or When two or more R ¹⁰ 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 ¹⁰ ) _3-a (Y) _a (14)
A compound having a crosslinkable group represented by the formula (wherein R ¹⁰ , Y and a are the same as described above) is preferable from the viewpoint of easy availability.

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 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 described 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, for example, JP-A-6-116312.

  (Bf) Hydrolysis of a vinyl polymer having at least one highly reactive carbon-halogen bond or reaction with a hydroxyl group-containing compound by a method such 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 the halogen.
^{M + C - (R 18)} (R 19) -R 20 -OH (16)
(In the formula, R ¹⁸ , R ¹⁹ and R ²⁰ 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)
(Wherein 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. Etc.

  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 halogen in 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 9) 2-b (Y) b O] m -Si (R 10) 3-a (Y) a (20)
(In the formula, R ⁹ , R ¹⁰ , R ¹⁴ , R ¹⁵ , Y, a, b and m are the same as above. R ²³ is a direct bond or a divalent organic group having 1 to 20 carbon atoms. The above ether bond may be included.)

  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 9) 2-b (Y) b O] m -Si (R 10) _3-a (Y) _a (21)
(In the formula, R ⁹ , R ¹⁰ , 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.
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.

<< About polyether polymer (II) having 1.2 or less crosslinkable silyl groups on average >>
<Main chain>
In the curable composition of the present invention, the main chain structure of the polyether polymer (II) having 1.2 or less crosslinkable silyl groups on average has a general formula — (— R—O—) _n. −
A polyoxyalkylene represented by the formula (wherein R is a divalent alkylene group having 1 to 4 carbon atoms) is preferred. Specific examples include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxyhexylene, polyoxytetramethylene, and copolymers thereof. Of these, polyoxypropylene is preferred from the viewpoint of easy availability. The polyoxypropylene may be linear or branched, or a mixture thereof. Of these, polyoxypropylene diol, polyoxypropylene triol, and mixtures thereof are particularly preferable. Further, other monomer units may be contained, but the monomer unit represented by the above formula is preferably present in the polymer in an amount of 50% by weight or more, preferably 80% by weight or more.

  The main chain may or may not contain a urethane bond or urea bond.

  The molecular structure of the polyether polymer (II) of the present invention varies depending on the intended use and intended properties, and the method described in JP-A-63-112642 can be used. From the viewpoint of achieving both low viscosity (workability) of the curable composition and low modulus and high elongation of the cured product obtained by curing the curable composition, the molecular weight distribution (Mw / Mn) is small and the functional group is low. It is preferable that it is an oxyalkylene polymer. Specifically, the number average molecular weight is preferably from 300 to 12,000, and more preferably from 300 to 8,000. Further, Mw / Mn is preferably 1.6 or less, and more preferably 1.5 or less. Such a polyoxyalkylene is difficult to obtain by a normal polymerization method (anionic polymerization method using caustic alkali) or a chain extension reaction method of this polymer. For example, a cesium metal catalyst, JP-A 61-197631. Porphyrin / aluminum complex catalysts exemplified in JP-A Nos. 61-215622, 61-215623 and 61-218632, JP-B-46-27250, JP-B-59-15336, etc. It can be obtained by a method using a double metal cyanide complex catalyst exemplified, a catalyst comprising a polyphosphazene salt exemplified in JP-A-10-273512, and the like. Practically, a method using a double metal cyanide complex catalyst is preferable.

<Crosslinkable silyl group>
In the polyether polymer (II) having an average of 1.2 or less crosslinkable silyl groups of the present invention, the bond between the crosslinkable silyl group and the polyether portion has hydrolysis resistance. Therefore, an alkylene group such as trimethylene and tetramethylene is preferred so 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.

Number and position of crosslinkable silyl groups The average number of crosslinkable silyl groups in the polyether polymer (II) in the present invention is 1.2 or less. On the other hand, if the number of silyl groups is too small, the effects of the present invention are not exhibited. Therefore, the number is preferably at least 0.1, more preferably 0.3, and more preferably 0.5. Is more preferable. It is preferably at the end of the molecular chain. Further, the crosslinkable silyl group of the polyether polymer (II) is preferably only at one terminal in the main chain and not at the other terminal, but it is 1.2 or less on average. If it is, it will not specifically limit.

Method for Introducing Crosslinkable Silyl Group A polyether polymer (II) having an average of 1.2 or less crosslinkable silyl groups in the present invention is obtained by adding a crosslinkable silyl group to a polyether polymer having a functional group. It is preferable to obtain by introduction.

  The introduction of the crosslinkable silyl group may be performed by a known method. That is, for example, the following method can be 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, JP-A-11-60723 is disclosed. It is described in.

  (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 the Y ′ functional group include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, and γ-aminopropyltriethoxysilane. Amino group-containing silanes; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane; γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxy Cyclohexyl) epoxy silanes such as ethyltrimethoxysilane; vinyl type unsaturated group-containing silanes such as vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane; - Chlorine atom-containing silanes such as ropropyltrimethoxysilane; Isocyanate-containing silanes such as γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropyltrimethoxysilane; methyldimethoxysilane Specific examples include hydrosilanes such as trimethoxysilane, methyldiethoxysilane, and triethoxysilane, but are not limited thereto.

  When introducing a crosslinkable silyl group, a polyether polymer having only one functional group in the molecule is used, and the functional group is reacted with a compound having a crosslinkable silyl group in an equivalent amount or a smaller amount. A method of obtaining a polyether polymer having an average of 1.2 or less crosslinkable silyl groups and a polyether polymer having an average of one or more functional groups in the molecule, There is a method in which a polyether polymer having an average of 1.2 or less crosslinkable silyl groups is obtained by reacting a compound having a crosslinkable silyl group smaller than the functional group.

<Use amount of polyether polymer (II) having 1.2 or less crosslinkable silyl groups on average>
The average amount of the polyether polymer (II) having 1.2 or less crosslinkable silyl groups is 1.2 or less on the average with respect to 100 parts by weight of the vinyl polymer (I). The polyether polymer (II) having a crosslinkable silyl group is preferably 1 part by weight or more and 200 parts or less, more preferably 3 parts by weight or more and 100 parts by weight or less, still more preferably 5 parts by weight or more and 80 parts by weight or less.

<< About a polyether polymer (III) having at least 1.2 crosslinkable functional groups >>
<Main chain>
In the curable composition of the present invention, as the polyether polymer (III) having at least 1.2 or more crosslinkable functional groups, a polyether having 1.2 or less crosslinkable silyl groups on average is used. As with the main chain structure of the polymer (II), the general formula — (— R—O—) _n —
A polyoxyalkylene represented by the formula (wherein R is a divalent alkylene group having 1 to 4 carbon atoms) is preferred. Specifically, it can be exemplified as described in the polyether polymer (II) having 1.2 or less crosslinkable silyl groups on average. Further, other monomer units may be contained, but the monomer unit represented by the above formula is preferably present in the polymer in an amount of 50% by weight or more, preferably 80% by weight or more.

  The main chain may or may not contain a urethane bond or urea bond.

  The molecular structure of the polyether polymer (III) of the present invention varies depending on the intended use and intended properties, and the method described in JP-A-63-112642 can be used. An oxyalkylene polymer having a high molecular weight and a small molecular weight distribution (Mw / Mn) from the viewpoint of achieving both low viscosity (workability) of a curable composition and low modulus and high elongation of a cured product obtained by curing the curable composition. It is preferable that Specifically, the number average molecular weight is preferably 5,000 or more and 50,000 or less, and more preferably 8,000 or more and 20,000 or less. Further, Mw / Mn is preferably 1.6 or less, and more preferably 1.5 or less. The method for producing such a polyoxyalkylene is the same as that described for the polyether polymer (II) having 1.2 or less crosslinkable silyl groups on average.

<Crosslinkable silyl group>
In the polyether polymer (III) having at least 1.2 crosslinkable functional groups of the present invention, the bond between the crosslinkable silyl group and the polyether portion has hydrolysis resistance. An alkylene group such as trimethylene and tetramethylene is preferred so 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.

Number and position of crosslinkable silyl groups The number of crosslinkable silyl groups in the polyether-based polymer (III) in the present invention is preferably more than 1.2 in view of the curability of the composition. The number is preferably 2 or more and 4.0 or less, and more preferably 1.5 to 2.5 or less. The crosslinkable silyl group of the polyether polymer (III) is preferably at the end of the molecular chain from the viewpoint of rubber elasticity of the cured product, and more preferably has functional groups at both ends of the polymer. It is.

Method for Introducing Crosslinkable Silyl Group The polyether polymer (III) having at least 1.2 crosslinkable functional groups of the present invention introduces a crosslinkable silyl group into the polyether polymer having a functional group. Is preferably obtained.

  The introduction of the crosslinkable silyl group may be performed by a known method. Specifically, the method described in the polyether polymer (II) having 1.2 or less crosslinkable silyl groups on average can be mentioned.

<Use amount of polyether polymer (III) having at least 1.2 crosslinkable functional groups>
The amount of the polyether polymer (III) having at least 1.2 crosslinkable functional groups is such that the mixing ratio of the vinyl polymer (I) and the polyether polymer (III) is by weight. The range of 100/1 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. If the amount of the vinyl polymer (I) is too small, the weather resistance and heat resistance may be lowered.

<< Curable composition >>
Some curable compositions of the present invention require a curing catalyst or a curing agent. Various compounding agents may be added according to the intended physical properties.

<Curing catalyst and curing agent>
The polymer having a crosslinkable silyl group is crosslinked and cured by forming a siloxane bond in the presence or absence of various conventionally known condensation catalysts. 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 a condensation catalyst include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutylmalate, dibutyltin diester. Isooctylmalate, dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, dioctyltin diisooctylmalate, etc. Tetravalent tin compounds; divalent tin compounds such as tin octylate, tin naphthenate and tin stearate; monobutyltin compounds such as monobutyltin trisoctoate and monobutyltin triisopropoxide; Monoalkyltins such as nooctyltin compounds; titanates such as tetrabutyl titanate and tetrapropyl titanate; 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, nickel carboxylate, carboxylic acid Carboxylic acids such as cobalt, zinc carboxylate and aluminum carboxylate (2-ethylhexanoic acid, neodecanoic acid, versatic acid, oleic acid, naphthenic acid, etc.) Metal salts, or reactants and mixtures of these with amine compounds such as laurylamine described below; chelating compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; methylamine, ethylamine, propylamine, isopropylamine, Aliphatic primary amines such as butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine, stearylamine, cyclohexylamine; dimethylamine, diethylamine, dipropylamine , Diisopropylamine, dibutylamine, diamylamine, dioctylamine, di (2-ethylhexyl) amine, didecylamine, dilaurylamine, dicetyla Aliphatic secondary amines such as amine, distearylamine, methylstearylamine, ethylstearylamine, butylstearylamine; aliphatic tertiary amines such as triamylamine, trihexylamine, trioctylamine; triallylamine, oleylamine Aliphatic unsaturated amines such as lauryl aniline, stearyl aniline, triphenylamine and the like; and other amines such as monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, Oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, ethylenediamine, hexamethylenediamine, triethylenediamine, guanidine, diphen Luguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) Amine compounds such as, or salts of these amine compounds with carboxylic acids, etc .; reactants and mixtures of amine compounds and organotin compounds such as laurylamine and tin octylate reactants or mixtures; excess Low molecular weight polyamide resin obtained from polyamine and polybasic acid; reaction product of excess polyamine and epoxy compound; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane , Γ-aminopropylmethyldimethoxysilane, γ-aminopro Rumethyldiethoxysilane, N- (β-aminoethyl) aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, N- (β-aminoethyl) aminopropyltriethoxysilane, N- (Β-aminoethyl) aminopropylmethyldiethoxysilane, N- (β-aminoethyl) aminopropyltriisopropoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- Examples thereof include benzyl-γ-aminopropyltrimethoxysilane and N-vinylbenzyl-γ-aminopropyltriethoxysilane. Silanol condensation 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., which are derivatives of these modified Examples of the catalyst include further known silanol condensation catalysts such as other acidic catalysts and basic catalysts.

  These catalysts may be used alone or in combination of two or more. The amount of the condensation catalyst is preferably about 0.1 to 20 parts, more preferably 1 to 10 parts, relative to 100 parts (parts by weight, the same applies hereinafter) of the vinyl polymer having at least one crosslinkable silyl group. . If the amount of the silanol condensation catalyst is less than 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 becomes too short, which is preferable from the viewpoint of workability. Absent. Although not particularly limited, it is preferable to use a tin-based curing catalyst in order to control curability.

  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. . This amino group-containing silane coupling agent is a group having a silicon atom to which a hydrolyzable group is bonded (hereinafter referred to as a hydrolyzable silicon group) and an amino group, and the groups already exemplified as this 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 organic polymer of the vinyl polymer (I). 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 become too short, which is not preferable from the viewpoint of workability.

  These amine compounds may be used alone or in combination of two or more.

Furthermore, the following general formula (37)
R ⁴⁹ _a Si (OR ⁵⁰ ) _4-a (37)
(In the formula, R ⁴⁹ and R ⁵⁰ are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Furthermore, a is 0, 1, 2, or 3.) A silicon compound having no amino group or silanol group represented by the above may be added as a promoter.

Examples of the silicon compound include, but are not limited to, R ^{49 in} the general formula (37) such as phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and triphenylmethoxysilane. Is preferably an aryl group having 6 to 20 carbon atoms because it has a large effect of accelerating the curing reaction of the composition. 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, relative to 100 parts of the vinyl polymer. 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.

  The type and amount of the curing catalyst / curing agent can be selected according to the type of Y and the number of a in the vinyl polymer represented by the general formula (1) or (6) of the present invention. The curability and mechanical properties of the present invention can be controlled according to the purpose and application. When Y is an alkoxy group, the smaller 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.

<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 or the like fluctuates due to an external force, so that the risk of the sealing material peeling off from the adherend such as a siding board can be further reduced. 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 silane coupling agents include amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurates, halogen and other functional groups such as halogens. Specific examples thereof As γ-isocyanatepropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatepropylmethyldimethoxysilane and other isocyanate group-containing silanes; γ-aminopropyltrimethoxysilane , Γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) amino Propyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ -(2-aminoethyl) aminopropyltriisopropoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl -Amino group-containing silanes such as γ-aminopropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, etc. Γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Epoxy group-containing silanes such as silane and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- Carboxysilanes such as (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyltrieth Examples thereof include vinyl unsaturated group-containing silanes such as xysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate. Further, 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 in the present invention is usually used in the range of 0.1 to 20 parts per 100 parts of the crosslinkable silyl group-containing vinyl polymer. 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.

  Specific examples other than the silane coupling agent are not particularly limited, and examples thereof include epoxy resins, phenol resins, sulfur, alkyl titanates, and aromatic polyisocyanates.

  The adhesiveness-imparting agent may be used alone or in combination of two or more. By adding these adhesion-imparting agents, the adhesion to the adherend can be improved. 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 depending on the type of Y and the number of a in the vinyl polymer represented by the general formula (1) or (6) of the present invention. It is possible to control the curability and mechanical properties of the present invention according to the application. In particular, care must be taken in selecting it 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, Phthalate esters, such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate, etc .; , Non-aromatic dibasic acid esters such as dioctyl sebacate, dibutyl sebacate and isodecyl succinate; aliphatic esters such as butyl oleate and methyl acetylricinoleate; diethylene glycol dibenzoate, triethylene glycol dibenzoate, penta Esters of polyalkylene glycols such as erythritol esters; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Polystyrene and poly-α-methylstyrene Polystyrene, polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; polyethylene glycol, polypropylene glycol, poly Polyether polyols such as tetramethylene glycol and polyethers such as derivatives obtained by converting hydroxyl groups of these polyether polyols to ester groups, ether groups, etc .; epoxy plasticizers such as epoxidized soybean oil and benzyl epoxy stearate; sebacic acid , Dibasic acids such as adipic acid, azelaic acid, phthalic acid and the like and ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, etc. Examples thereof include polyester plasticizers obtained from coal; vinyl polymers obtained by polymerizing vinyl monomers such as acrylic plasticizers by various methods.

  Among them, the polymer plasticizer which is a polymer having a number average molecular weight of 500 to 15000 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, Mechanical properties such as 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. The drying property (also called paintability) when a paint is applied can be improved. 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 500-15000 above, Preferably it is 800-10000, More preferably, it is 1000-8000. If the molecular weight is too low, the plasticizer flows out over time due to heat and rain, the initial physical properties cannot be maintained over a long period of time, and the alkyd paintability cannot be improved. Moreover, when molecular weight is too high, a viscosity will become high and workability | operativity will worsen.

  Of these polymer plasticizers, those compatible with the vinyl polymer are preferred. Of these, vinyl polymers are preferred from the viewpoints of compatibility, weather resistance, and heat resistance. Among the vinyl polymers, (meth) acrylic polymers are preferable, and acrylic polymers are more preferable. Examples of the method for synthesizing 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 limited to, Toagosei UP series and the like (see the Industrial Materials October 1999 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 and is preferably less than 1.8. 1.7 or less is more preferable, 1.6 or less is still more preferable, 1.5 or less is more preferable, 1.4 or less is especially preferable, and 1.3 or less is the most preferable.

  The plasticizer containing the above-mentioned polymer plasticizer may be used alone or in combination of two or more, but is not necessarily required. Further, if necessary, a high molecular plasticizer may be used, and a low molecular plasticizer may be further used in a range that does not adversely affect the physical properties.

  These plasticizers can also be blended at the time of polymer production.

  Although the usage-amount in the case of using a plasticizer is not limited, It is 5-150 weight part with respect to 100 weight part of vinyl polymers, Preferably it is 10-120 weight part, More preferably, it is 20-100 weight part. If it is less than 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product will 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, etc.), reinforcing filler such as carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, Fillers such as clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, red pepper, fine aluminum powder, flint powder, zinc oxide, activated zinc white, zinc dust, zinc carbonate and shirasu balloon; asbestos, Glass fiber and glass filament, carbon fiber, Kevlar fiber, polyethylene fiber They include fibrous fillers such as is.

  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 strength using these fillers, fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, crystalline silica, molten A filler selected from silica, calcined clay, clay and activated zinc white can be added. Among them, the specific surface area (according to BET adsorption method) of ^{50 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, but are those of Nippon Aerosil Co., Ltd., which is one of fumed silica, and Nippon Silica Co., Ltd., which is one of precipitated silica. Nipsil etc. are mentioned.

  In addition, 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.

  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, adhesiveness and weather resistance of the cured product is expected, the specific surface area value is 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 ^{50m 2 / g, 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 reduced or when the purpose is only to increase the viscosity.

  In addition, the value of the specific surface area means a measurement value by an air permeation method (a method for obtaining a specific surface area from air permeability with respect to a powder packed bed) performed according to JIS K 5101 as a measurement 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. In particular but not limited, for example, if the value of the specific surface area as required combine heavy calcium and colloidal calcium carbonate of more than 1.5 m 2 / ^g, suppressing the increase of viscosity of the formulation in moderation, the cured product The effect of improving the breaking strength, breaking elongation, adhesiveness and weathering adhesion can be greatly expected.

  When the filler is used, it is preferable to use the filler in the range of 5 to 1000 parts by weight and preferably in the range of 20 to 500 parts by weight with respect to 100 parts by weight of the vinyl polymer. It is more preferable to use in the range of 40 to 300 parts by weight. If 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 if it exceeds 1000 parts by weight, the work of the curable composition May decrease. A filler may be used independently and may be used together 2 or more types.

<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 balloons include silicate balloons and non-silicate balloons, silicate balloons include shirasu balloons, perlite, glass balloons, silica balloons, fly ash balloons, etc., and non-silicate balloons include alumina. Examples include balloons, zirconia balloons, and carbon balloons. Specific examples of these inorganic balloons include Shirasu balloons made by Idichi Kasei Co., Ltd., Sankilite made by Sanki Kogyo Co., Ltd., Nippon Glass Co., Ltd., Caloon made by Sumitomo 3M, Cellstar Z-28 made by Sumitomo 3M, and MICRO made by EMERSON & CUMING. BALLON, PELTSBURGE CORNING's CELAMIC GLASSMMODULES, 3M's GLASS BUBBLES, Asahi Glass's Q-CEL, Taiheiyo Cement's E-SPHERES, Fly Ash Balloon's, PERAMARKET's CEROSPHERES S. FILLITE manufactured by A, BW manufactured by Showa Denko as an alumina balloon, HOLLOW ZIRCONIUM SPHEES manufactured by ZIRCOA as a zirconia balloon, clecas sphere manufactured by Kureha Chemical, and CARBOS sphere manufactured by GENERAL TECHNOLOGIES as a carbon balloon are commercially available.

  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 made by Nippon Filament, Matsumoto Microsphere made by Matsumoto Yushi Seiyaku, DYLITE EXPANDABLE POLYSTYRENE made by ARCOPOLYMERS as polystyrene balloon, EXPANDABLE POLYSTYRENE BEADS made by BASF WYANDOTE, Bridge-type styrene - SX863 is acrylic acid balloon made by Japan Synthetic Rubber (P) are commercially available.

  The balloons may be used alone or in combination of two or more. In order to improve the dispersibility and the workability of the compound by using fatty acid, fatty acid ester, rosin, rosin 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 used for weight reduction and cost reduction without impairing flexibility and elongation / strength among physical properties when the compound is cured.

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

<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

A chain polysiloxane compound containing a silanol group such as

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,

A compound having a silanol group bonded to the polysilane main chain terminal, such as

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, the compound represented by the following general formula (45) is preferable.
(R ⁵⁸ ) ₃ SiOH (45)
(In the formula, R ⁵⁸ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. The plurality of R ⁵⁸ may be the same or different.)
^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.

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 the crosslinkable silyl group of the vinyl polymer or the siloxane bond formed by the crosslinking, thereby reducing the number of crosslinking points and making the cured product flexible. It is estimated that Moreover, the compound which can produce | generate the compound which has one silanol group in a molecule | numerator by reacting with water | moisture content which is one of the components of this invention is although it does not specifically limit, In the molecule | numerator produced | generated by reacting with a water | moisture content The compound (hydrolysis product) having one silanol group is preferably a compound represented by the general formula (45). For example, although not particularly limited, the following compounds may be mentioned in addition to the compound represented by the general formula (46) as described later.

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 of glycerol Chirushiriru) iodide, tris (trimethylsilyl) ated trimethylolpropane, tris (trimethylsilyl) ated pentaerythritol, pentaerythritol tetra (trimethylsilyl) ated _{product, (CH 3) 3 SiNHSi (} CH 3) 3, (CH 3) 3 SiNSi (CH ₃ ) ₂ ,

However, from the amount of silanol groups contained in the hydrolysis product, (CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ is particularly preferable.

Furthermore, the compound that can generate a compound having one silanol group in the molecule by reacting with moisture, which is one of the components of the present invention, is not particularly limited. ) Is preferred.
((R ⁵⁸ ) ₃ SiO) _n R ⁵⁹ (46)
(In the formula, R ⁵⁸ is the same as described above. N represents a positive number, and R ⁵⁹ represents a group obtained by removing some or all of the active hydrogen from the active hydrogen-containing 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 R ⁵⁹ 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.

The 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 Silylation product, triethylsilylation product of 2-ethylhexanol, tris (trimethylsilyl) ation product of glycerin, tris (trimethylsilyl) ation product of trimethylolpropane, tris (trimethylsilyl) ation product of pentaerythritol, tetra (trimethylsilyl) ation product of pentaerythritol, etc. However, it is not limited to these. 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
(In the formula, 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 1-6, s × t is 5 or more, Z is a 1-6 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 generate a compound having one silanol group in the molecule by reacting with moisture, the active hydrogen-containing compound generated after hydrolysis in that it does not adversely affect storage stability, weather resistance, etc. Phenols, acid amides, and alcohols are preferable, and phenols and alcohols in which the active hydrogen-containing compound is a hydroxyl group 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 or the siloxane bond formed by crosslinking as described above, thereby reducing the number of crosslinking points. It is presumed that it is reduced and the cured product is given flexibility.

  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 vinyl polymer. If the amount is less than 0.1 parts by weight, the effect of addition does not appear. If the amount exceeds 50 parts by weight, the crosslinking becomes insufficient, and the strength and gel fraction of the cured product are too low.

  Moreover, the time which adds a silanol containing compound to a vinyl polymer is not specifically limited, You may add at the time of manufacture of a vinyl 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.

  The sagging preventing agent is not particularly limited, and examples thereof include polyamide waxes, hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more.

<Photo-curing substance>
You may add a photocurable substance to the curable composition of this invention as needed. The photo-curing substance is a substance in which the molecular structure undergoes a chemical change in a short time due to 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 and azido resins.

The unsaturated acrylic compound is a monomer, oligomer or mixture thereof having an unsaturated group represented by the following general formula (47).
^{_{CH 2 = CHR 62 CO (O}} ) - (47)
In the formula, ^R62 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.

  Specific examples of unsaturated acrylic compounds include (meth) acrylic acid esters of low molecular weight alcohols such as ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, and neopentyl alcohol; bisphenol A, isocyanuric acid, and the like. (Meth) acrylic acid esters of alcohols obtained by modifying acids or the above low molecular weight alcohols with ethylene oxide or propylene oxide; polyether polyols having a main chain as a polyether and having a hydroxyl group at the terminal, in a polyol having a main chain as a polyether A polymer polyol obtained by radical polymerization of a vinyl monomer, a polyester polyol having a main chain of polyester and a hydroxyl group at the terminal, a main chain of a vinyl or (meth) acrylic polymer, and a hydroxyl group in the main chain (Meth) acrylic acid esters such as polyols having epoxy; epoxy acrylate oligomers obtained by reacting bisphenol A type or novolak type epoxy resins with (meth) acrylic acid; containing polyols, polyisocyanates and hydroxyl groups ( Examples thereof include urethane acrylate oligomers having a urethane bond and a (meth) acryl group in a molecular chain obtained by reacting meth) 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.

  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 vinyl polymer. 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 oxidative curable substance in the present invention is a substance that can be cured by contact with air, and more specifically, has a property of being cured by reacting with oxygen in the air. A typical air oxidative curable substance can be cured by, for example, standing in air indoors for 1 day.

  Examples of the air oxidative curable substance include drying oils such as paulownia oil and linseed oil; various alkyd resins obtained by modifying these drying oils; acrylic polymers, epoxy resins and silicone resins modified with drying oils; 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymers and copolymers, and various modified products of the polymers and copolymers (maleinized modified products, boiled oil modified products, etc.) A specific example is given. 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 is preferably added in an amount of 0.01 to 20 parts by weight with respect to 100 parts by weight of the vinyl polymer. 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 CMC Chemical, and the like. Although various things are mentioned, it is not necessarily limited to these.

  For example, phosphorus antioxidants such as thioethers such as MARK PEP-36 and MARK AO-23 (all manufactured by Adeka Gas Chemical Co., Ltd.), Irgafos 38, Irgafos 168, Irgafos P-EPQ (all manufactured by Ciba Geigy Japan) Etc. 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 (4methyl-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-4hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (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-t-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-trimethyl -2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate 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-hydroxyphenyl) Benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chloro Benzotriazole, 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-pentamethyl) -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 Also 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 Adeka Argus Chemical), IRGANOX-245, IRGANOX-259, IRGANOX-565, IRGANOX-1010, IRGANOX-1024, IRG NOX-1035, IRGANOX-1076, IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330, IRGANOX-1425WL (all of which are manufactured by Ciba Geigy Japan), Sumizer GM, Sumilizer GA-80 (all of which are manufactured by Sumitomo Chemical), etc. However, it is not limited to these.

  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 (all of which are manufactured by Ciba Geigy Japan, Inc.) 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 vinyl polymers. 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.

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

  Although not particularly limited, among the light stabilizers, an ultraviolet absorber is preferable, and specifically, Tinuvin P, Tinuvin 234, Tinuvin 320, Tinuvin 326, Tinuvin 327, Tinuvin 329, Tinuvin 213 (all of these are manufactured by Ciba Geigy Japan) Benzotriazole compounds such as TINUVIN 1577, benzophenone compounds such as CHIMASSORB 81, and benzoate compounds such as TINUVIN 120 (manufactured by Ciba Geigy Japan).

  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 Geigy Japan), MARK LA-52, MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-67 63, MARK LA-68, MARK LA-82, MARK LA-87 (all manufactured by Adeka Gas Chemical), Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS -1114, Sanol LS-744, Sanol LS-440 (all of which are manufactured by Sankyo) and the like, but are not limited thereto.

  Furthermore, since the combination of the ultraviolet absorber and the hindered amine compound may exhibit more effect, it is not particularly limited but may be used in combination, and it is preferable to use in combination.

  The light stabilizer may be used in combination with the above-described antioxidant, and it is particularly preferable because the effect is further exhibited and the weather resistance may be improved. Tinuvin C353, Tinuvin B75 (all of which are manufactured by Ciba Geigy Japan, Inc.) in which a light stabilizer and an antioxidant are mixed in advance may be used.

  The amount of the light stabilizer used is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl polymer. 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.

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, for example, flame retardants, curability modifiers, anti-aging agents, radical inhibitors, UV absorbers, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers , Lubricants, pigments, foaming agents, photocurable resins, 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, the specifications of JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, and JP-A-64-22904. Yes.

  The curable composition of the present invention may be prepared as a one-component type in which all the components are pre-blended and stored in a sealed state and cured by moisture in the air after construction. Components such as an agent and water may be blended and adjusted as a two-component type in which the blending material and the polymer composition are mixed before use. 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 easy to cope with the increase in the number of colors requested from the market, and is preferable for low-rise buildings. 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.

<< cured product >>
<Application>
The curable composition of the present invention is not limited, but is a sealing material such as an elastic sealing material for construction and a sealing material for double-glazed glass, and electrical / electronic component materials such as a solar cell back surface sealing material, insulation for electric wires and cables. Electrical insulation materials such as coating materials, adhesives, adhesives, elastic adhesives, paints, powder paints, coating materials, foams, potting agents for electrical and electronic equipment, films, gaskets, casting materials, various molding materials, and It can be used for various applications such as rustproofing and waterproofing sealing materials for meshed glass and laminated glass end faces (cut parts), liquid sealants used in automobile parts, electrical parts, various machine parts, and the like.

  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 examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. In this example, “triamine” refers to pentamethyldiethylenetriamine.

  In the following 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.

(Production Example 1)
(Synthesis of carboxylate having alkenyl group)
10-Undecenoic acid (150 g, 0.814 mol) and potassium-tert-butoxide (91.3 g, 0.814 mol) were added to methanol (250 mL), and the mixture was stirred at 0 ° C. Volatile components were distilled off under reduced pressure to obtain potassium undecenoate represented by the following formula.
_{CH 2 = CH- (CH 2)} 8 -CO 2 - + K
(BA semi-batch polymerization-1 kg)

  In a 2 L glass reaction vessel, cuprous bromide (8.39 g, 0.0585 mol) and acetonitrile (112 mL) were added under a nitrogen atmosphere and heated at 70 ° C. for 60 minutes. To this was added butyl acrylate (224 mL, 1.56 mol), diethyl 2,5-dibromoadipate (17.6 g, 0.0488 mol), and the mixture was further stirred for 30 minutes. To this was added triamine (0.41 mL, 1.95 mmol) to initiate polymerization. Thereafter, the reaction solution was sampled and triamine (5.66 mL, 27.1 mmol) was added while monitoring the reaction, and butyl acrylate (895 mL, 6.24 mol) was added over 140 minutes 55 minutes after the start of the reaction. added. Heating was continued for an additional 170 minutes after the addition of butyl acrylate. At this time, the consumption rate of butyl acrylate was 92.9% from GC measurement. The mixture was diluted with toluene and treated with activated alumina, and then the volatile component was heated and distilled off under reduced pressure to obtain a colorless transparent polymer [1]. The number average molecular weight of the obtained polymer [1] was 21,000, and the molecular weight distribution was 1.1.

The polymer [1] (0.35 kg), the potassium undecenoate (8.85 g) and 350 mL of dimethylacetamide were added to a glass container, and the mixture was heated and stirred at 70 ° C. for 3 hours in a nitrogen atmosphere. Volatiles of the reaction solution were removed by heating under reduced pressure, diluted with toluene, and filtered. Volatiles were removed from the filtrate by heating under reduced pressure, and the solution was concentrated. 20 wt% of aluminum silicate (Kyowa Kagaku, Kyoward 700PEL) was added to the polymer, and the mixture was heated and stirred at 100 ° C for 3 hours. The reaction solution was diluted with toluene and filtered, and the volatile component was distilled off from the filtrate under reduced pressure heating to obtain an alkenyl group-terminated polymer (polymer [2]). ¹ H-NMR measurement alkenyl groups introduced per polymer molecule was 1.9.

In a 1 L pressure-resistant reactor, polymer [2] (350 g), trimethoxysilane (15.0 mL), methyl orthoformate (3.6 mL), and 1,1,3,3-tetramethyl-1 of zerovalent platinum , 3-Divinyldisiloxane complex was charged. However, the platinum catalyst was used in an amount of 5 × 10 −4 equivalent in molar ratio to the alkenyl group of the polymer. After the reaction mixture was heated and reacted, the volatile content of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated vinyl polymer (polymer [P1]). The number average molecular weight of the obtained polymer was 26000, and the molecular weight distribution was 1.2. When the average number of silyl groups introduced per molecule of the polymer was determined by ¹ H NMR analysis, it was 1.4.

Similarly, the polymer [2], trimethoxysilane, methyl orthoformate, and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zerovalent platinum are charged into a 1 L pressure-resistant reaction vessel, After sufficiently heating and reacting, the volatile content of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated vinyl polymer (polymer [P2]). The number average molecular weight of the obtained polymer was 26000, and the molecular weight distribution was 1.2. The average number of silyl groups introduced per molecule of the polymer was determined by ¹ H NMR analysis and found to be 2.0.

Similarly, the polymer [2], dimethoxymethylhydrosilane, methyl orthoformate, and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zerovalent platinum are charged into a 1 L pressure-resistant reaction vessel, After making it heat-react, the volatile content of the mixture was depressurizingly distilled and the silyl group terminal vinyl polymer (polymer [P3]) was obtained. The number average molecular weight of the obtained polymer was 26000, and the molecular weight distribution was 1.2. When the average number of silyl groups introduced per molecule of the polymer was determined by ¹ H NMR analysis, it was 1.4.

(Production Example 2)
CuBr (8.39 g, 0.0585 mol) was charged into a 2 L separable flask equipped with a reflux tube and a stirrer, and the inside of the reaction vessel was purged with nitrogen. Acetonitrile (112 mL) was added, and the mixture was stirred in an oil bath at 70 ° C. for 30 minutes. To this was added butyl acrylate (224 mL), diethyl 2,5-dibromoadipate (23.4 g, 0.0650 mol), and triamine (0.500 mL, 0.244 mmol) to initiate the reaction. While heating and stirring at 70 ° C., butyl acrylate (895 mL) was continuously added dropwise over 150 minutes. Triamine (2.50 mL, 12.0 mmol) was added during the dropwise addition of butyl acrylate. After 310 minutes from the start of the reaction, 1,7-octadiene (288 mL, 1.95 mol) and triamine (4.0 mL, 0.0195 mol) were added, followed by heating and stirring at 70 ° C. for 240 minutes. The reaction mixture was diluted with hexane, passed through an activated alumina column, and then the volatile component was distilled off under reduced pressure to obtain an alkenyl group-terminated polymer (polymer [3]). The number average molecular weight of the polymer [3] was 20000, and the molecular weight distribution was 1.3. A 2 L separable flask equipped with a reflux tube was charged with the polymer [3] (1.0 kg), potassium benzoate (34.8 g), and N, N-dimethylacetamide (1 L), and the nitrogen flow was at 70 ° C. for 15 hours. Stir with heating. N, N-dimethylacetamide was removed under heating and reduced pressure, and then diluted with toluene. Solids insoluble in toluene (KBr and excess potassium benzoate) were filtered through an activated alumina column. The volatile matter in the filtrate was distilled off under reduced pressure to obtain a polymer [4].

  A 2 L round bottom flask with a reflux tube was charged with polymer [4] (1 kg), aluminum silicate (200 g, manufactured by Kyowa Chemical Co., Kyward 700PEL), toluene (1 L), and heated at 100 ° C. for 5.5 hours in a nitrogen stream. Stir. After removing the aluminum silicate by filtration, the toluene in the filtrate was distilled off under reduced pressure to obtain a polymer [5].

In a 1 L pressure-resistant reaction vessel, polymer [5] (720 g), trimethoxysilane (31.7 mL), methyl orthoformate (8.1 mL), and 1,1,3,3-tetramethyl-1 of zerovalent platinum , 3-Divinyldisiloxane complex was charged. However, the amount of the platinum catalyst used was 5 × 10 ⁻⁴ equivalent in terms of molar ratio to the alkenyl group of the polymer. After the reaction mixture was heated and reacted, the volatile component of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated vinyl polymer (polymer [P4]). The number average molecular weight of the obtained polymer was 23000 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.4. The average number of silyl groups introduced per polymer molecule was determined by ¹ H NMR analysis and found to be 1.7.

Similarly, a 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of polymer [5], trimethoxysilane, dimethoxymethylhydrosilane, methyl orthoformate, and zerovalent platinum was added to a 1 L pressure-resistant reaction vessel. Was charged. However, the input amounts of trimethoxysilane and dimethoxymethylhydrosilane were 70 to 30 in molar ratio. The reaction mixture was heated and reacted, and then the volatile content of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated vinyl polymer (polymer [P5]). The number average molecular weight of the obtained polymer was 23000 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.4. When the average number of silyl groups introduced per molecule of the polymer was determined by ¹ H NMR analysis, it was 1.2 trimethoxy groups and 0.5 dimethoxymethyl groups.

Similarly, polymer [5], dimethoxymethylhydrosilane, methyl orthoformate, and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zerovalent platinum are charged into a 1 L pressure-resistant reaction vessel and heated. After the reaction, the volatile component of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated vinyl polymer (polymer [P6]). The number average molecular weight of the obtained polymer was 23000 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.4. The average number of silyl groups introduced per polymer molecule was determined by ¹ H NMR analysis and found to be 1.7.

(Production Example 3)
CuBr (251.82 g, 1.76 mol) was charged into a 50 L polymerization machine equipped with a reflux tower and a stirrer, and the inside of the reaction vessel was purged with nitrogen. Acetonitrile (3360 mL) was added and stirred at 68 ° C. for 20 minutes. To this was added butyl acrylate (6.80 L), diethyl 2,5-dibromoadipate (526.70 g, 1.46 mol) and triamine (12.0 mL, 0.0585 mol) to initiate the reaction. While heating and stirring at 70 ° C., butyl acrylate (26.80 L) was continuously added dropwise over 204 minutes. Triamine (36.0 mL, 0.176 mol) was added during the dropwise addition of butyl acrylate. After 397 minutes from the start of the reaction, 1,7-octadiene (8640 mL, 58.5 mol) and triamine (120 mL, 0.585 mol) were added, and the mixture was heated and stirred at 80 ° C. for 240 minutes. Thereafter, triamine (80 mL, 0.390 mol) was added, and the mixture was stirred with heating at 90 ° C. for 240 minutes.

  The reaction mixture was diluted with toluene, the insoluble copper complex was removed using a separator-type centrifugal sedimentator, passed through an activated alumina column, and then the volatile component was distilled off under reduced pressure to remove the alkenyl group-terminated polymer (polymer). [6]) was obtained. The number average molecular weight of the polymer [6] was 24,000, and the molecular weight distribution was 1.21. A 10 L separable flask equipped with a reflux tube was charged with polymer [6] (3.0 kg), potassium acetate (24.5 g) and N, N-dimethylacetamide (3 L), and heated at 100 ° C. for 10 hours under a nitrogen stream. Stir. N, N-dimethylacetamide was removed under heating and reduced pressure, and then diluted with toluene. Solids insoluble in toluene (KBr and excess potassium acetate) were filtered through an activated alumina column. The polymer [7] was obtained by distilling off the volatile matter of the filtrate under reduced pressure.

  A 10 L round bottom flask equipped with a reflux tube was charged with polymer [7] (3 kg), hydrotalcite (450 g, manufactured by Kyowa Chemical, Kyoward 500SH, Kyoward 700SL), and xylene (0.6 L) under a nitrogen stream 130 The mixture was heated and stirred at ° C for 5.0 hours. After removing the aluminum silicate by filtration, the filtrate was distilled off under reduced pressure to obtain a polymer [8].

In a 2 L reaction vessel, polymer [8] (1000 g), trimethoxysilane (52 mL), methyl orthoformate (13.3 mL), and 1,1,3,3-tetramethyl-1,3- Divinyldisiloxane complex was charged. A platinum catalyst and trimethoxysilane were added during the reaction. The total amount of trimethoxysilane used was 69 mL, and the total amount of platinum catalyst used was 1 × 10 ⁻³ equivalent in molar ratio to the alkenyl group of the polymer. After making it heat-react, the volatile component of the mixture was depressurizingly distilled and the silyl group terminal vinyl polymer (polymer [P7]) was obtained. The number average molecular weight of the obtained polymer was 28500 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.4. When the average number of silyl groups introduced per molecule of the polymer was determined by ¹ H NMR analysis, it was 2.5.

Similarly, the polymer [8], 3-mercaptopropyltrimethoxysilane, and 2,2′-azobis-2-methylbutyronitrile are charged into a 2 L reaction vessel and heated to react. The silyl group-terminated vinyl polymer (polymer [P8]) was obtained by sufficiently distilling under reduced pressure (so that no 3-mercaptopropyltrimethoxysilane was left). The number average molecular weight of the obtained polymer was 28500 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.4. When the average number of silyl groups introduced per molecule of the polymer was determined by ¹ H NMR analysis, it was 2.8.

Similarly, polymer [8] (1000 g), dimethoxymethylhydrosilane (45 mL), methyl orthoformate (13.3 mL), and 1,1,3,3-tetramethyl-1, zero-valent platinum were added to a 2 L reaction vessel. A 3-divinyldisiloxane complex was charged. In addition, like the polymer [P7], a platinum catalyst and dimethoxymethylsilane were added during the reaction. After sufficiently heating and reacting, the volatile content of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated vinyl polymer (polymer [P9]). The number average molecular weight of the obtained polymer was 28500 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.4. When the average number of silyl groups introduced per molecule of the polymer was determined by ¹ H NMR analysis, it was 2.5.

(Production Example 4)
Based on the method described in Example 2 described in JP-A-11-080249, using hydroxyethyl-2-bromopropionate as an initiator, cuprous bromide and 2,2-bipyridyl as a polymerization catalyst, Acrylic acid-n-butyl was polymerized, and at the end of polymerization, 2-hydroxyethyl methacrylate was added to obtain poly-n-butyl acrylate (polymer [9]) having a hydroxyl group at the terminal. The number average molecular weight of the obtained polymer was 6100 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.3.

Isocyanatopropyltrimethoxysilane was added to this for urethanation reaction, and the terminal hydroxyl group was converted to a trimethoxysilyl group to obtain a vinyl polymer having a trimethoxysilyl group (polymer [P10]). The average number of silyl groups introduced per polymer molecule was determined by ¹ H NMR analysis to be 3.3.

(Production Example 5)
CuBr (923.3 g, 6.44 mol) was charged into a 250 L reaction kettle equipped with a stirrer, and after the reaction kettle was sealed with nitrogen, acetonitrile (6671 g) was added and stirred at 65 ° C. for 15 minutes. To this was added butyl acrylate (22.0 kg), diethyl 2,5-dibromoadipate (1931.2 g, 5.36 mol), acetonitrile (3000 g), triamine (44.8 mL, 214.6 mmol), and the reaction was started. did. While heating and stirring at 80 ° C., butyl acrylate (88.0 kg) was continuously added dropwise. Triamine (179.2 mL, 859.5 mmol) was added during the dropwise addition of butyl acrylate. Subsequently, after heating and stirring at 80 ° C., 1,7-octadiene (15.847 kg) and triamine (672.0 mL, 3.21 mol) were added, and heating and stirring were further continued at 80 ° C. for 10 hours, whereby the polymer [10 ] Containing a reaction mixture (polymerization reaction mixture [10 ′]) was obtained. The volatile component of the reaction mixture [10 ′] was distilled off under reduced pressure to obtain an alkenyl group-terminated polymer (polymer [10]).

  Polymer [10] (100 kg), methylcyclohexane (100 kg), adsorbent (2 kg each, manufactured by Kyowa Chemical, Kyoward 500SH, Kyoward 700SL) are charged into a 250 L reaction kettle equipped with a stirrer, and an oxygen / nitrogen mixed gas atmosphere Under stirring at 150 ° C. for 2 hours, the solid content was separated to obtain a polymer [11].

  A 10 L separable flask equipped with a reflux tube was charged with the polymer [11] (3.2 kg), potassium acetate (74.1 g), N, N-dimethylacetamide (3.2 L), and the mixture was heated at 100 ° C. under a nitrogen stream at 8 ° C. Stir for hours. N, N-dimethylacetamide was removed under heating and reduced pressure, and then diluted with toluene. Solids insoluble in toluene (KBr and excess potassium acetate) were filtered through an activated alumina column. The volatile matter in the filtrate was distilled off under reduced pressure to obtain a polymer [12].

  A 10 L separable flask equipped with a reflux tube was charged with polymer [12] (3 kg), adsorbent (1800 g, manufactured by Kyowa Chemical, Kyoward 500SH, Kyoward 700SL), xylene (1.5 L), and 130 ° C. under a nitrogen stream. And stirred for 5.0 hours. After removing the adsorbent by filtration, the filtrate was distilled off under reduced pressure to obtain a polymer [13].

In a 2 L reaction vessel, the polymer [13] (1300 g) obtained in Production Example 1, dimethoxymethylhydrosilane (58.5 mL), methyl orthoformate (17.3 mL), and 1,1,3 of zerovalent platinum A 3-tetramethyl-1,3-divinyldisiloxane complex was charged. In addition, the usage-amount of a platinum catalyst is 30 mg in conversion of platinum with respect to 1 kg of polymers. After heating at 100 ° C. for 3.5 hours, the volatile content of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated vinyl polymer (polymer [P11]). The number average molecular weight of the obtained polymer was 27000 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.4. The average number of silyl groups introduced per polymer molecule was determined by ¹ H NMR analysis and found to be 1.8.

(Production Example 6)
Using a 50 L polymerization machine equipped with a reflux tower and a stirrer, CuBr (188.02 g, 1.3107 mol), acetonitrile (3226 mL), butyl acrylate (9396 mL), ethyl acrylate (13060 mL), as in Production Example 3 2-methoxyethyl acrylate (9778 mL), diethyl 2,5-dibromoadipate (786.55 g), triamine (187.76 mL) and 1,7-octadiene (6452 mL) were used as raw materials, and the reaction mixture reacted was toluene. After diluting with an activated alumina column, the volatile component was distilled off under reduced pressure to obtain an alkenyl-terminated copolymer {copolymer of alkenyl-terminated poly (butyl acrylate, ethyl acrylate, methoxyethyl acrylate): Copolymer [14]} was obtained.

  A 10 L separable flask equipped with a reflux tube was charged with the copolymer [14] (3.0 kg), potassium acetate (24.5 g), and N, N-dimethylacetamide (3 L), and at 100 ° C. for 10 hours under a nitrogen stream. Stir with heating. N, N-dimethylacetamide was removed under heating and reduced pressure, and then diluted with toluene. Solids insoluble in toluene (KBr and excess potassium acetate) were filtered through an activated alumina column. The volatile component of the filtrate was distilled off under reduced pressure to obtain an alkenyl-terminated copolymer {copolymer of alkenyl-terminated poly (butyl acrylate, ethyl acrylate, methoxyethyl acrylate): copolymer [15]}. It was.

  A 10 L round bottom flask with a reflux tube was charged with copolymer [15] (3 kg), hydrotalcite (450 g, manufactured by Kyowa Chemical Co., Ltd., Kyoward 500SH, Kyoward 700SL), and xylene (0.6 L) under a nitrogen stream. The mixture was heated and stirred at 130 ° C. for 5.0 hours. After the aluminum silicate was removed by filtration, the filtrate was distilled off under reduced pressure to obtain a copolymer [16].

Copolymer [16] (1000 g), dimethoxymethylhydrosilane (29.8 mL), methyl orthoformate (11.7 mL), and 1,1,3,3-tetramethyl-1 of zerovalent platinum in a 2 L reaction vessel , 3-Divinyldisiloxane complex was charged. A platinum catalyst and dimethoxymethylsilane were added during the reaction. After sufficient heating reaction, the volatile content of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated vinyl copolymer (copolymer [P12]). The number average molecular weight of the obtained copolymer was 21500 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.3. The average number of silyl groups introduced per molecule of copolymer was determined by ¹ H NMR analysis and found to be 2.3.

(Production Example 7)
Isocyanate propyltrimethoxysilane is added to polypropylene alcohol having a number average molecular weight of 1200 blocked at one end with a butoxy group (commercial product Newpol LB-285, manufactured by Sanyo Kasei), and a urethanization reaction is carried out. Conversion into a methoxysilyl group yielded a polyether polymer (polymer [P13]) having a crosslinkable silyl group.

(Production Example 8)
Propylene oxide was subjected to ring-opening polymerization using allyl alcohol as an initiator to form a polyoxypropylene monool having a molecular weight of 2000 and containing one terminal allyloxy group, and subsequently reacted with equimolar benzoyl chloride in the presence of triethylamine. The reaction mixture was diluted with 5 times the amount of hexane and washed with water to remove triethylamine hydrochloride, and hexane was distilled off to obtain a compound having one end having a benzoyloxy group and the other end having an allyl group. Next, dimethoxymethylsilane and chloroplatinic acid were used to convert one terminal allyl group to dimethoxymethylsilylpropyl group to obtain a polyether polymer (polymer [P14]) having a crosslinkable silyl group. The molecular weight was 2500, and the viscosity was 0.7 Pa · s (23 ° C.).

(Production Example 9)
Using 2-ethylhexanol as an initiator, a polyoxypolypropylene monool is produced by reacting propylene oxide in the presence of a double metal cyanide complex catalyst by the method described in JP-A-3-72527, After allyl chloride was reacted to introduce unsaturated groups, trimethoxysilane was further reacted to obtain a polyether polymer (polymer [P15]) having a crosslinkable silyl group at one end. The number average molecular weight was 3000, and the viscosity was 0.6 Pa · s (23 ° C.).

(Production Example 10)
Polypropylene glycol having a hydroxyl group at both ends and a molecular weight of 3000 is used as an initiator to react with propylene oxide in the presence of a double metal cyanide complex catalyst to obtain a polyoxypolypropylene monool by the method described in JP-A-3-72527. After the introduction of an unsaturated group by reacting the terminal hydroxyl group with an equivalent amount of allyl chloride or less, the compound is further reacted with an equivalent amount or less of methyldimethoxysilane to have an average of 1.2 or less crosslinkable silyl groups. An ether polymer (polymer [P16]) was obtained. The number average molecular weight was 8000, and the average number of silyl groups introduced per molecule of the polymer was determined by ¹ H NMR analysis to be 0.9.

(Production Example 11)
Polypropylene glycol having a molecular weight of 3000 having hydroxyl groups at both ends is used as an initiator, and a method described in JP-A-3-72527 is used to react with propylene oxide in the presence of a double metal cyanide complex catalyst to obtain polyoxypolypropylene monool. A polyether polymer having a crosslinkable silyl group at the molecular end by reacting allyl chloride with a terminal hydroxyl group to introduce an unsaturated group and then reacting an equivalent group with methyldimethoxysilane. (Polymer [P17]) was obtained. The number average molecular weight was 16000, and the average number of silyl groups introduced per molecule of the polymer was determined by ¹ H NMR analysis to be 1.6.

(Examples 1 to 16)
100 parts of the polymers [P1 to P12] obtained in Production Examples 1 to 4 include 150 parts of colloidal calcium carbonate (Shiraka Hana CCR: manufactured by Shiraishi Calcium), 20 parts of heavy calcium carbonate (Nanox 25A: manufactured by Maruo Calcium), titanium oxide. (Taipeke R-820 (rutile type): manufactured by Ishihara Sangyo Co., Ltd.) 10 parts, polymer [P13-P16] obtained in Production Examples 7-10 (described in Table 1) as a plasticizer, 50 parts, thixotropic agent 2 parts (Disparon 6500 manufactured by Enomoto Kasei), 1 part each of anti-aging agents (Sanol LS-765 (HALS): Sankyo, Tinuvin 213: Ciba Specialty Chemicals) are added, and three more paint rolls are used. After mixing well, mix various other additives, apply to a sheet of about 2mm thickness using various curing catalysts, cure at room temperature, and further store the cured product in the chamber. The flexibility of the cured product of the mixture was allowed to stand for one week at was evaluated by finger touch. Table 1 shows the number of parts added and the evaluation results of various compounding agents and curing agents. In the evaluation of the flexibility of the present invention, ◯ indicates a good level as a sealant for low modulus, and x indicates a level that is too hard as a sealant for low modulus (that is, inappropriate). For oil bleed, the cured product was allowed to stand in an atmosphere of 30 ° C. × 80% for 1 week, and then the surface state of the cured product was confirmed by visual observation and finger touch. In the evaluation of the oil bleed according to the present invention, ◯ indicates a state where no oil bleed is observed (that is, a good state), × indicates that the surface is oily and sticky (that is, defective), and △ indicates an intermediate state between them. ing. All the cured products maintained sufficient flexibility as a sealant for low modulus, and no oil bleed was observed even under conditions of high temperature and high humidity.

(Comparative Example 1)
Example 1 except that 2-ethylhexyl phthalate was used in place of the polymer [P13 to P16] used as the plasticizer in Examples 1 to 16 for the polymer [P3] obtained in Production Example 1. A cured product was prepared in the same manner as in -16, and the flexibility and oil bleed of the cured product were similarly observed and evaluated. Table 1 shows the number of parts added and various results of various compounding agents and curing agents.

(Comparative Example 2)
Examples 1-16 except that the polymer [P13-P16] used as a plasticizer in Examples 1-16 was used instead of the polymer [P6-P16] obtained in Production Example 2 instead of phthalate-isodecyl. A cured product was prepared in the same manner as above, and the flexibility and oil bleed of the cured product were observed and evaluated. Table 1 shows the number of parts added and various results of various compounding agents and curing agents. The results are shown in Table 1.

(Comparative Example 3)
The polymer [P9] obtained in Production Example 3 was cured in the same manner as in Examples 1 to 16, except that the polymer [P13 to P16] used as a plasticizer in Examples 1 to 16 was not used. A product was prepared, and the flexibility and oil bleed of the cured product were observed and evaluated. Table 1 shows various compounding agents and curing agents, and the number of addition parts of the curing agents and the results. The results are shown in Table 1.

Flexibility: ○… good, ×… bad (hard… unsuitable as low modulus sealant)
Oil bleed: Good ← ○>△> × → Defective (solid)
(1) Plasticizer: P12 to P15, DOP (dioctyl phthalate: manufactured by Kyowa Hakko), DIDP (diisodecyl phthalate: manufactured by Kyowa Hakko)
(2) Curing catalyst: Cat. A ... U-220 (dibutyltin diacetylacetonate, 2 parts), Cat. B ... (tin octylate / laurylamine = 3 parts / 1 part)
(3) Air oxidation curable substance: C ... Tung oil, D ... linseed oil, E ... 1,2-polybutadiene (4) Photocurable substance: F ... pentaerythritol triacrylate, G ... trimethylolpropane triacrylate (5) Silanol compound: H ... hexamethyldisilazane, I ... trimethylphenoxysilane, J ... trimethylolpropane tris (trimethylsilyl)

(Examples 17 to 18)
100 parts of the polymer [P11] obtained in Production Example 5 are mixed with 150 parts of colloidal calcium carbonate (Shiraka Hana CCR: manufactured by Shiroishi Calcium), 20 parts of heavy calcium carbonate (Nanox 25A: manufactured by Maruo Calcium), titanium oxide (Taipeke R- 820 (rutile type): manufactured by Ishihara Sangyo Co., Ltd. 10 parts, [P15 and P14] plasticizer 60 parts, thixotropic agent (Disparon 6500 manufactured by Enomoto Kasei), anti-aging agent (Sanol LS-765 (HALS)): Sankyo manufactured, Tinuvin 213: manufactured by Ciba Specialty Chemicals) 1 part each and mixed thoroughly with a planetary mixer, each silanol-containing compound (A-1120, A-171: both manufactured by Nihon Unicar) 1 each And 2 parts of a curing catalyst (U-220 (dibutyltin diacetylacetonate): manufactured by Nitto Kasei) are further added, The composition was prepared. The viscosity at 23 ° C. of the composition was measured. Furthermore, it applied to the sheet form of about 2 mm thickness, it was made to harden | cure at room temperature, and the softness | flexibility of the hardened | cured material and oil bleed were observed and evaluated similarly to Examples 1-17. Table 2 shows the number of parts added and various results of various compounding agents and curing agents.

(Example 19)
100 parts of 50 parts of [P10] obtained in Production Example 4 and 50 parts of [P17] obtained in Production Example 11 were mixed with 40 parts of [P15] obtained in Production Example 9 and colloidal calcium carbonate. (Shiraka Hana CCR: Shiraishi Calcium) 150 parts, Heavy Calcium Carbonate (Nanox 25A: Maruo Calcium) 20 parts, Titanium Oxide (Taipek R-820 (rutile type): Ishihara Sangyo) 10 parts, thixotropic agent ( After adding 2 parts of Disparon 6500 Enomoto Kasei) and 1 part of anti-aging agent (Sanol LS-765 (HALS): Sankyo, Tinuvin 213: Ciba Specialty Chemicals) and mixing well in a planetary mixer , Silanol-containing compounds (A-1120, A-171: manufactured by Nihon Unicar Co., Ltd.) 1 part each and a curing catalyst (U-220 (dibutyltin diacetylamine) Tonato) Nitto Kasei Co., Ltd.) was further added 2 parts, to prepare a curable composition. The curable composition was applied to a sheet having a thickness of about 2 mm as in Examples 1 to 18, cured at room temperature, and the cured product was allowed to stand at room temperature for 1 week. Sex was evaluated. The cured product was allowed to stand in an atmosphere of 30 ° C. × 80% for 1 week, and then the surface state of the cured product was observed. The results are shown in Table 3.
(Example 20)
[P16] obtained in Production Example 4 and 50 parts of [P17] obtained in Production Example 11 were mixed with 100 parts, and [P16] obtained in Production Example 10 was 70 parts, and colloidal calcium carbonate. (Shiraka Hana CCR: Shiraishi Calcium) 150 parts, Heavy Calcium Carbonate (Nanox 25A: Maruo Calcium) 20 parts, Titanium Oxide (Taipek R-820 (rutile type): Ishihara Sangyo) 10 parts, thixotropic agent ( After adding 2 parts of Disparon 6500 Enomoto Kasei) and 1 part of anti-aging agent (Sanol LS-765 (HALS): Sankyo, Tinuvin 213: Ciba Specialty Chemicals) and mixing well in a planetary mixer , Silanol-containing compounds (A-1120, A-171: manufactured by Nihon Unicar Co., Ltd.) 1 part each and curing catalyst (U-220 (dibutyltin diacetyl) Setonato) Nitto Kasei Co., Ltd.) was further added 2 parts, to prepare a curable composition. The curable composition was applied to a sheet having a thickness of about 2 mm as in Examples 1 to 18, cured at room temperature, and the cured product was allowed to stand at room temperature for 1 week. Sex was evaluated. The cured product was allowed to stand in an atmosphere of 30 ° C. × 80% for 1 week, and then the surface state of the cured product was observed. The results are shown in Table 3.
(Example 21)
[P12] obtained in Production Example 6 and 70 parts of [P17] obtained in Production Example 11 were mixed with 100 parts, and [P15] in 40 parts obtained in Production Example 9 and colloidal calcium carbonate. (Shiraka Hana CCR: Shiraishi Calcium) 150 parts, Heavy Calcium Carbonate (Nanox 25A: Maruo Calcium) 20 parts, Titanium Oxide (Taipek R-820 (rutile type): Ishihara Sangyo) 10 parts, thixotropic agent ( After adding 2 parts of Disparon 6500 Enomoto Kasei) and 1 part of anti-aging agent (Sanol LS-765 (HALS): Sankyo, Tinuvin 213: Ciba Specialty Chemicals) and mixing well in a planetary mixer , Silanol-containing compounds (A-1120, A-171: manufactured by Nihon Unicar Co., Ltd.) 1 part each and a curing catalyst (U-220 (dibutyltin diacetylamine) Tonato) Nitto Kasei Co., Ltd.) was further added 2 parts, to prepare a curable composition. The curable composition was applied to a sheet having a thickness of about 2 mm as in Examples 1 to 18, cured at room temperature, and the cured product was allowed to stand at room temperature for 1 week. Sex was evaluated. The cured product was allowed to stand in an atmosphere of 30 ° C. × 80% for 1 week, and then the surface state of the cured product was observed. The results are shown in Table 3.
(Example 22)
70 parts of [P12] obtained in Production Example 6 and 30 parts of [P17] obtained in Production Example 11 were mixed with 100 parts, [P16] obtained in Production Example 10 and 70 parts of colloidal calcium carbonate (Shiraka Hana CCR: Shiraishi Calcium) 150 parts, Heavy Calcium Carbonate (Nanox 25A: Maruo Calcium) 20 parts, Titanium Oxide (Taipek R-820 (rutile type): Ishihara Sangyo) 10 parts, thixotropic agent ( After adding 2 parts of Disparon 6500 Enomoto Kasei) and 1 part of anti-aging agent (Sanol LS-765 (HALS): Sankyo, Tinuvin 213: Ciba Specialty Chemicals) and mixing well in a planetary mixer , Silanol-containing compounds (A-1120, A-171: manufactured by Nihon Unicar Co., Ltd.) 1 part each and curing catalyst (U-220 (dibutyltin diacetyl) Setonato) Nitto Kasei Co., Ltd.) was further added 2 parts, to prepare a curable composition. The curable composition was applied to a sheet having a thickness of about 2 mm as in Examples 1 to 18, cured at room temperature, and the cured product was allowed to stand at room temperature for 1 week. Sex was evaluated. The cured product was allowed to stand in an atmosphere of 30 ° C. × 80% for 1 week, and then the surface state of the cured product was observed. The results are shown in Table 3.

  The curable composition using a vinyl polymer having at least one crosslinkable silyl group and a polyether polymer having 1.2 or less crosslinkable silyl groups on average has a good viscosity and flexibility. Showed sex. Oil bleed was also good.

Claims (17)

Contains the following two components: a vinyl polymer (I) having at least one crosslinkable silyl group, and a polyether polymer (II) having an average of 1.2 or less crosslinkable silyl groups A curable composition characterized by that. The curable composition according to claim 1, wherein the crosslinkable silyl group of the polyether polymer (II) is present at the end of the main chain. The curable composition according to claim 2, wherein the crosslinkable silyl group of the polyether polymer (II) is present only at one terminal in the main chain and not at the other terminal. The curable composition according to any one of claims 1 to 3, comprising a vinyl polymer (I) having a molecular weight distribution of less than 1.8. The main chain is produced by mainly polymerizing a monomer 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, comprising a vinyl polymer (I). 6. The curable composition according to claim 5, wherein the main chain contains a vinyl polymer (I) which is a (meth) acrylic polymer. The curable composition according to claim 6, wherein the main chain contains a vinyl polymer (I) which is an acrylic polymer. The curable composition according to claim 7, wherein the main chain contains a vinyl polymer (I) which is an acrylate ester polymer. The curable composition according to claim 8, wherein the main chain contains a vinyl polymer (I) which is a butyl acrylate polymer. Curing as described in any one of Claims 1-9 containing 5-100 weight part of polyether polymers (II) with respect to 100 weight part of vinyl polymers (I). Sex composition. The curing according to any one of claims 1 to 10, further comprising a polyether polymer (III) having at least 1.2 crosslinkable functional groups as a third component. Sex composition. 10 to 50 parts by weight of a polyether polymer (II) having 1.2 or less crosslinkable silyl groups on the average with respect to 100 parts by weight of the vinyl polymer (I), and at least 1.2 or more The curable composition according to claim 11, comprising a polyether polymer (III) having a crosslinkable functional group. The main chain of vinyl polymer (I) contains the vinyl polymer which is manufactured by a living radical polymerization method, The hardening as described in any one of Claims 1-12 characterized by the above-mentioned. Sex composition. The curable composition according to claim 13, wherein the living radical polymerization contains a vinyl polymer which is atom transfer radical polymerization. The atom transfer radical polymerization contains a vinyl polymer catalyzed by a complex selected from a transition metal complex having a group 7 element, group 8, group 9, group 10, or group 11 element as a central metal in the periodic table. The curable composition according to claim 14. 16. The curable composition according to claim 15, wherein the metal complex used as a catalyst contains a vinyl polymer that is a complex selected from the group consisting of copper, nickel, ruthenium, and iron complexes. The curable composition according to claim 16, wherein the metal complex used as a catalyst contains a vinyl polymer which is a copper complex.