JP2007182590A - Curable compositions - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition which contains a cross-linkable silyl group-having vinylic polymer as a curing agent to reduce the surface adhesiveness of a cured product, facilitates the coating of an alkyd coating on the cured product, has a low viscosity, and gives a flexible cured product. <P>SOLUTION: The present invention relates to a curable composition comprising the following two components: (A) a vinyl polymer having at least one cross-linking silyl group on the average per molecule: and (B) a photocurable substance, (C) an air oxidation-curable substance, (D) a high molecular plasticizer, (E) a reactive plasticizer comprising a vinylic polymer having one silyl group in its molecule or (F) a compound having one silanol group in its molecule and/or a compound capable of reacting with moisture to give a compound having one silanol group in the molecule. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a curable composition. More specifically, the present invention relates to a curable composition containing a vinyl polymer having a crosslinkable functional group such as a crosslinkable silyl group.

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 the above polyether polymers, hydrocarbon polymers, or polyester polymers, such as high weather resistance and transparency. 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 related to vinyl polymers having various crosslinkable silyl groups at their terminals, their production methods, curable compositions, and applications. (See Patent Documents 5 to 16).

For example, a vinyl polymer having a silicon-containing group (hereinafter also referred to as “crosslinkable silyl group”) having a hydroxyl group or hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond, or The cured product obtained from the composition is excellent in heat resistance or weather resistance, and is used for various applications such as an elastic sealant for construction, a sealing material for double-glazed glass, a paint, a coating material, and a sealing material.
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, these vinyl polymer cured products having a crosslinkable silyl group tend to have a contradiction in hardness and surface tackiness (also referred to as stickiness or residual tack). There is a problem that stickiness remains on the surface and it is easily soiled. For example, when it is used as a sealing material for buildings, dirt and dust may adhere to the surface if the adhesiveness remains, and the appearance of the building may be impaired. Therefore, the first aspect of the present invention aims to reduce the tackiness (also referred to as residual tack) on the surface of a cured product of a vinyl polymer having a crosslinkable silyl group.

In addition, a cured product comprising a vinyl polymer having a crosslinkable functional group such as a crosslinkable silyl group as a curing component has good heat resistance and weather resistance, and is excellent when a coating is applied thereon. Has paintability. However, if a plasticizer having a relatively low molecular weight such as phthalate, which has been well known in the past, is used to lower the viscosity of the compound, the cured product will flow out over time due to heat or rain. This makes it difficult to maintain the initial physical properties for a long time. In addition, when a paint called an alkyd paint is applied, the paint has a drawback that it is difficult to dry and harden.

Therefore, the second aspect of the present invention reduces the stickiness (residual tack) on the surface of the cured product while maintaining the good mechanical properties of the cured product comprising a vinyl polymer having a crosslinkable silyl group as a curing component, and adheres to dust. The purpose of this is to improve the paintability of the alkyd paint on the cured product. Another object of the present invention is to maintain the heat resistance and weather resistance of a cured product of a vinyl polymer having a crosslinkable functional group for a long period of time, and to improve the paintability of an alkyd paint on the cured product. And

On the other hand, in order to give flexibility to these cured products by lowering the modulus, it is generally necessary to increase the molecular weight of the polymer. In this case, however, the viscosity of the polymer is increased, causing a problem in workability. come. Another method is to reduce the amount of crosslinkable silyl groups introduced without increasing the molecular weight of the polymer. In this case, however, the proportion of uncrosslinked components increases, resulting in a decrease in curing rate or curing. There are problems such as adversely affecting physical properties other than flexibility, such as a reduction in the gel fraction of materials. For this reason, in order to reduce the viscosity while maintaining flexibility, a method of adding various plasticizers has been generally employed.

Examples of such plasticizers include aromatic carboxylic acid esters, aliphatic carboxylic acid esters, phosphoric acid esters, glycols, epoxy plasticizers, chlorinated paraffins, and the like. However, since these plasticizers have migration properties, when used in sealing materials, adhesives, etc., there are problems such as contamination around the sealing area, adverse effects on adhesiveness, and reduced flexibility due to plasticizer extraction during long-term curing. May occur. Therefore, a fourth aspect of the present invention aims to improve the workability during the blending step or the construction of the curable composition, to impart flexibility to the cured product, and to suppress the adverse effects due to the plasticizer migration.

A method for reducing the content of the crosslinkable silyl group in the vinyl polymer without reducing the amount of the crosslinkable silyl group introduced in order to impart flexibility to these cured products by reducing the modulus. 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 (hereinafter, these are also referred to as “silanol-containing compounds”) ) Is disclosed in JP-A-61-34067, JP-A-64-9268, and the like.

However, the organic vinyl polymer having at least one reactive silicon functional group in the molecule disclosed in JP-A-61-34067 is a general free radical polymerization method using a chain transfer agent. In order to provide flexibility while maintaining a high gel fraction, a large amount of unsaturated organosilicon compound monomer and a large amount of silanol-containing compound must be used. There is a problem that must be. Therefore, the fifth aspect of the present invention is to obtain a curable composition having a low viscosity, a high gel fraction when cured, a low surface stickiness, a low modulus, a high elongation and flexibility. Objective.

That is, the first present invention includes the following two components:
(A1) A vinyl polymer having an average of at least one crosslinkable silyl group represented by the general formula (1),-[Si (R ¹ ) _2-b (Y) _b O] _m -Si (R ² ) _3-a (Y) _a (1)
(In the formula, R ¹ and R ² are the same or different and each represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO. (In the formula, R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. The plurality of R ′ may be the same or different. When two or more R ¹ or R ² are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and two or more Y are present. , They may be the same or different, a represents 0, 1, 2, or 3. b represents 0, 1, or 2. m represents an integer of 0 to 19. A + mb ≧ 1) (B) a photocurable substance. A curable composition.

The second aspect of the present invention contains (A2) a vinyl polymer having an average of at least one crosslinkable silyl group represented by the general formula (1), and (C) an air oxidation curable substance. It is a curable composition.

The third aspect of the present invention is a curable composition containing (A3) a vinyl polymer having an average of at least one crosslinkable functional group, and (D) a polymer plasticizer.

According to a fourth aspect of the present invention, (A4) a vinyl polymer having 1.1 or more crosslinkable silyl groups represented by the general formula (1) on average, and (E) 1 or less on average. It is a curable composition containing the reactive plasticizer which is a vinyl polymer which has a crosslinkable silyl group represented by the said General formula (1).

Finally, the fifth aspect of the present invention is (A5) a vinyl polymer polymer having a polymer main chain having at least one crosslinkable silyl group represented by the general formula (1) on average obtained by a living polymerization method. Combined (however, in general formula (1), R ¹ and R ² are the same or different and are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms) And (F) 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. It is a curable composition. The present invention is described in detail below.

Since the curable composition according to the first aspect of the present invention has the above-described configuration, it reduces the adhesiveness (also referred to as residual tack) of the cured product surface using a vinyl polymer having a crosslinkable silyl group as a curing component. Can do. Since the curable composition according to the second aspect of the present invention has the above-described configuration, the cured product surface of the cured product is maintained while maintaining the good mechanical properties of the cured product containing a vinyl polymer having a crosslinkable silyl group as a curing component. Stickiness (residual tack) can be reduced, dust adhesion can be suppressed, and alkyd paint can be easily applied to the cured product. Since the curable composition according to the third aspect of the present invention has the above-described configuration, it retains the heat resistance and weather resistance of the cured product of the vinyl polymer having a crosslinkable functional group over a long period of time, and can be applied to the cured product. Alkyd paint can be easily applied. Since the curable composition which is the fourth aspect of the present invention has the above-described configuration, workability can be improved by reducing the viscosity during the blending process or curable composition construction, and the cured product is given flexibility, Moreover, adverse effects due to plasticizer migration can be suppressed. Since the curable composition according to the fifth aspect of the present invention has the above-described configuration, a cured product having low viscosity, high gel fraction, low surface stickiness, low modulus, high elongation and flexibility. Obtainable.

<< Regarding the First Invention >> First, the curable composition of the first invention will be described in detail. The curable composition of 1st this invention contains the vinyl-type polymer which has a crosslinkable silyl group which is (A1) component, and the photocurable substance which is (B) component.

[Vinyl polymer of component (A1)] A vinyl polymer having an average of at least one crosslinkable silyl group represented by formula (1) as component (A1) forms a siloxane bond. It crosslinks by doing.

<Main chain> The vinyl monomer constituting the main chain of the vinyl polymer (A1) is not particularly limited, and various kinds of monomers can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n- Butyl, isobutyl (meth) acrylate, (tert-butyl) (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl Acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) Phenyl acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate (Meth) acrylic acid-3-methoxybutyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid stearyl, (meth) acrylic acid glycidyl, (meth) 2-aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate , 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate , (Perfluoromethylmethyl) (meth) acrylate, (me T) 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluoro (meth) acrylate (Meth) acrylic acid monomers such as hexadecylethyl; styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and their salts; perfluoroethylene, perfluoropropylene, vinylidene fluoride, etc. Fluorine-containing vinyl monomers; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters of fumaric acid and Dialkyl esters; maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitrile groups such as acrylonitrile and methacrylonitrile Vinyl monomers; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; butadiene And conjugated dienes such as 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. Of these, a styrene monomer and a (meth) acrylic acid monomer are preferable from the physical properties of the product. More preferred are acrylate monomers and methacrylate monomers, particularly preferred are acrylate monomers, and even more preferred is butyl acrylate. In the present invention, these 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 (A1), that is, the ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography is not particularly limited, but is preferably less than 1.8, preferably 1. 7 or less, more preferably 1.6 or less, still more preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less. In the GPC measurement in the present invention, chloroform is usually used as the mobile phase, the measurement is performed with a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene.

The number average molecular weight of the vinyl polymer (A1) is not particularly limited, but is preferably in the range of 500 to 1,000,000, more preferably 1000 to 100,000.

<Synthesis Method of Main Chain> The method for synthesizing the vinyl polymer (A1) 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 uses an azo compound, a peroxide or the like as a polymerization initiator to simply copolymerize a monomer having a specific functional group and a vinyl monomer. It can be classified into “polymerization method” and “controlled radical polymerization method” in which a specific functional group can be introduced at a controlled position such as a terminal.

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

The “controlled radical polymerization method” further includes a “chain transfer agent method” in which a vinyl polymer having a functional group at a terminal is obtained by polymerization using a chain transfer agent having a specific functional group, It can be classified as “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 in the production of the vinyl polymer (A1) described later, a chain transfer agent was used. The polymerization will be described. 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.

As reported in Macromolecules 1995, 28, 2993, instead of using a radical capping agent and a radical generator together, 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, an atom transfer radical polymerization method more preferable as the living radical polymerization of the present invention will be described.

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

If Specific _{examples, 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 ( where upper In which C ₆ H ₅ is a phenyl group, X is chlorine, bromine, or iodine)
^{_{R 3 -C (H) (X}} ) -CO 2 R 4, R 3 -C (CH 3) (X) -CO 2 R 4, R 3 -C (H) (X) -C (O) R 4 , R ³ —C (CH ₃ ) (X) —C (O) R ⁴ , wherein R ³ and R ⁴ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, X Is chlorine, bromine, or iodine)
R ³ —C ₆ H ₄ —SO ₂ X (in the above formulas, R ³ is 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), etc. Is mentioned.

As an initiator of atom transfer radical polymerization, an organic halide or a sulfonyl halide compound having a functional group other than the functional group for initiating polymerization can also be used. In such a case, a vinyl polymer having a functional group at one end of the main chain and a growth terminal structure of atom transfer radical polymerization at the other main chain end is produced. Examples of such functional groups include alkenyl groups, crosslinkable silyl groups, hydroxyl groups, epoxy groups, amino groups, amide groups, and the like.

It does not limit as an organic halide which has an alkenyl group, For example, what has a structure shown in General formula (2) is illustrated.
^{R 6 R 7 C (X)} -R 8 -R 9 -C (R 5) = CH 2 (2)
(Wherein R ⁵ is hydrogen or a methyl group, R ⁶ and R ⁷ are hydrogen, or a monovalent alkyl group having 1 to 20 carbon atoms, an aryl group, or aralkyl, or those interconnected at the other end. , R ⁸ is —C (O) O— (ester group), —C (O) — (keto group), or o-, m-, p-phenylene group, R ⁹ is a direct bond, or 1 carbon atom -20 divalent organic groups which may contain one or more ether linkages, X is chlorine, bromine or iodine)

Specific examples of the substituents R ⁶ and R ⁷ include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, pentyl group, hexyl group and the like. R ⁶ and R ⁷ may be linked at the other end to form a cyclic skeleton.

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

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

(In 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 each formula above, X is Chlorine, bromine, or iodine, n is an integer of 0-20)
_{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 formula above, X is chlorine, bromine or iodine, n represents an integer of 1 to 20, m is 0 to 20 integer,)
_{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 In each formula, 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 , wherein X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is 0 to 20 Integer)

Examples of the organic halide having an alkenyl group further include a compound represented by the general formula (3).
_{^{H 2 C = C (R 5}} ) -R 9 -C (R 6) (X) -R 10 -R 7 (3)
(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁹ and X are the same as above, R ¹⁰ is a direct bond, —C (O) O— (ester group), —C (O) — (keto group) Or an o-, m-, p-phenylene group)

R ⁸ is a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds). Is a halogenated allylic compound. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, it is not always necessary to have a C (O) O group, a phenylene group or the like as R ¹⁰ , and a direct bond may be used. In the case where R ⁹ is not a direct bond, R ¹⁰ is preferably a C (O) O group, a C (O) group, or a phenylene group in order to activate the carbon-halogen bond.

Specific examples of a compound of the general formula _{(3), 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, C _{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 each formula above, X is chlorine, bromine, or iodine, and R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group).

Specific examples of a halogenated sulfonyl compound having an alkenyl _{group, 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, n is an integer of 0 to 20), etc. is there.

It does not specifically limit as said organic halide which has a crosslinkable silyl group, For example, what has a structure shown in General formula (4) is illustrated.
^{R 6 R 7 C (X)} -R 8 -R 9 -C (H) (R 5) CH 2 - [Si (R 11) 2-b (Y) b O] m -Si (R 12) 3- _a (Y) _a (4)
(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are the same as above, R ¹¹ and R ¹² are all alkyl groups, 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 ¹¹ or R ¹² 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)

Specific examples of a compound of the general formula _{(4), 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 each formula above, X is chlorine, bromine, iodine, n represents 0 to 20 integer,)
_{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 each formula above, X is chlorine, bromine, iodine, n represents 1 to 20 integer, m is from 0 to 20 integer)
_{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 each formula above, X is chlorine, bromine or iodine) and the like can be mentioned.

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

If specifically exemplified such _{compounds, (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 , wherein X is chlorine, bromine, or iodine, R is the number of carbons 1-20 alkyl groups, aryl groups, aralkyl groups) and the like.

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

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

The organic halide having the epoxy group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.

(In the above formulas, 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 terminal structures of the present invention 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 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 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.

<Crosslinkable silyl group>
The crosslinking silyl group crosslinkable silyl group <br/> vinyl polymer (A1) has the general formula (1);
^{_{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
{In the formula, R ¹ and R ² are 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 ¹ or When two or more R ² are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are 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 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.

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, the number is preferably 20 or less. In particular, the general formula (6)
-Si (R ¹² ) _3-a (Y) _a (6)
A crosslinkable silyl group represented by the formula (wherein R ¹² , Y and a are the same as described above) is preferable because it is easily available.

Number of crosslinkable silyl groups On average, at least one crosslinkable silyl group represented by the general formula (1) is present in one molecule of the polymer (A1). If the crosslinkable silyl group is less than 1 on average in one molecule, a sufficient cured product cannot be obtained. The number of crosslinkable silyl groups represented by the general formula (1) necessary for obtaining a sufficient cured product is usually 1.1 to 5 on average per molecule, and 1. Those having 2 to 4 are preferred, and those having 1.3 to 3 on average are more preferred.

Position of the crosslinkable silyl group When a rubber-like property is particularly required for a cured product obtained by curing the curable composition of the present invention, the molecular weight between crosslinking points that greatly affects rubber elasticity is used. It is preferable that at least one of the crosslinkable silyl groups is at the end of the molecular chain because it can be taken large. More preferably, all the crosslinkable silyl groups have 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.

<Crosslinkable silyl group introduction method>
Hereinafter, a method for introducing a functional group into a vinyl polymer will be described, but the method is not limited thereto.
[A] A method of adding a hydrosilane compound having a crosslinkable silyl group to a vinyl polymer having at least one alkenyl group in the presence of a hydrosilylation catalyst.
[B] A method of reacting a vinyl polymer having at least one hydroxyl group with a compound having a functional group capable of reacting with a hydroxyl group such as a crosslinkable silyl group and an isocyanate group.
[C] A method of reacting a compound having a polymerizable alkenyl group and a crosslinkable silyl group together with a predetermined vinyl monomer when a vinyl polymer is synthesized by radical polymerization.
[D] A method of radical polymerization of a vinyl monomer using a chain transfer agent having a crosslinkable silyl group.
[E] A method of reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a stable carbanion having a crosslinkable silyl group.

The method for synthesizing the vinyl polymer having at least one alkenyl group used in the synthesis method [A] is not particularly limited, and examples thereof include the methods [Aa] to [Aj] described below. be able to.

[Aa] When synthesizing a vinyl polymer by radical polymerization, it has a polymerizable alkenyl group represented by the following general formula (7) and the like and a low polymerizable alkenyl group together with a predetermined vinyl monomer. A method in which a compound is also reacted.
_{^{H 2 C = C (R 3}} ) -R 4 -R 5 -C (R 6) = CH 2 (7)
In the formula, R ³ represents hydrogen or a methyl group. R ⁴ represents —C (O) O—, or o-, m- or p-phenylene group. R ⁵ represents a direct bond or a divalent organic group having 1 to 20 carbon atoms which may have one or more ether bonds. R ⁶ 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.

The timing of reacting the compound having both the polymerizable alkenyl group and the low polymerizable alkenyl group is not particularly limited, but in the case of expecting rubber-like properties to the obtained crosslinked product, in living radical polymerization, It is preferable to react as the second monomer at the end of the polymerization reaction or after completion of the reaction of the predetermined vinyl monomer.

[Ab] When synthesizing a vinyl polymer by living radical polymerization, 1,5-hexadiene, 1,7-octadiene, 1,9-, at the end of the polymerization reaction or after completion of the reaction of the predetermined vinyl monomer. A method of reacting a compound having at least two alkenyl groups having low polymerizability such as decadiene.

In the following methods [Ac] to [Af], a vinyl polymer having at least one alkenyl group is obtained from a vinyl polymer having at least one carbon-halogen bond having high reactivity. Is the method. The polymer having at least one highly reactive carbon-halogen bond can be obtained by the methods [Ea] and [Eb] described later.

[Ac] A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with an alkenyl group-containing organometallic compound typified by organotin such as allyltributyltin and allyltrioctyltin. , A method of substituting the halogen with an alkenyl group-containing substituent.

[Ad] A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having an alkenyl group represented by the following general formula (8) or the like to alkenylate the halogen. Substitution method.
^{M + C - (R 7)} (R 8) -R 9 -C (R 6) = CH 2 (8)
In the formula, R ⁶ is the same as described above. R ⁷ and R ⁸ are both carbanion C ^- shows the electron withdrawing group or one the other by the electron-withdrawing group having 1 to 10 carbon hydrogen or carbon alkyl group or a phenyl group, stabilized. R ⁹ represents a direct bond or a divalent organic group having 1 to 10 carbon atoms which 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 ⁷ and R ⁸ , —CO ₂ R, —C (O) R and —CN are preferable. Here, R 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.

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

[Af] A vinyl polymer having at least one highly reactive carbon-halogen bond is represented by an alkenyl group-containing oxyanion represented by the following general formula (9) or the following general formula (10) or the like. The alkenyl group-containing carboxylate anion is reacted to replace the halogen with an alkenyl group-containing substituent.
_{^{H 2 C = C (R 6}} ) -R 10 -O - M + (9)
In the formula, R ⁶ and M ⁺ are the same as those described above. R ¹⁰ represents a C 1-20 divalent organic group which may contain one or more ether bonds.
_{^{H 2 C = C (R 6}} ) -R 11 -C (O) O - M + (10)
In the formula, R ⁶ and M ⁺ are the same as those described above. R ¹¹ represents a direct bond or a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds.

Furthermore, the vinyl polymer having at least one alkenyl group can be obtained from a vinyl polymer having at least one hydroxyl group, but the specific method is not particularly limited. For example, the following [A- g] to [A-j]. The vinyl polymer having at least one hydroxyl group can be obtained by the methods [Ba] to [Bi] described later.

[Ag] A method in which a base such as sodium hydroxide or sodium methoxide is allowed to act on a vinyl polymer having at least one hydroxyl group and then reacted with an alkenyl group-containing halide such as allyl chloride.

[Ah] A method in which a vinyl polymer having at least one hydroxyl group is reacted with an alkenyl group-containing isocyanate compound such as allyl isocyanate.

[Ai] A method of reacting a vinyl polymer having at least one hydroxyl group with an alkenyl group-containing acid halide such as (meth) acrylic acid chloride in the presence of a base such as pyridine.

[Aj] A method in which a vinyl polymer having at least one hydroxyl group is reacted with an alkenyl group-containing carboxylic acid such as acrylic acid in the presence of an acid catalyst.

In the method for synthesizing a vinyl polymer having at least one alkenyl group, when the halogen atom is not directly involved in introducing the alkenyl group, such as the methods [Aa] and [Ab] described above, It is preferable to use a living radical polymerization method. In this case, the method [Ab] is more preferable because the control is easier. Among the living radical polymerization methods, the atom transfer radical polymerization method is more preferable.

On the other hand, in the case of introducing an alkenyl group by converting the halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, such as the methods [Ac] to [Af] described above. At least one highly reactive carbon-halogen bond at the end obtained by radical polymerization (atom transfer radical polymerization method) using an organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst It is preferable to use a vinyl polymer having the same. From the viewpoint of easier control, the method [Af] is more preferable.

It does not specifically limit as a hydrosilane compound which has a crosslinkable silyl group used in the said synthesis method [A], For example, the compound etc. which are shown by following General formula (11) can be mentioned.
^{_{H- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (11)
In the formula, R ¹ , R ² , a, b, m and Y are the same as those described above.

Among these, from the viewpoint of easy availability, a compound represented by the following general formula (12) is preferably used.
_{^{H-Si (R 2) 3}} -a (Y) a (12)
In the formula, R ² , Y and a are the same as those described above.

In the synthesis method [A], when the hydrosilane compound having the crosslinkable silyl group is added to the alkenyl group of the polymer, a transition metal catalyst is usually used as a hydrosilylation catalyst.

The transition metal catalyst is not particularly limited. For example, a platinum solid dispersed in a carrier such as platinum alone, alumina, silica, carbon black; chloroplatinic acid; chloroplatinic acid and alcohol, aldehyde, ketone, etc. complex; platinum - olefin complexes, platinum (0) - divinyltetramethyldisiloxane _{complex; RhCl (PPh 3) 3,} RhCl 3, RuCl 3, IrCl 3, FeCl 3, AlCl 3, PdCl 2 · H 2 O, NiCl 2 And compounds other than platinum compounds such as TiCl ₄ . These may be used alone or in combination of two or more.

In the synthesis method [B], the method for synthesizing the vinyl polymer having at least one hydroxyl group, which is also used in the methods [Ag] to [Aj], is not particularly limited. [Ba] to [Bi] described in the above.

[Ba] When synthesizing a vinyl polymer by radical polymerization, a compound having both a polymerizable alkenyl group and a hydroxyl group represented by the following general formula (13) and the like is reacted with a predetermined vinyl monomer. Method.
_{^{H 2 C = C (R 3}} ) -R 4 -R 5 -OH (13)
In the formula, R ³ , R ⁴ and R ⁵ are the same as those described above.

The timing of reacting the compound having both the polymerizable alkenyl group and the hydroxyl group is not particularly limited. However, when the obtained crosslinked product is expected to have rubber-like properties, it may be the living radical polymerization, the end of the polymerization reaction or It is preferable to react as the second monomer after completion of the reaction of the predetermined vinyl monomer.

[Bb] When synthesizing a vinyl polymer 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 the above-mentioned vinyl monomer is radically polymerized using a large amount of a hydroxyl group-containing chain transfer agent such as a hydroxyl group-containing polysulfide by a method as disclosed in JP-A-5-262808.

[Bd] A method in which the vinyl monomer is radically polymerized using hydrogen peroxide or a hydroxyl group-containing initiator by the methods disclosed in JP-A-6-239912, JP-A-8-283310, and the like.

[Be] A method in which a vinyl monomer is radically polymerized by using an excessive amount of alcohol by a method disclosed in JP-A-6-116312.

[Bf] The halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond is hydrolyzed or reacted with a hydroxyl group-containing compound by the method disclosed in JP-A-4-132706. To introduce a hydroxyl group into the terminal.

[Bg] A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having a hydroxyl group represented by the following general formula (14), etc. A method of substitution with a hydroxyl group-containing substituent.
^{M + C - (R 7)} (R 8) -R 9 -OH (14)
In the formula, R ⁷ , R ⁸ and R ⁹ are the same as those described above. As the electron withdrawing group for R ⁷ and R ⁸ , —CO ₂ R, —C (O) R and —CN are preferable. Here, R is the same as described above.

[Bh] An enolic anion prepared by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a metal alone or an organometallic compound such as zinc, an aldehyde or a ketone How to react.

[Bi] A vinyl polymer having at least one highly reactive carbon-halogen bond is represented by a hydroxyl group-containing oxyanion represented by the following general formula (15) or the following general formula (16) A method of reacting a hydroxyl group-containing carboxylate anion to replace the halogen with a hydroxyl group-containing substituent.
HO—R ¹⁰ —O ^— M ⁺ (15)
In the formula, R ¹⁰ and M ⁺ are the same as those described above.
^{HO-R 11 -C (O)} O - M + (16)
In the formula, R ¹¹ and M ⁺ are the same as those described above.

In the method for synthesizing a vinyl polymer having at least one hydroxyl group, when a halogen atom is not directly involved in introducing a hydroxyl group such as [Ba] to [Be], the living radical polymerization method is used. It is preferable to use it. In this case, the method [Bb] is more preferable because the control is easier. Among the living radical polymerization methods, the atom transfer radical polymerization method is more preferable.

In addition, when the hydroxyl group is introduced by converting the halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, such as the methods [Bf] to [Bi] described above. Is obtained by radical polymerization (atom transfer radical polymerization method) using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, and has at least one highly reactive carbon-halogen bond at the terminal. It is preferable to use a vinyl polymer having the same. In this case, the method [Bi] is more preferable because control is easier.

The compound having a functional group capable of reacting with a hydroxyl group such as a crosslinkable silyl group and an isocyanate group used in the synthesis method [B] is not particularly limited. For example, γ-isocyanatopropyltrimethoxysilane, γ-isocyanate. Examples thereof include propylmethyldimethoxysilane and γ-isocyanatopropyltriethoxysilane. These may be used alone or in combination of two or more.

Moreover, in the case of reaction in the said synthesis method [B], the catalyst of a well-known urethanation reaction can also be used if necessary.

The compound having both a polymerizable alkenyl group and a crosslinkable silyl group used in the synthesis method [C] is not particularly limited, and examples thereof include trimethoxysilylpropyl (meth) acrylate and methyldimethoxysilylpropyl (meth) acrylate. The compound etc. which are represented with the following general formula (17) can be mentioned.
_{^{H 2 C = C (R 3}} ) -R 4 -R 12 - [Si (R 1) 2-b (Y) b O] m -Si (R 2) 3-a (Y) a (17)
In the formula, R ¹ , R ² , R ³ , R ⁴ , Y, a, b and m are the same as those described above. R ¹² represents a direct bond or a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds. These may be used alone or in combination of two or more.

In the synthesis method [C], the timing for reacting the compound having the polymerizable alkenyl group and the crosslinkable silyl group is not particularly limited. However, when the obtained crosslinked product is expected to have rubber-like properties, a living radical is used. In the polymerization, it is preferable to react as the second monomer at the end of the polymerization reaction or after completion of the reaction of the predetermined vinyl monomer.

The chain transfer agent having a crosslinkable silyl group used in the synthesis method [D] is not particularly limited, and is disclosed in, for example, Japanese Patent Publication Nos. 3-14068 and 4-55444. And mercaptans having a crosslinkable silyl group, hydrosilanes having a crosslinkable silyl group, and the like.

Compound having both a polymerizable alkenyl group and a crosslinkable silyl group represented by the general formula (17) together with a chain transfer agent having a crosslinkable silyl group and a predetermined vinyl monomer when radically polymerizing the vinyl monomer The amount of the crosslinkable silyl group introduced can be adjusted by reacting. Further, in order to increase the introduction rate of the crosslinkable silyl group, a radical initiator having a crosslinkable silyl group may be used in combination.

In the synthesis method [E], at least a highly reactive carbon-halogen bond used also in the methods [Ac] to [Af] and [Bf] to [Bi] is used. The method for synthesizing one vinyl polymer is not particularly limited, and examples thereof include the following methods [Ea] and [Eb].

[Ea] Radical polymerization using a halide such as carbon tetrachloride, ethylene chloride, carbon tetrabromide or methylene bromide as a chain transfer agent by the method disclosed in JP-A-4-132706. Method to perform (chain transfer agent method).

[Eb] An atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst.

It does not specifically limit as a stabilized carbanion which has a crosslinkable silyl group used in the said synthesis method [E], The compound etc. which are represented by following General formula (18) can be mentioned.
^{M + C - (R 7)} (R 8) -R 13 -C (H) (R 14) -CH 2 - [Si (R 1) 2-b (Y) b O] m -Si (R 2) _3-a (Y) _a (18)
In the formula, R ¹ , R ² , R ⁷ , R ⁸ , Y, a, b and m are the same as those described above. R ¹³ represents a direct bond or a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds. R ¹⁴ 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 ⁷ and R ⁸ , —CO ₂ R, —C (O) R and —CN are preferable. Here, R is the same as described above.

When the cured product obtained by curing the curable composition of the first aspect of the present invention is particularly required to have rubber-like properties, the molecular weight between crosslinking points that greatly affects rubber elasticity can be increased. At least one of the groups is preferably at the end of the molecular chain. More preferably, all the crosslinkable silyl groups have 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.

Therefore, the vinyl polymer having at least one hydroxyl group, halogen or alkenyl group used when synthesizing the vinyl polymer having at least one crosslinkable silyl group has these functional groups at the molecular chain ends. Those are preferred.

In order to obtain a vinyl polymer having at least one crosslinkable silyl group at the molecular chain terminal using the “atom transfer radical polymerization method” more preferable among the “living radical polymerization methods”, as an initiator, It is preferable to use an organic halide or a sulfonyl halide compound having two or more starting points. The vinyl polymer having at least one highly reactive carbon-halogen bond at the molecular chain end thus obtained is converted into a vinyl polymer having at least one crosslinkable silyl group at the molecular chain end by the above-described method. It can be easily changed.

It does not specifically limit as an organic halide which has two or more of the said starting points, or a halogenated sulfonyl compound, For example, the following compound can be mentioned.
_{o-, m-, p-XCH 2} -C 6 H 4 -CH 2 X, o-, m-, p-CH 3 C (H) (X) -C 6 H 4 -C (H) (X) CH ₃ , o-, m-, p- (CH ₃ ) ₂ C (X) —C ₆ H ₄ —C (X) (CH ₃ ) ₂ (wherein C ₆ H ₄ represents a phenylene group. X represents chlorine, bromine or iodine)
_{RO 2 C-C (H)} (X) - (CH 2) n -C (H) (X) -CO 2 R, RO 2 C-C (CH 3) (X) - (CH 2) n -C _{(CH 3) (X) -CO} 2 R, RC (O) -C (H) (X) - (CH 2) n -C (H) (X) -C (O) R, RC (O) - _{C (CH 3) (X)} - (CH 2) n -C (CH 3) (X) -C (O) R ( in the formula, R represents an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group N represents an integer of 0 to 20, and X represents chlorine, bromine, or iodine.
_{XCH 2 -C (O) -CH 2} X, H 3 C-C (H) (X) -C (O) -C (H) (X) -CH 3, (H 3 C) 2 C (X) _{-C (O) -C (X)} (CH 3) 2, C 6 H 5 C (H) (X) - (CH 2) n -C (H) (X) C 6 H 5 ( in the above formulas, X represents chlorine, bromine or iodine, and n represents an integer of 0 to 20)
_{XCH 2 CO 2 - (CH 2} ) n -OCOCH 2 X, CH 3 C (H) (X) CO 2 - (CH 2) n -OCOC (H) (X) CH 3, (CH 3) 2 C ( _{X) CO 2 - (CH 2} ) n -OCOC (X) (CH 3) ₂ above formulas, n is an integer of 1-20.
_{XCH 2 C (O) C (} O) CH 2 X, CH 3 C (H) (X) C (O) C (O) C (H) (X) CH 3, (CH 3) 2 C (X) _{C (O) C (O)} C (X) (CH 3) 2, o-, m-, p-XCH 2 CO 2 -C 6 H 4 -OCOCH 2 X, o-, m-, p-CH 3 _{C (H) (X) CO} 2 -C 6 H 4 -OCOC (H) (X) CH 3, o-, m-, p- (CH 3) 2 C (X) CO 2 -C 6 H 4 - _{OCOC (X) (CH 3)} 2, o-, m-, in _{p-XSO 2 -C 6 H 4} -SO 2 X above formulas, X is denotes chlorine, bromine, or iodine. Is mentioned. These may be used alone or in combination of two or more.

In addition, in order to obtain a vinyl polymer having a crosslinkable silyl group at both molecular chain ends, an organic halide or sulfonyl halide compound having two starting points is used as an initiator in the “atom transfer radical polymerization method”. In addition to the method using, a method using an organic halide having a crosslinkable silyl group (synthesis method [F]) is also preferable.

It does not specifically limit as said organic halide which has a crosslinkable silyl group, For example, the compound etc. which are represented with the following general formula (19) or (20) can be mentioned.
^{R 15 R 16 C (X)} -R 17 -R 18 -C (H) (R 19) CH 2 - [Si (R 1) 2-b (Y) b O] m -Si (R 2) 3- _a (Y) _a (19)
In the formula, R ¹ , R ² , a, b, m, X and Y are the same as those described above. R ¹⁵ and R ¹⁶ are the same or different and each represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. R ¹⁵ and R ¹⁶ may be connected to each other at the other end. R ¹⁷ represents —C (O) O—, —C (O) —, or o-, m-, p-phenylene group. R ¹⁸ represents a direct bond or a divalent organic group having 1 to 10 carbon atoms which may contain one or more ether bonds. R ¹⁹ 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.
_{^{(R 2) 3-a (}} Y) a Si- [OSi (R 1) 2-b (Y) b] m -CH 2 -C (H) (R 19) -R 18 -C (R 15) ( X) -R ¹⁷ -R ¹⁶ (20)
In the formula, R ¹ , R ² , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , a, b, m, X and Y are the same as those described above.

When the above-mentioned “atom transfer radical polymerization method” is performed using the organic halide having a crosslinkable silyl group as an initiator, a carbon-halogen having a crosslinkable silyl group at one end and a high reactivity at the other end. A vinyl polymer having a bond is obtained. A vinyl polymer having a crosslinkable silyl group at both molecular chain ends can be obtained by converting the terminal halogen atom of this vinyl polymer into a crosslinkable silyl group-containing substituent using the method described above.

The crosslinkable silyl group can also be obtained by coupling the halogen atoms of the vinyl polymer with a compound having two or more of the same or different functional groups that can replace the halogen atom at the terminal end. Can be obtained at both molecular chain terminals.

The compound having two or more of the same or different functional groups that can replace the halogen atom at the terminal end is not particularly limited, and examples thereof include polyols, polyamines, polycarboxylic acids, polythiols, salts thereof; alkali metal sulfides, etc. Can give.

Further, in the above “atom transfer radical polymerization method”, when an organic halide having an alkenyl group is used as an initiator, a vinyl polymer having an alkenyl group at one end and a halogen atom at the other end can be obtained. If the halogen atom at the terminal of this vinyl polymer is converted into an alkenyl-containing substituent using the method described above, a vinyl polymer having an alkenyl group at both molecular chain terminals can be obtained. If these alkenyl groups are converted into a crosslinkable silyl group by the above-described method or the like, a vinyl polymer having the crosslinkable silyl group at both molecular chain ends can be obtained.

The vinyl polymer having at least one crosslinkable silyl group at the end of the molecular chain can be obtained by combining the above-described methods and the like as needed, but the following synthesis examples A and B can be given as typical synthesis steps. it can.
Synthesis process A
(1) A step of synthesizing a vinyl polymer having a halogen atom at the terminal by polymerizing a vinyl monomer by an atom transfer radical polymerization method, (2) A terminal having the halogen atom obtained in the above step (1) A step of synthesizing a vinyl polymer having an alkenyl group at a terminal by reacting a vinyl polymer with an oxyanion having an alkenyl group to substitute a halogen, and (3) obtained in the step (2). By adding a hydrosilane compound having a crosslinkable silyl group represented by the general formula (1) to a terminal alkenyl group of a vinyl polymer having an alkenyl group at the terminal, a substituent containing a crosslinkable silyl group is added. A synthesis process consisting of a conversion process.

Synthesis process B
(1) A step of forming a vinyl polymer by polymerizing a vinyl monomer by a living radical polymerization method, and (2) a terminal compound by reacting with a compound having at least two alkenyl groups having low polymerizability. (3) synthesizing a vinyl polymer having an alkenyl group at the terminal, and (3) an alkenyl group at the terminal of the vinyl polymer having an alkenyl group at the terminal obtained in the above step (2) by the general formula (1) A synthesis step comprising a step of converting a substituent containing a crosslinkable silyl group by adding a hydrosilane compound having a crosslinkable silyl group.

[(B) Component Photocurable Material] The (B) component photocurable material used in the first aspect of the present invention is such that the molecular structure undergoes a chemical change in a short time due to the action of light, such as curing. It causes a change in physical properties. The photocurable substance (B) in the first aspect of the present invention is a substance that can be cured by exposure to light, but a typical photocurable substance is, for example, 1 at a position where the sun is exposed indoors (near the window). It is a substance that can be cured by standing at room temperature for days. 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 (21).
^{_{CH 2 = CHR 6 CO (O}} ) - (21)
In the formula, R ⁶ is the same as described above.

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 photocurable materials of the component (B), unsaturated acrylic compounds are preferable because they are easy to handle.

The component (B) 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 having a crosslinkable silyl group as the component (A1). 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.

[Regarding Optional Components] In the curable composition of the first present invention, a curing catalyst or a curing agent may be required. Moreover, you may add various compounding agents according to the target physical property.

<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 such as: tetrabutyl titanate, tetrapropyl titanate, etc .; aluminum trisacetylacetonate, aluminum trisethylacetoacetate, Organoaluminum compounds such as isopropoxyaluminum ethyl acetoacetate; Chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; Lead octylate; Butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine , Triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo 5,4,0) amine compounds such as undecene-7 (DBU), or salts of these amine compounds with carboxylic acids, etc .; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; excess A reaction product of a polyamine and an epoxy compound; a silane coupling agent having an amino group such as γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane; a silanol condensation catalyst such as Examples include other known silanol condensation catalysts such as 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 with respect to 100 parts (parts by weight, hereinafter the same) of the vinyl polymer (A1) having at least one crosslinkable silyl group. Is more preferable. 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 amount of the silanol condensation catalyst exceeds this range, local heat generation and foaming will occur during curing, and it will be difficult to obtain a good cured product, and the pot life will be too short, which is preferable from the viewpoint of workability. Absent.

In the curable composition of the first invention, in order to further increase the activity of the condensation catalyst, the general formula (22)
R ⁴⁹ _a Si (OR ⁵⁰ ) _4-a (22)
(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.) You may add the silicon compound which does not have a silanol group shown by these.

Examples of the silicon compound include, but are not limited to, R ^{49 in} the general formula (22) 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 compounding amount of the silicon compound is preferably about 0.01 to 20 parts, more preferably 0.1 to 10 parts with respect to 100 parts of the vinyl polymer (A1) having at least one crosslinkable silyl group. When the compounding amount of the silicon compound is below this range, the effect of accelerating the curing reaction may be reduced. On the other hand, when the compounding amount of the silicon compound exceeds this range, the hardness and tensile strength of the cured product may decrease.

<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. Specific examples of the silane coupling agent include isocyanate group-containing silanes such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatopropylmethyldimethoxysilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- ( 2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ-ureido Amino group-containing silanes such as propyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane Epoxy group-containing silanes such as lan; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane, etc. Carboxysilanes of vinyl type; vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyltriethoxysilane; γ-chloropropyltri Halogen-containing silanes such as methoxysilane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate; In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, and the like, which are derivatives of these, can also be used as silane coupling agents. .

The silane coupling agent used for this invention is normally used in 0.1-20 parts with respect to 100 parts of crosslinkable silyl group containing polymers (A1). 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 on organic substrates such as polyethylene, polypropylene, polycarbonate, etc., it exhibits a significant adhesive improvement effect under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving the 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.

<Filler>
Various fillers are used in the curable composition of the present invention as needed. Specific examples of the filler include, for example, wood powder, parv, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, rice husk powder, graphite, diatomaceous earth, white clay, fumed silica, sedimentation Reinforcing fillers such as silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, Fillers such as organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, zinc dust and shirasu balloon; fibrous fillers such as asbestos, glass fiber and filament It is done. 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. 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. These fillers may be used alone or in combination of two or more. Although the usage-amount in the case of using a filler is not limited, 10-1000 parts are preferable with respect to 100 parts of vinyl polymer (A1), and 50-300 parts are more preferable.

<Plasticizer>
Various plasticizers are used in the curable composition of the present invention as necessary. 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; Chlorinated paraffins; Alkyldiphenyl Partially hydrogenated terphenyl and other hydrocarbon oils; Process oils; Polyethers such as polyethylene glycol and polypropylene glycol; Epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate; Polyester plasticizers, etc. Can be used alone or in admixture of two or more, but this is not always necessary. These plasticizers can also be blended at the time of polymer production.

<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.

<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.

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, ultraviolet absorbers, metal deactivators, ozone degradation inhibitors, light stabilizers, phosphorous peroxides. Examples include oxide decomposing agents, lubricants, pigments, foaming agents, and photocurable resins. These various additives may be used alone or in combination of two or more. Specific examples of such additives are described in, for example, each specification 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 can also be prepared as a one-component type in which all the blended components are pre-blended and sealed and cured by moisture in the air after construction. It is also possible to prepare a two-component type in which components such as a plasticizer and water are blended and the compounding material and the polymer composition are mixed before use.

[Usage]
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 electric / electronic component materials such as a solar cell back surface sealing material, insulation for electric wires and cables. Electrical insulating 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 rust-proof and waterproof sealing materials for meshed glass and laminated glass end faces (cut parts).

<About the Second Invention>
Next, the curable composition of the second invention will be described in detail. The curable composition of the second aspect of the present invention comprises a vinyl polymer having a crosslinkable silyl group as component (A2) and an air oxidation curable material as component (C). Here, the vinyl polymer as the component (A2) is the same as the vinyl polymer (A1) described above.

[Air oxidation curable substance of component (C)]
The air oxidation curable substance of component (C) used in the second present invention is a compound having an unsaturated group that can be crosslinked and cured by oxygen in the air. The air oxidation curable substance (C) in the second aspect of the present invention is a substance that can be cured by contact with air, and more specifically, has a property of curing by reacting with oxygen in the air. is there. 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 tung 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 component (C) 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 having a crosslinkable silyl group as the component (A2). 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.

To the curable composition of the second invention, optional components similar to those described above for the first invention can be added.

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

The curable composition of the second aspect 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 multi-layer glass, and electric / electronic component materials such as a solar cell back surface sealing material, Electrical insulation materials such as insulation coating materials for cables, 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 rust-proof and waterproof sealing materials for meshed glass and laminated glass end faces (cut parts).

<About the Third Invention>
Next, the curable composition of 3rd this invention is explained in full detail. The curable composition of the third aspect of the present invention comprises a vinyl polymer having a crosslinkable functional group as the component (A3) and a polymer plasticizer as the component (D).

[Vinyl polymer of component (A3)]
The main chain of the vinyl polymer as the component (A3) and the production method thereof are the same as those of the vinyl polymer (A1) described above.

<Crosslinkable functional group>
The crosslinkable functional group of the vinyl polymer (A3) is not limited, but is preferably a crosslinkable silyl group, an alkenyl group, a hydroxyl group, an amino group, a polymerizable carbon-carbon double bond, an epoxy group, or the like. All of these crosslinkable functional groups can be used properly according to the use / purpose.

Number of crosslinkable functional groups On average, at least one crosslinkable functional group is present in one molecule of the polymer (A3). If this crosslinkable functional group has an average of less than 1 per molecule, a sufficient cured product cannot be obtained. The number of crosslinkable functional groups necessary to obtain a sufficient cured product is usually 1.1 to 5 on average per molecule, and preferably 1.2 to 4 on average. What has 1.3-3 on average is more preferable.

Position of the crosslinkable functional group When a rubber property is particularly required for a cured product obtained by curing the curable composition of the third invention, a crosslinking point that greatly affects rubber elasticity. Since the intermolecular weight can be increased, at least one of the crosslinkable functional groups is preferably at the end of the molecular chain. More preferably, all the crosslinkable functional groups have at the molecular chain ends.

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

Alkenyl group Although the alkenyl group in this invention is not limited, It is preferable that it is what is represented by General formula (23).
H ₂ C═C (R ¹¹ ) −
(23)
(Wherein R ¹¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms)

In the general formula (23), R ¹¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and specific examples thereof include the following groups.
_{- (CH 2) n -CH 3} , -CH (CH 3) - (CH 2) n -CH 3, -CH (CH 2 CH 3) - (CH 2) n -CH 3, -CH (CH 2 CH _{3) 2, -C (CH 3} ) 2 - (CH 2) n -CH 3, -C (CH 3) (CH 2 CH 3) - (CH 2) n -CH 3, -C 6 H 5, - _{C 6 H 5 (CH 3)} , - C 6 H 5 (CH 3) 2, - (CH 2) n -C 6 H 5, - (CH 2) n -C 6 H 5 (CH 3), - ( _{CH 2) n -C 6 H 5} (CH 3) 2 (n is an integer of 0 or more, and the total number of carbon atoms in each group is 20 or less)
Among these, a hydrogen atom is preferable.

Further, although not limited, it is preferable that the alkenyl group of the polymer (A3) is not activated by a carbonyl group, an alkenyl group, or an aromatic ring conjugated with the carbon-carbon double bond.

The bonding mode of the alkenyl group and the main chain of the polymer is not particularly limited, but is preferably bonded via a carbon-carbon bond, an ester bond, an ester bond, a carbonate bond, an amide bond, a urethane bond, or the like.

Amino group The amino group in the present invention is not limited, but is -NR ¹² ₂ (R ¹² is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and two R ¹² are May be the same or different, and may be linked to each other at the other end to form a cyclic structure.)-(NR ¹² ₃ ) ⁺ X ⁻ (R ¹² is hydrogen or It is a monovalent organic group having 1 to 20 carbon atoms, and two R ¹² may be the same or different from each other, and may be connected to each other at the other end to form a cyclic structure. X ^- is no problem even ammonium salt represented in counter anion)..

In the above formula, R ¹² is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, for example, hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 20 carbon atoms. And an aralkyl group. Two R ¹² may be the same as or different from each other. Further, they may be connected to each other at the other end to form an annular structure.

Polymerizable carbon - carbon double bond <br/> polymerizable carbon - groups having carbon double bond, preferably the general formula ^{(24): - OC (O} ) C (R 13) = CH 2 ( 24)
(Wherein, R ¹³ represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms), and more preferably, R ¹³ is hydrogen or a methyl group. It is a group.

In the general formula (24) ^is not particularly limited as specific examples of ^{R 13,} for _{example, -H, -CH 3, -CH 2} CH 3, - (CH 2) n CH 3 (n is an integer of 2 to 19 Represents —C ₆ H ₅ , —CH ₂ OH, —CN, and the like, preferably —H and —CH ₃ .

<Crosslinkable functional group introduction method>
Hereinafter, a method for introducing a functional group into a vinyl polymer will be described, but the method is not limited thereto. In order to introduce a crosslinkable silyl group, alkenyl group or hydroxyl group by terminal functional group conversion, the above-described method can be preferably used.

Epoxy group In the present invention, the vinyl polymer having an epoxy group is not limited, but includes the following steps: (1) A vinyl polymer is produced by polymerizing a vinyl monomer by a living radical polymerization method. And
(2) Subsequently, a compound having both an epoxy group and an ethylenically unsaturated group is reacted; Further, in atom transfer radical polymerization, there is a method in which allyl alcohol is reacted at the end of polymerization and then epoxy cyclized with a hydroxyl group and a halogen group.

Amino group Examples of the method for producing a vinyl polymer having at least one amino group at the end of the main chain include the following steps.
(1) A vinyl polymer having at least one halogen group at the end of the main chain is produced, and (2) the terminal halogen is converted to a substituent having an amino group using an amino group-containing compound.

Although it does not specifically limit as a substituent which has an amino group, Group shown by General formula (25) is illustrated.
—O—R ²⁶ —NR ¹² ₂ (25)
(In the formula, R ²⁶ represents a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds or ester bonds. R ¹² is hydrogen or monovalent having 1 to 20 carbon atoms. And two R ¹² may be the same or different from each other, and may be connected to each other at the other end to form a cyclic structure.)

In the general formula (25), R ²⁶ is a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds or ester bonds, for example, an alkylene group having 1 to 20 carbon atoms, Examples thereof include an arylene group having 6 to 20 carbon atoms and an aralkylene group having 7 to 20 carbon atoms, but —C ₆ H ₄ —R ²⁷ — (wherein C ₆ H ₄ is a phenylene group, and R ²⁷ is a direct bond. Or a divalent organic group having 1 to 14 carbon atoms which may contain one or more ether bonds or ester bonds.), Or —C (O) —R ²⁸ — (wherein R ²⁸ represents And a divalent organic group having 1 to 19 carbon atoms that may contain a direct bond or one or more ether bonds or ester bonds.

By converting the terminal halogen of the vinyl polymer, an amino group can be introduced at the end of the polymer. Although it does not specifically limit as a substitution method, The nucleophilic substitution reaction which uses an amino group containing compound as a nucleophile from the point that reaction is easy to control is preferable. Examples of such a nucleophile include a compound having both a hydroxyl group and an amino group represented by the general formula (26).
HO-R ²⁶ -NR ¹² ₂ (26)
(In the formula, R ²⁶ represents a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds or ester bonds. R ¹² is hydrogen or monovalent having 1 to 20 carbon atoms. And two R ¹² may be the same or different from each other, and may be connected to each other at the other end to form a cyclic structure.)

In the general formula (26), R ²⁶ is a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds or ester bonds, for example, an alkylene group having 1 to 20 carbon atoms, Examples thereof include an arylene group having 6 to 20 carbon atoms and an aralkylene group having 7 to 20 carbon atoms. Among these compounds having both a hydroxyl group and an amino group, R ²⁶ represents —C ₆ H ₄ —R ²⁷ — (wherein C ₆ H ₄ represents a phenylene group and R ²⁷ represents a direct bond or one or more ethers). An aminophenol represented by a divalent organic group having 1 to 14 carbon atoms which may contain a bond or an ester bond;
—C (O) —R ²⁸ — (wherein R ²⁸ represents a C 1-19 divalent organic group which may contain a direct bond or one or more ether bonds or ester bonds). The amino acids represented are preferred.

Specific examples of the compound include ethanolamine; o, m, p-aminophenol; o, m, p-NH ₂ —C ₆ H ₄ —CO ₂ H; glycine, alanine, aminobutanoic acid, and the like.

A compound having both an amino group and an oxyanion can also be used as a nucleophile. Although it does not specifically limit as such a compound, For example, the compound shown by General formula (27) is mentioned.
M ⁺ O ⁻ —R ²⁶ —NR ¹² ₂ (27)
(In the formula, R ²⁶ represents a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds or ester bonds. R ¹² is hydrogen or monovalent having 1 to 20 carbon atoms. And two R ^{12 s} may be the same as or different from each other, and may be linked to each other at the other end to form a cyclic structure, where M ⁺ is an alkali metal ion or 4 Represents a class ammonium ion.)

In the general formula (27), M ⁺ is a counter cation of the oxyanion and represents an alkali metal ion or a quaternary ammonium ion. Examples of the alkali metal ions include lithium ions, sodium ions, potassium ions, and the like, preferably sodium ions or potassium ions. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, trimethylbenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion, dimethylpiperidinium ion, and the like.

Of the compounds having both an amino group and an oxyanion, the salts of aminophenols represented by the general formula (28) or the general formula (29) are easily obtained because the substitution reaction can be easily controlled. The salts of the amino acids shown are preferred.
^{_{M + O - -C 6 H 4}} -R 27 -NR 12 2 (28)
M ⁺ O ⁻ —C (O) —R ²⁸ —NR ¹² ₂ (29)
(Wherein C ₆ H ₄ is a phenylene group, R ² is a direct bond or a divalent organic group having 1 to 14 carbon atoms which may contain one or more ether bonds or ester bonds, R ³ is A direct bond or a divalent organic group having 1 to 19 carbon atoms which may contain one or more ether bonds or ester bonds, R ¹² is hydrogen or a monovalent organic group having 1 to 20 carbon atoms. Two R ^{12 s} may be the same or different from each other, and may be connected to each other at the other end to form a cyclic structure, and M ⁺ is the same as above.)

Compounds having an oxyanion represented by general formulas (27) to (29) can be easily obtained by reacting the compound represented by general formula (26) with a basic compound.

Various compounds can be used as the basic compound. For example, sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, sodium tert-butoxide, potassium tert-butoxide, sodium carbonate, potassium carbonate, lithium carbonate, hydrogen carbonate Examples include sodium, sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, methyl lithium, ethyl lithium, n-butyl lithium, tert-butyl lithium, lithium diisopropylamide, lithium hexamethyldisilazide and the like. Although the usage-amount of the said base does not have a restriction | limiting in particular, It is 0.5-5 equivalent with respect to the said precursor, Preferably it is 0.8-1.2 equivalent.

Examples of the solvent used in the reaction of the precursor with the base include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated hydrocarbon systems such as methylene chloride and chloroform. Solvents; Ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; Alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, and tert-butyl alcohol; Nitriles such as acetonitrile, propionitrile, and benzonitrile Solvents; ester solvents such as ethyl acetate and butyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate; amide solvents such as dimethylformamide and dimethylacetamide; Sulfoxide solvents such as Sid the like. These can be used individually or in mixture of 2 or more types.

A compound having an oxyanion in which M ⁺ is a quaternary ammonium ion is obtained by preparing a compound in which M ⁺ is an alkali metal ion and allowing a quaternary ammonium halide to act on the compound. Examples of the quaternary ammonium halide include tetramethylammonium halide, tetraethylammonium halide, trimethylbenzylammonium halide, trimethyldodecylammonium halide, and tetrabutylammonium halide.

Various solvents may be used for the substitution reaction of the polymer terminal halogen. For example, hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated hydrocarbon solvents such as methylene chloride and chloroform; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; methanol, Alcohol solvents such as ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile, benzonitrile; ester solvents such as ethyl acetate, butyl acetate; ethylene carbonate, propylene Examples thereof include carbonate solvents such as carbonate; amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide. These can be used individually or in mixture of 2 or more types.

The reaction temperature can be 0-150 degreeC. Moreover, the usage-amount of an amino group containing compound is although it does not restrict | limit in particular, It is 1-5 equivalent with respect to a polymer terminal halogen, Preferably it is 1-1.2 equivalent.

In order to accelerate the nucleophilic substitution reaction, a basic compound may be added to the reaction mixture. Examples of such basic compounds include, in addition to those already exemplified, alkylamines such as trimethylamine, triethylamine and tributylamine; polyamines such as tetramethylethylenediamine and pentamethyldiethylenetriamine; and pyridine compounds such as pyridine and picoline.

When the amino group of the amino group-containing compound used for the nucleophilic substitution reaction affects the nucleophilic substitution reaction, it is preferably protected with an appropriate substituent. Examples of such substituents include benzyloxycarbonyl group, tert-butoxycarbonyl group, 9-fluorenylmethoxycarbonyl group and the like.

Further, a method of substituting the halogen terminal of the vinyl polymer with an azide anion and then reducing with LAH or the like can be mentioned.

Polymerizable carbon-carbon double bond The method for introducing the polymerizable carbon-carbon double bond into the vinyl polymer is not limited, and examples thereof include the following methods.
(1) A method for producing a vinyl polymer by replacing the halogen group with a compound having a radical polymerizable carbon-carbon double bond. As a specific example, a method of reacting a vinyl polymer having a structure represented by the general formula (30) with a compound represented by the general formula (31).
-CR ²⁹ R ³⁰ X
(30)
(In the formula, R ²⁹ and R ³⁰ are groups bonded to the ethylenically unsaturated group of the vinyl monomer. X represents chlorine, bromine or iodine.)
M ⁺ -OC (O) C (R ¹³ ) ═CH ₂ (31)
(In the formula, R ¹³ represents hydrogen or an organic group having 1 to 20 carbon atoms. M ⁺ represents an alkali metal or a quaternary ammonium ion.)

(2) A method of reacting a vinyl polymer having a hydroxyl group with a compound represented by the general formula (32).
XC (O) C (R ¹³ ) ═CH ₂ (32)
(In the formula, R ¹³ represents hydrogen or an organic group having 1 to 20 carbon atoms. X represents chlorine, bromine, or a hydroxyl group.)

(3) A method in which a diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group, and the remaining isocyanate group reacts with a compound represented by the general formula (33).
^{HO-R 31} - OC (O) C (R ¹³ ) ═CH ₂ (33)
(In the formula, R ¹³ represents hydrogen or an organic group having 1 to 20 carbon atoms. R ³¹ represents a divalent organic group having 2 to 20 carbon atoms.)

Each of these methods will be described in detail below. The method (1) will be described.
(1) A method of reacting a vinyl polymer having a terminal structure represented by the general formula (30) with a compound represented by the general formula (31).
-CR ²⁹ R ³⁰ X
(30)
(In the formula, R ²⁹ and R ³⁰ are groups bonded to the ethylenically unsaturated group of the vinyl monomer. X represents chlorine, bromine or iodine.)
M ⁺ -OC (O) C (R ¹³ ) ═CH ₂ (31)
(In the formula, R ¹³ represents hydrogen or an organic group having 1 to 20 carbon atoms. M ⁺ represents an alkali metal or a quaternary ammonium ion.)

The vinyl polymer having a terminal structure represented by the general formula (30) is a method of polymerizing a vinyl monomer using the above-described organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or Although it is produced by a method of polymerizing a vinyl monomer using a halogen compound as a chain transfer agent, the former is preferred.

As the compound represented by the general formula (31) is not particularly ^limited, specific examples of ^{R 13} are, for _{example, -H, -CH 3, -CH 2} CH 3, - (CH 2) n CH 3 (n It represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -CN, etc., and is preferably -H, -CH _3.

M ⁺ is a counter cation of an oxyanion, and examples of M ⁺ include alkali metal ions, specifically lithium ions, sodium ions, potassium ions, and quaternary ammonium ions. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion, dimethylpiperidinium ion, and the like, preferably sodium ion and potassium ion.

The usage-amount of the oxyanion of General formula (31) becomes like this. Preferably it is 1-5 equivalent with respect to the halogen group of General formula (30), More preferably, it is 1.0-1.2 equivalent. The solvent for carrying out this reaction is not particularly limited but is preferably a polar solvent because it is a nucleophilic substitution reaction. For example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric Triamide, acetonitrile, etc. are used. Although the temperature which performs reaction is not limited, Generally it is 0-150 degreeC, In order to hold | maintain a polymeric terminal group, Preferably it carries out at room temperature-100 degreeC.

The method (2) will be described.
(2) A method of reacting a vinyl polymer having a hydroxyl group with a compound represented by the general formula (32).
XC (O) C (R ¹³ ) ═CH ₂ (32)
(In the formula, R ¹³ represents hydrogen or an organic group having 1 to 20 carbon atoms. X represents chlorine, bromine, or a hydroxyl group.)

As the compound represented by the general formula (32) is not particularly ^limited, specific examples of ^{R 13} are, for _{example, -H, -CH 3, -CH 2} CH 3, - (CH 2) n CH 3 (n It represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -CN, etc., and is preferably -H, -CH _3.

The vinyl polymer having a hydroxyl group, preferably at the terminal, is a method of polymerizing a vinyl monomer using the above-described organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or a compound having a hydroxyl group The chain transfer agent is used to polymerize vinyl monomers, and the former is preferred. The method for producing a vinyl polymer having a hydroxyl group by these methods is not limited, but the following methods are exemplified.

(A) When a vinyl polymer is synthesized by living radical polymerization, a compound having a polymerizable alkenyl group and a hydroxyl group in one molecule represented by the following general formula (34) is reacted as a second monomer. Method.
_{^{H 2 C = C (R 32}} ) -R 33 -R 34 -OH (34)
(In the formula, R ³² is an organic group having 1 to 20 carbon atoms, preferably hydrogen or methyl group, and may be the same as or different from each other. R ³³ is —C (O) O— (ester group), Or represents an o-, m-, or p-phenylene group, and R ³⁴ represents a direct bond or a divalent organic group having 1 to 20 carbon atoms which may have one or more ether bonds R ³³ ) Is an (meth) acrylate-based compound, and R ³³ is a styrene-based compound.

Although there is no limitation on the timing of reacting the compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule, particularly when a rubber-like property is expected, at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer, It is preferable to react as the second monomer.

(B) When synthesizing a vinyl polymer by living radical polymerization, the second monomer has a low polymerizable alkenyl group and hydroxyl group as the second monomer after the end of the polymerization reaction or after completion of the reaction of the predetermined monomer. A method of reacting a compound.

Although it does not specifically limit as such a compound, The compound etc. which are shown by General formula (35) are mentioned.
_{^{H 2 C = C (R 32}} ) -R 35 -OH (35)
(In the formula, R ³² is the same as described above. R ³⁵ represents a C 1-20 divalent organic group which may contain one or more ether bonds.)

Although it does not specifically limit as a compound shown by the said General formula (35), From an easy acquisition, alkenyl alcohol like 10-undecenol, 5-hexenol, and allyl alcohol is preferable.

(C) A vinyl system having at least one carbon-halogen bond represented by the general formula (30) obtained by atom transfer radical polymerization by a method as disclosed in JP-A-4-132706. A method of introducing a hydroxyl group into a terminal by hydrolyzing or reacting a halogen of a polymer with a hydroxyl group-containing compound.

(D) A vinyl polymer having at least one carbon-halogen bond represented by the general formula (30) obtained by atom transfer radical polymerization and having a hydroxyl group as listed in the general formula (36). A method of replacing halogen by reacting a carbanion.
^{M + C - (R 36)} (R 37) -R 35 -OH (36)
(Wherein, R ³⁵ are the same as those described above .R ³⁶ and R ³⁷ together carbanion C ^- an electron-withdrawing group stabilizing or one of the electron-withdrawing several other is hydrogen or a carbon in the group 1 to 10, And an electron withdrawing group of R ³⁶ and R ³⁷ includes —CO ₂ R (ester group), —C (O) R (keto group), —CON (R ₂ ) (amide group) ), - COSR (thioester group), - CN (nitrile group), -. NO ₂ (nitro group), etc. the substituent R is an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms An aralkyl group having 7 to 20 carbon atoms, preferably an alkyl group or phenyl group having 1 to 10 carbon atoms, and R ³⁶ and R ³⁷ include —CO ₂ R, —C (O) R and —CN, Especially preferred Yes.)

(E) A vinyl polymer having at least one carbon-halogen bond represented by the general formula (30) obtained by atom transfer radical polymerization is allowed to react with a metal simple substance or an organometallic compound such as zinc, for example. A method in which a rate anion is prepared and then an aldehyde or a ketone is reacted.

(F) a hydroxyl group-containing oxyanion represented by the following general formula (37) or the like, or a general polymer represented by the following general formula (37) A method of reacting a hydroxyl group-containing carboxylate anion represented by the formula (38) or the like to substitute the halogen with a hydroxyl group-containing substituent.
HO-R ^{< 35 >} -O ^- M ^<+> (37)
(Wherein R ³⁵ and M ⁺ are the same as those described above.)
^{HO-R 35 -C (O)} O - M + (38)
(Wherein R ³⁵ and M ⁺ are the same as those described above.)

In the present invention, when halogen is not directly involved in the method of introducing a hydroxyl group as in (a) to (b), the method of (b) is more preferable because control is easier. In addition, when a hydroxyl group is introduced by converting a halogen of a vinyl polymer having at least one carbon-halogen bond such as (c) to (f), control of (f) is easier. The method is further preferred.

The method (3) will be described.
(3) A method in which a diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group, and the residual isocyanate group reacts with a compound represented by the general formula (39).
^{HO-R 31} - OC (O) C (R ¹³ ) ═CH ₂ (39)
(In the formula, R ¹³ represents hydrogen or an organic group having 1 to 20 carbon atoms. R ³¹ represents a divalent organic group having 2 to 20 carbon atoms.)

As the compound represented by the general formula (39) is not particularly ^limited, specific examples of ^{R 13} are, for _{example, -H, -CH 3, -CH 2} CH 3, - (CH 2) n CH 3 (n It represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -CN, etc., and is preferably -H, -CH _3. A specific compound includes 2-hydroxypropyl methacrylate.

The vinyl polymer having a hydroxyl group at the terminal is as described above. The diisocyanate compound is not particularly limited, and any conventionally known diisocyanate compound can be used. For example, toluylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethyl diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1 , 5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and the like; and the like. These can be used alone or in combination of two or more. Moreover, you may use block isocyanate.

In order to make better weather resistance, it is preferable to use a diisocyanate compound having no aromatic ring such as hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate as the polyfunctional isocyanate compound (b).

[Polymer plasticizer of component (D)]
The polymer plasticizer of the component (D) used in the third invention is a polymer having a number average molecular weight of 500 to 15000. By adding this polymer plasticizer, the viscosity and slump property of the curable composition and Mechanical properties such as tensile strength and elongation of the cured product obtained by curing the composition can be adjusted, and compared with the case of using a low molecular plasticizer that is a plasticizer that does not contain a polymer component in the molecule. The initial physical properties can be maintained over a long period of time, and the drying property (also referred to as paintability) when an alkyd paint is applied to the cured product can be improved. In addition, the polymer plasticizer by 3rd this invention does not have group represented by the said General formula (1).

The number average molecular weight of the polymer plasticizer is 500 to 15000, preferably 800 to 10000, and more preferably 1000 to 8000. If the molecular weight is too low, the plasticizer will flow 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.

Specific examples of such polymer plasticizers include, for example, vinyl polymers obtained by polymerizing the aforementioned vinyl monomers by various methods; two bases such as sebacic acid, adipic acid, azelaic acid, and phthalic acid. Polyester plasticizers obtained from acids and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol; polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and these polyether polyols Polyethers such as derivatives obtained by converting hydroxyl groups of ester groups to ether groups; polystyrenes such as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylic Nitrile, polychloroprene, although paraffin chloride and the like, but is not limited thereto.

Among these polymer plasticizers, those compatible with the crosslinkable functional group-containing polymer of the component (A3) are preferable. 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. The polymer synthesis method is preferably a living radical polymerization method and more preferably an atom transfer radical polymerization method because the molecular weight distribution is narrow and viscosity can be lowered.

The molecular weight distribution of the component (D) polymeric plasticizer is not particularly limited, but is preferably narrow and 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 said polymeric plasticizer may be used independently and may use 2 or more types together. Moreover, you may use together with a low molecular plasticizer in the range which does not have a bad influence on a physical property if needed.

The amount of the polymer plasticizer used as the component (D) is 5 to 150 parts by weight, preferably 10 to 120 parts per 100 parts by weight of the vinyl polymer having at least one crosslinkable functional group as the component (A3). Part by weight, more preferably 20 to 100 parts by weight. 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.

The curable composition of the third aspect of the present invention may require a curing catalyst or a curing agent depending on each crosslinkable functional group. Moreover, you may add various compounding agents according to the target physical property.

<Curing catalyst and curing agent>
In the case of a crosslinkable silyl group A 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 those described above.

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 with respect to 100 parts (parts by weight, hereinafter the same) of the vinyl polymer (A3) having at least one crosslinkable silyl group. Is more preferable. 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 amount of the silanol condensation catalyst exceeds this range, local heat generation and foaming will occur during curing, and it will be difficult to obtain a good cured product, and the pot life will be too short, which is preferable from the viewpoint of workability. Absent.

In the curable composition of the present invention, in order to further increase the activity of the condensation catalyst, the general formula (40)
R ⁴⁹ _a Si (OR ⁵⁰ ) _4-a (40)
(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.) You may add the silicon compound which does not have a silanol group shown by these.

Examples of the silicon compound include, but are not limited to, R ^{49 in} the general formula (40) 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 compounding amount of the silicon compound is preferably about 0.01 to 20 parts, more preferably 0.1 to 10 parts with respect to 100 parts of the vinyl polymer (A3) having at least one crosslinkable silyl group. When the compounding amount of the silicon compound is below this range, the effect of accelerating the curing reaction may be reduced. On the other hand, when the compounding amount of the silicon compound exceeds this range, the hardness and tensile strength of the cured product may decrease.

In the case of an alkenyl group When crosslinking is performed using an alkenyl group, it is not limited, but it is preferable to crosslink by a hydrosilylation reaction using a hydrosilyl group-containing compound as a curing agent and a hydrosilylation catalyst.

The hydrosilyl group-containing compound is not particularly limited as long as it is a hydrosilyl group-containing compound that can be cured by crosslinking with a polymer having an alkenyl group, and various compounds can be used. For example, a linear polysiloxane represented by the general formula (41) or (42);
^{_{R 51 3 SiO- [Si (R}} 51) 2 O] a - [Si (H) (R 52) O] b - [Si (R 52) (R 53) O] c -SiR 51 3 (41)
HR ⁵¹ ₂ SiO- [Si (R ⁵¹ ) ₂ O] _a- [Si (H) (R ⁵² ) O] _b- [Si (R ⁵² ) (R ⁵³ ) O] _c -SiR ⁵¹ ₂ H (42)
(In the formula, R ⁵¹ and R ⁵² represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ⁵³ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group. A represents 0 ≦ a ≦ 100, b Represents an integer satisfying 2 ≦ b ≦ 100 and c represents 0 ≦ c ≦ 100.) Cyclic siloxane represented by the general formula (43);

In the formula, R ⁵⁴ and R ⁵⁵ represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ⁵⁶ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group. d represents an integer of 0 ≦ d ≦ 8, e represents 2 ≦ e ≦ 10, f represents an integer of 0 ≦ f ≦ 8, and satisfies 3 ≦ d + e + f ≦ 10. ) And the like can be used.

These may be used alone or in combination of two or more. Among these siloxanes, from the viewpoint of compatibility with (meth) acrylic polymers, chain siloxanes represented by the following general formulas (44) and (45) having a phenyl group, and general formulas (46), ( The cyclic siloxane represented by 47) is preferred.
_{(CH 3) 3 SiO- [Si} (H) (CH 3) O] g - [Si (C 6 H 5) 2 O] h -Si (CH 3) 3 (44)
_{(CH 3) 3 SiO- [Si} (H) (CH 3) O] g - [Si (CH 3) {CH 2 C (H) (R 57) C 6 H 5} O] h -Si (CH 3 ₃ (45)
(In the formula, R ⁵⁷ represents hydrogen or a methyl group. G represents an integer of 2 ≦ g ≦ 100 and h represents an integer of 0 ≦ h ≦ 100. C ₆ H ₅ represents a phenyl group.)

(In the formula, R ⁵⁷ represents hydrogen or a methyl group. I represents an integer satisfying 2 ≦ i ≦ 10, j represents 0 ≦ j ≦ 8, and 3 ≦ i + j ≦ 10. C ₆ H ₅ represents a phenyl group. Is shown.)

Further, as the hydrosilyl group-containing compound, the hydrosilyl group-containing compound represented by the general formulas (41) to (47) may be partially modified even after the reaction with respect to a low molecular compound having two or more alkenyl groups in the molecule. A compound obtained by addition reaction such that a hydrosilyl group remains can also be used. Various compounds can be used as the compound having two or more alkenyl groups in the molecule. For example, hydrocarbon compounds such as 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, O, O Ether compounds such as' -diallyl bisphenol A, 3,3'-diallyl bisphenol A, ester compounds such as diallyl phthalate, diallyl isophthalate, triallyl trimellitate, tetraallyl pyromellitate, carbonates such as diethylene glycol diallyl carbonate System compounds.

It is possible to obtain the compound by slowly dropping the above-mentioned alkenyl group-containing compound in the presence of a hydrosilylation catalyst with respect to the excessive amount of the hydrosilyl group-containing compound represented by the general formulas (41) to (47). it can. Of these compounds, the following are preferred in view of the availability of raw materials, the ease of removal of the excessively used siloxane, and the compatibility of the component (A) with the polymer.

The polymer and the curing agent can be mixed at an arbitrary ratio, but from the viewpoint of curability, the molar ratio of the alkenyl group to the hydrosilyl group is preferably in the range of 5 to 0.2, and 2.5 It is especially preferable that it is -0.4. When the molar ratio is 5 or more, curing is insufficient and only a cured product having low tackiness and a low strength can be obtained. When the molar ratio is less than 0.2, a large amount of active hydrosilyl groups remain in the cured product even after curing. Cracks and voids are generated, and a uniform and strong cured product cannot be obtained.

The curing reaction between the polymer and the curing agent proceeds by mixing and heating the two components, but a hydrosilylation catalyst can be added to advance the reaction more rapidly. Such hydrosilylation catalyst is not particularly limited, and examples thereof include radical initiators such as organic peroxides and azo compounds, and transition metal catalysts.

The radical initiator is not particularly limited, and examples thereof include di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di ( t-butylperoxy) -3-hexyne, dicumyl peroxide, t-butylcumyl peroxide, dialkyl peroxides such as α, α′-bis (t-butylperoxy) isopropylbenzene, benzoyl peroxide, p-chlorobenzoyl peroxide, m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diacyl peroxide such as lauroyl peroxide, peracid esters such as t-butyl perbenzoate, diisopropyl percarbonate, di-2-ethylhexyl percarbonate Peroxydicarbonate such as 1,1 Examples thereof include peroxyketals such as -di (t-butylperoxy) cyclohexane and 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane.

Also, it is not particularly limited as a transition metal catalyst, for example, platinum simple substance, alumina, silica, carbon black or the like dispersed in a platinum solid, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone, etc. And a platinum-olefin complex and a platinum (0) -divinyltetramethyldisiloxane complex. 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. These catalysts may be used alone or in combination of two or more. Although there is no restriction | limiting in particular as a catalyst amount, It is good to use in the range of 10 ^{< -1} > ^-10 <^-8> mol with respect to 1 mol of alkenyl groups of a vinyl type polymer (A3), Preferably it is 10 ^<-3 > ^-10 <^-6> mol. It is good to use in the range. If it is less than 10 ⁻⁸ mol, curing does not proceed sufficiently. Further, since the hydrosilylation catalyst is expensive, it is preferable not to use 10 ⁻¹ mol or more.

Although there is no restriction | limiting in particular about hardening temperature, Generally it is good to make it harden | cure at 0 to 200 degreeC, Preferably it is 30 to 150 degreeC, More preferably, it is 80 to 150 degreeC.

In the case of hydroxyl group A polymer having a hydroxyl group is uniformly cured by using a compound having two or more functional groups capable of reacting with the hydroxyl group as a curing agent. Specific examples of the curing agent include, for example, a polyisocyanate compound having two or more isocyanate groups in one molecule, an aminoplast resin such as methylolated melamine and an alkyl etherified product or a low-condensed product thereof, a polyfunctional carboxylic acid, and Examples thereof include halides thereof. In producing a cured product using these curing agents, an appropriate curing catalyst can be used.

In the case of an amino group A polymer having an amino group is uniformly cured by using a compound having two or more functional groups capable of reacting with the amino group as a curing agent. Specific examples of the curing agent include, for example, a polyisocyanate compound having two or more isocyanate groups in one molecule, an aminoplast resin such as methylolated melamine and an alkyl etherified product or a low-condensed product thereof, a polyfunctional carboxylic acid, and Examples thereof include halides thereof. In producing a cured product using these curing agents, an appropriate curing catalyst can be used.

In the case of an epoxy group The curing agent for a polymer having an epoxy group is not particularly limited. For example, aliphatic amines, alicyclic amines, aromatic amines; acid anhydrides; polyamides; imidazoles Amine imide, urea, melamine and its derivatives, polyamine salt, phenol resin, polymercaptan, polysulfide, aromatic diazonium salt, diallyl iodonium salt, triallyl sulfonium salt, triallyl selenium salt, etc. It is done.

In the case of a polymerizable carbon-carbon double bond A polymer having a polymerizable carbon-carbon double bond can be crosslinked by a polymerization reaction of the polymerizable carbon-carbon double bond. Examples of the crosslinking method include a method of curing with active energy rays and a method of curing with heat. In the active energy ray-curable composition, the photopolymerization initiator is preferably a photoradical initiator or a photoanion initiator. In the thermosetting composition, the thermal polymerization initiator is preferably selected from the group consisting of an azo initiator, a peroxide, a persulfate, and a redox initiator. Hereinafter, these crosslinking reactions will be described in detail.

When cross-linking a polymer having a polymerizable carbon-carbon double bond, a polymerizable monomer and / or oligomer or various additives may be used in combination depending on the purpose. As the polymerizable monomer and / or oligomer, a monomer and / or oligomer having a radical polymerizable group or a monomer and / or oligomer having an anion polymerizable group are preferable. Examples of radical polymerizable groups include acrylic functional groups such as (meth) acrylic groups, styrene groups, acrylonitrile groups, vinyl ester groups, N-vinylpyrrolidone groups, acrylamide groups, conjugated diene groups, vinyl ketone groups, vinyl chloride groups, and the like. Is mentioned. Especially, what has a (meth) acryl group is preferable. Examples of the anionic polymerizable group include a (meth) acryl group, a styrene group, an acrylonitrile group, an N-vinylpyrrolidone group, an acrylamide group, a conjugated diene group, and a vinyl ketone group. Among these, those having an acrylic functional group are preferable.

Specific examples of the monomer include (meth) acrylate monomers, cyclic acrylates, N-vinyl pyrrolidone, styrene monomers, acrylonitrile, N-vinyl pyrrolidone, acrylamide monomers, conjugated diene monomers, vinyl ketone monomers, and the like. It is done. Examples of (meth) acrylate monomers include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and compounds of the following formula. it can.

Styrene monomers include styrene and α-methylstyrene, acrylamide monomers include acrylamide, N, N-dimethylacrylamide, conjugated diene monomers include butadiene and isoprene, and vinyl ketone monomers include methyl vinyl ketone. Etc.

Examples of polyfunctional monomers include neopentyl glycol polypropoxydiacrylate, trimethylolpropane polyethoxytriacrylate, bisphenol F polyethoxydiacrylate, bisphenol A polyethoxydiacrylate, dipentaerythritol polyhexanolide hexaacrylate, tris (hydroxy) Ethyl) isocyanurate polyhexanolide triacrylate, tricyclodecane dimethylol diacrylate 2- (2-acryloyloxy-1,1-dimethyl) -5-ethyl-5-acryloyloxymethyl-1,3-dioxane, tetra Bromobisphenol A diethoxydiacrylate, 4,4-dimercaptodiphenyl sulfide dimethacrylate, polytetraethylene glycol diacrylate, 1,9 Nonanediol diacrylate, and ditrimethylolpropane tetraacrylate.

As the oligomer, epoxy acrylate resins such as bisphenol A type epoxy acrylate resin, phenol novolac type epoxy acrylate resin, cresol novolak type epoxy acrylate resin, COOH group-modified epoxy acrylate type resin, polyol (polytetramethylene glycol, ethylene glycol and adipine) Acid polyester diol, ε-caprolactone-modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisobutylene, etc.) and organic isocyanates (tolylene diisocyanate, isophorone diisocyanate, diphenylmethane) Diisocyanate, hexamethylene diisocyanate (Hydroxylate, xylylene diisocyanate, etc.) Urethane resin obtained from hydroxyl group-containing (meth) acrylate {hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, etc.} Examples thereof include urethane acrylate resins obtained by the above, resins obtained by introducing (meth) acrylic groups into the above polyols through ester bonds, polyester acrylate resins, and the like.

These monomers and oligomers are selected depending on the initiator used and the curing conditions. Further, the number average molecular weight of the monomer and / or oligomer having an acrylic functional group is preferably 2000 or less, and more preferably 1000 or less, from the reason that the compatibility is good.

As a method for crosslinking a polymer having a polymerizable carbon-carbon double bond, it is preferable to use an active energy ray such as UV or electron beam.

In the case of crosslinking by active energy rays, it is preferable to contain a photopolymerization initiator. Although there is no restriction | limiting in particular as a photoinitiator used for this invention, A photoradical initiator and a photoanion initiator are preferable, and a photoradical initiator is especially preferable. For example, acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophene, 3-bromo Acetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone, 3-chloroxanthone 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoyl, benzoin methyl ether, benzoin butyl ether, bis (4-dimethyl) Minofeniru) ketone, benzyl methoxy ketal, 2-chlorothioxanthone tone, and the like. These initiators may be used alone or in combination with other compounds. Specifically, combinations with amines such as diethanolmethylamine, dimethylethanolamine, and triethanolamine, further combinations with iodonium salts such as diphenyliodonium chloride, and combinations with dyes and amines such as methylene blue are included. It is done.

Moreover, you may use a near-infrared light absorptive cationic dye as a near-infrared photoinitiator. As the near-infrared light-absorbing cationic dye, it is excited by light energy in the region of 650 to 1500 nm, for example, near-infrared light absorption disclosed in JP-A-3-111402, JP-A-5-194619, etc. It is preferable to use a cationic cationic dye-borate anion complex or the like, and it is more preferable to use a boron sensitizer together.

The addition amount of the photopolymerization initiator is not particularly limited since it only needs to slightly functionalize the system, but 0.001 to 10 parts by weight is preferable with respect to 100 parts of the polymer of the composition.

The method for curing the active energy ray-curable composition of the present invention is not particularly limited, but depending on the nature of the photopolymerization initiator initiator, a high-pressure mercury lamp, a low-pressure mercury lamp, an electron beam irradiation device, a halogen lamp, a light-emitting diode, Light and electron beam irradiation with a semiconductor laser or the like can be mentioned.

Further, it is preferable to use heat as a method for crosslinking the polymer having a polymerizable carbon-carbon double bond. When crosslinking by active energy rays, it is preferable to contain a thermal polymerization initiator. Although there is no restriction | limiting in particular as a thermal-polymerization initiator used for this invention, An azo initiator, a peroxide, a persulfuric acid, and a redox initiator are contained.

Suitable azo initiators include, but are not limited to, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (VAZO 33), 2,2'-azobis (2- Amidinopropane) dihydrochloride (VAZO 50), 2,2'-azobis (2,4-dimethylvaleronitrile) (VAZO 52), 2,2'-azobis (isobutyronitrile) (VAZO 64), 2, 2'-azobis-2-methylbutyronitrile (VAZO 67), 1,1-azobis (1-cyclohexanecarbonitrile) (VAZO 88) (all available from DuPont Chemical), 2,2'-azobis (2- Cyclopropylpropionitrile), 2,2'-azobis (methylisobutyrate) (V-601) (available from Wako Pure Chemical Industries), etc. I can get lost.

Suitable peroxide initiators include, but are not limited to, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di (4-t-butylcyclohexyl). Peroxydicarbonate (Perkadox 16S) (available from Akzo Nobel), di (2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate (Lupersol 11) (available from Elf Atochem), t-butyl per Oxy-2-ethylhexanoate (Trigonox 21-C50) (available from Akzo Nobel), dicumyl peroxide, and the like.

Suitable persulfate initiators include, but are not limited to, potassium persulfate, sodium persulfate, and ammonium persulfate.

Suitable redox initiators include, but are not limited to, combinations of the above persulfate initiators with reducing agents such as sodium metabisulfite and sodium bisulfite; Examples include systems based on tertiary amines, such as systems based on benzoyl peroxide and dimethylaniline; and systems based on organic hydroperoxides and transition metals, such as systems based on cumene hydroperoxide and cobalt naphthate.

Other initiators include, but are not limited to, pinacol such as tetraphenyl 1,1,2,2-ethanediol.

A preferred thermal radical initiator is selected from the group consisting of azo initiators and peroxide initiators. More preferred are 2,2'-azobis (methylisobutylate), t-butyl peroxypivalate, and di (4-t-butylcyclohexyl) peroxydicarbonate, and mixtures thereof.

The thermal initiator used in the present invention is present in a catalytically effective amount, and such amount is typically, but not limited to, a polymer having an acrylic functional group at at least one end of the present invention. When the total amount of the combined monomer and other monomer and oligomer mixture is 100 parts by weight, it is about 0.01 to 5 parts by weight, more preferably about 0.025 to 2 parts by weight. If a mixture of initiators is used, the total amount of initiator mixture is as if only one initiator was used.

The method for curing the thermosetting composition of the present invention is not particularly limited, but the temperature varies depending on the type of the thermal initiator, the polymer (A3) and the compound to be added, but is usually 50 ° C. to 250 ° C. Within the range of ° C is preferred, and within the range of 70 ° C to 200 ° C is more preferred. The curing time varies depending on the polymerization initiator, monomer, solvent, reaction temperature, etc. used, but is usually in the range of 1 minute to 10 hours.

In addition, the additives mentioned as the adhesiveness-imparting agent, filler, physical property modifier, thixotropic property-imparting agent (anti-sagging agent), and other additives mentioned in the first aspect of the present invention can be similarly blended.

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

The curable composition of the third aspect 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 multi-layer glass, and electric / electronic component materials such as a solar cell back surface sealing material, Electrical insulation materials such as insulation coating materials for cables, 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 rust-proof and waterproof sealing materials for meshed glass and laminated glass end faces (cut parts).

<About the Fourth Invention>
Next, the curable composition of 4th this invention is explained in full detail. The curable composition of the fourth aspect of the present invention is a vinyl polymer having a crosslinkable silyl group as the component (A4) and a reactive plasticizer as a component (E) (generally also referred to as a reactive diluent). ).

[Vinyl polymer of component (A4)]
The component (A4) in the fourth aspect of the present invention is a vinyl polymer having an average of 1.1 or more crosslinkable silyl groups represented by the general formula (1) in one molecule, and has a siloxane bond. It forms and crosslinks and hardens. In addition, General formula (1) showing the crosslinkable silyl group in (A4) component is the same as General formula (1) showing the crosslinkable silyl group in (A1) component used by 1st this invention.

If the crosslinkable silyl group represented by the general formula (1) is less than 1.1 on average in one molecule, a sufficient cured product cannot be obtained. The number of crosslinkable silyl groups represented by the general formula (1) necessary for obtaining a sufficient cured product is usually 1.1 to 5 on average per molecule, and 1 on average. Those having 2 to 4 are preferred, and those having 1.3 to 3 on average are more preferred.

The monomer constituting the main chain is not particularly limited as long as it is a vinyl monomer, and examples thereof include those exemplified in the first aspect of the present invention. From the viewpoint of physical properties, the vinyl polymer having 1.1 or more crosslinkable silyl groups on average is obtained by synthesizing using 40% by weight or more of the (meth) acrylic acid monomer among the above monomers. Preferred is a (meth) acrylic polymer. Furthermore, an acrylic polymer obtained by synthesizing using 30% by weight or more of an acrylic acid monomer among the above monomers is more preferable.

The number average molecular weight of the vinyl polymer having 1.1 or more crosslinkable silyl groups on average is not particularly limited, but is preferably in the range of 500 to 100,000. When the molecular weight is 500 or less, the original characteristics of the vinyl polymer are hardly expressed, and when it is 100,000 or more, handling becomes difficult.

The molecular weight distribution of the vinyl polymer having 1.1 or more crosslinkable silyl groups on average, that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is not particularly limited. However, it is preferable that the molecular weight distribution is narrow in order to make the curable composition low in viscosity and facilitate handling, and to obtain sufficient cured product properties. The molecular weight distribution is preferably less than 1.8, more preferably 1.7 or less, still more preferably 1.6 or less, still more preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1. 3 or less. The molecular weight distribution is most commonly measured by gel permeation chromatography (GPC). Chloroform or THF is used as the mobile phase, and a polystyrene gel column is used as the column, and the number average molecular weight and the like can be determined by a value in terms of polystyrene.

The method for synthesizing the vinyl polymer having 1.1 or more crosslinkable silyl groups on average is not particularly limited, and various methods as described above in the first invention can be used. Among them, a synthesis method using living radical polymerization is preferable, and a synthesis method using atom transfer radical polymerization is more preferable. As a typical manufacturing process, the manufacturing process similar to the synthesis | combining process A and B of (A1) component mentioned above can be mentioned.

When rubber properties are particularly required for the cured product obtained from the curable composition according to the fourth aspect of the present invention, the molecular weight between crosslinking points that greatly affects rubber elasticity can be increased. On average, 1.1 or more are preferably at the ends of the molecular chain. More preferably, all the crosslinkable silyl groups have at the molecular chain ends.

[Reactive plasticizer of component (E)]
The reactive plasticizer which is a vinyl polymer having a crosslinkable silyl group represented by the general formula (1) having an average of 1 or less of the component (E) used in the fourth invention is A vinyl polymer having a crosslinkable silyl group represented by the general formula (1) only at the molecular chain terminal, that is, having a crosslinkable silyl group represented by the general formula (1) only at one molecular chain terminal. The other terminal is mainly composed of a vinyl polymer having no crosslinkable silyl group. The addition of the reactive plasticizer of component (E) can improve the workability during the blending process or curable composition construction, impart flexibility to the cured product, and suppress adverse effects due to plasticizer migration. Can do.

The number of crosslinkable silyl groups in the component (E) according to the fourth aspect of the present invention is set to “1 or less on average”, but this is a value that considers the inclusion of impurities that do not have a crosslinkable silyl group. It is. For example, even when a vinyl polymer having one crosslinkable silyl group is produced by the method shown below in the present specification, it is very difficult to avoid by-production of a vinyl polymer having no crosslinkable silyl group. difficult. Moreover, it is difficult (unlike low molecular weight compounds) to remove only those that do not have a crosslinkable silyl group from the reactive plasticizer that is a polymer. Therefore, the number of crosslinkable silyl groups in the reactive plasticizer is 1 or less on average. Furthermore, when the component (E) according to the fourth invention is specified by analysis, the number of crosslinkable silyl groups in the reactive plasticizer may be obtained only as an average value. The average value is adopted.

The reactive plasticizer of the component (E) according to the fourth invention has a crosslinkable silyl group only at one molecular chain end, so that it is different from the vinyl polymer of the component (A4) and is a crosslinked product alone. It is virtually impossible to form. However, when cured together with the component (A4), one molecular chain end having a crosslinkable silyl group reacts with the crosslinkable silyl group of the component (A4), so that the reactive plasticizer of the component (E) is the result. Is incorporated into the crosslinked product. However, since the component (E) has molecular chain terminals that are not incorporated into the crosslinks, this serves as a plasticizer. Since the component (E) is incorporated into the cured product by cross-linking, it is virtually not extracted to the outside environment such as water, oil, solvent, air, etc. Deterioration and contamination of the surrounding environment are less likely to occur.

A preferable crosslinkable silyl group of the reactive plasticizer of the component (E) is the same as that of the polymer of the component (A4).

As a vinyl-type monomer which comprises the principal chain of the reactive plasticizer of the said (E) component, the vinyl-type monomer which can be used by the above-mentioned (A1) component can be used. These may be used alone or in combination of two or more. However, since the component (E) is a vinyl polymer having a crosslinkable silyl group only at one molecular chain end, the crosslinkable silyl group is excluded except when a crosslinkable silyl group is introduced at the molecular chain end. Monomers contained cannot be used.

The reactive plasticizer of the component (E) is preferably a (meth) acrylic polymer obtained by synthesizing the above monomer using 40% by weight or more of a (meth) acrylic acid monomer. The reactive plasticizer of the component (E) is preferably an acrylic polymer obtained by synthesizing 30% by weight or more of an acrylic acid monomer among the above monomers.

The reactive plasticizer of the component (E) is preferably one that becomes liquid during the blending process or curable composition construction, and at this time, the viscosity is lower than that of the vinyl polymer having a crosslinkable silyl group of the component (A4). It is preferable that Moreover, what takes a compatible state or a micro phase-separation state when both are mixed is preferable.

The number average molecular weight of the reactive plasticizer as the component (E) is preferably 500 to 15000, and more preferably 800 to 10,000. Further, 1000 to 8000 is more preferable. When the molecular weight is lower than 500, the effect as a reactive plasticizer does not appear, and when it is higher than 15000, the effect of reducing the viscosity does not appear.

The molecular weight distribution of the reactive plasticizer as the component (E) is not particularly limited, but is preferably narrow because the effect of reducing viscosity is larger, 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 vinyl polymer having a crosslinkable silyl group represented by the general formula (1) having an average of one or more components (E) can be produced by various methods. The production methods [G] to [K] are described below, but are not limited thereto.

[G] A method of adding a hydrosilane compound having a crosslinkable silyl group to a vinyl polymer having an alkenyl group only at one molecular chain end. The production method [G] is the same as the production method [A] for the component (A1), and is a production method that is different in that a vinyl polymer having an alkenyl group only at one molecular chain end is used for the polymer. is there. A vinyl polymer having an alkenyl group only at one molecular chain end can be obtained by a production method such as [G-a] to [G-j] described later, but is not limited thereto.

[H] A method of reacting a vinyl polymer having a hydroxyl group only at one molecular chain end with a compound having a functional group capable of reacting with a hydroxyl group such as a crosslinkable silyl group and an isocyanate group. The above production method [H] is the same method as the production method [B] for the component (A1), except that a vinyl polymer having a hydroxyl group only at one molecular chain end is used for the polymer. It is. A vinyl polymer having a hydroxyl group only at one molecular chain end can be obtained, for example, by a production method such as [Ha] to [Hf] described later, but is not limited thereto.

[I] When synthesizing a vinyl polymer by living radical polymerization using an initiator having one initiation point, the polymerizable alkenyl group and the crosslinkability at the end of the polymerization reaction or after completion of the reaction of the predetermined vinyl monomer A method of reacting a compound having a silyl group. Examples of the compound having a polymerizable alkenyl group and a crosslinkable silyl group used in the production method [I] include compounds represented by the general formula (17). The initiator having one starting point used for living radical polymerization will be described later.

[J] A method in which a vinyl monomer is radically polymerized using a chain transfer agent having a crosslinkable silyl group. The chain transfer agent having a crosslinkable silyl group used in the above synthesis method [J] is not particularly limited as long as the crosslinkable silyl group can be introduced only at one molecular chain end. Mercaptan having a crosslinkable silyl group such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and the like disclosed in Japanese Patent No. 14068 and the like, Japanese Patent Publication No. 4-55444 And hydrosilanes having a crosslinkable silyl group as disclosed in Japanese Laid-Open Patent Publications. Moreover, the radical initiator which has a crosslinkable silyl group can also be used.

[K] A method in which a stabilized carbanion having a crosslinkable silyl group is reacted with a vinyl polymer having a highly reactive carbon-halogen bond only at one molecular chain end. The production method [K] is the same as the production method [E] of the component (A1), and a vinyl polymer having a highly reactive carbon-halogen bond only at one molecular chain end is used for the polymer. This is a different manufacturing method. A vinyl polymer having a highly reactive carbon-halogen bond only at one molecular chain end can be obtained by a production method such as [Ka] described later, but is not limited thereto.

The production methods [Ga] to [Gj] of the vinyl polymer having an alkenyl group only at one molecular chain terminal used in the production method [G] described above will be described below. In the following production methods [Ga] to [Gb], a vinyl polymer having an alkenyl group only at one molecular chain end is directly formed by living radical polymerization using an initiator having one starting point. It is an example of the method of synthesize | combining. An initiator having one starting point used for living radical polymerization will be described later.

[Ga] When synthesizing a vinyl polymer by living radical polymerization using an initiator having one initiation point, a polymerizable alkenyl group and the end of the polymerization reaction or after completion of the reaction of a predetermined vinyl monomer A method of reacting a compound having an alkenyl group having a low polymerization property. Examples of the compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group used in the production method [G-a] include a compound represented by the aforementioned general formula (7).

[Gb] When synthesizing a vinyl polymer by living radical polymerization using an initiator having one starting point, a compound having at least two alkenyl groups having low polymerization properties is added at the end of the polymerization reaction or at a predetermined level. A method of reacting after completion of the reaction of the vinyl monomer. The compound having at least two alkenyl groups having low polymerizability is not particularly limited, and examples thereof include 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene and the like.

The following production methods [Gc] to [Gf] are methods for converting a halogen of a vinyl polymer having a carbon-halogen bond having a high reactivity only at one molecular chain end to an alkenyl group. It is an example.

The method for converting halogen of a vinyl polymer having a highly reactive carbon-halogen bond only at one molecular chain end to an alkenyl group is the above-described production method [Ac] to [A] of the component (A1). -F] is possible. In the production methods [Ac] to [Af], a method using a vinyl polymer having a highly reactive carbon-halogen bond only at one molecular chain end for each polymer is used as the production method [Gc]. ] To [Gf], a vinyl polymer having an alkenyl group only at one molecular chain end can be obtained by these production methods [Gc] to [Gf]. Polymers having an average of 1.1 or more carbon-halogen bonds having high reactivity at only one molecular chain end can be obtained by, for example, the production method [Ka] described later, but are not limited thereto. It is not a thing.

The following production methods [Gg] to [Gj] are examples of methods for converting a hydroxyl group of a vinyl polymer having a hydroxyl group only at one molecular chain end to an alkenyl group.

A method for converting a hydroxyl group of a vinyl polymer having a hydroxyl group only at one molecular chain end to an alkenyl group is the same as the above-described production methods [Ag] to [Aj] of the component (A1). Is possible. In the production methods [Ag] to [Aj], the production method [Gg] to [Gj] is a method in which a vinyl polymer having a hydroxyl group only at one molecular chain end is used as the polymer. Then, a vinyl polymer having an alkenyl group only at one molecular chain end can be obtained by these production methods [Gg] to [Gj]. The polymer having a hydroxyl group only at one molecular chain end can be obtained by, for example, production methods [Ha] to [Hf] described later, but is not limited thereto.

In the above method for producing a vinyl polymer having an alkenyl group only at one molecular chain end, a halogen atom is introduced when an alkenyl group is introduced, such as the production methods [Ga] and [Gb] described above. In the case of a production method in which is not directly involved, it is preferable to use a living radical polymerization method. In this case, the method [Gb] is more preferable because control is easier. Among the living radical polymerization methods, the atom transfer radical polymerization method is more preferable.

On the other hand, in the case of a production method in which an alkenyl group is introduced by converting halogen of a vinyl polymer having a highly reactive carbon-halogen bond, such as the production methods [Gc] to [Gf] described above. One obtained by radical polymerization (atom transfer radical polymerization method) using an organic halide having a highly reactive carbon-halogen bond, which will be described later, or a halogenated sulfonyl compound as an initiator and using a transition metal complex as a catalyst. It is preferable to use a vinyl polymer having a highly reactive carbon-halogen bond only at the molecular chain end. The method [Gf] is more preferable because it is easier to control.

Production method [Ha] to [H] of a polymer having a hydroxyl group only at one molecular chain end in the molecule used in the above production methods [H] and [Gg] to [Gj] -F] will be described below. In the following production methods [Ha] to [Hb], a vinyl polymer having a hydroxyl group only at one molecular chain end is directly synthesized by living radical polymerization using an initiator having one initiation point. It is an example of how to do. An initiator having one starting point used for living radical polymerization will be described later.

[Ha] When synthesizing a vinyl polymer by living radical polymerization using an initiator having one initiation point, a polymerizable alkenyl group and A method of reacting a compound having a hydroxyl group. Examples of the compound having both a polymerizable alkenyl group and a hydroxyl group used in the above production method [Ha] include a compound represented by the aforementioned general formula (13).

[Hb] When synthesizing a vinyl polymer by living radical polymerization using an initiator having one initiation point, for example, 10-undecenol, 5-hexenol at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer. A method of reacting an alkenyl alcohol such as allyl alcohol.

The following production method [Hc] is an example of a method using a hydroxyl group-containing chain transfer agent or initiator in radical polymerization.
[Hc] A method of radical polymerization of the vinyl monomer using a hydroxyl group-containing chain transfer agent such as mercaptoethanol or a hydroxyl group-containing azo initiator.

The following production methods [Hd] to [Hf] are examples of a method of converting this halogen of a vinyl polymer having a highly reactive carbon-halogen bond only at one molecular chain end to a hydroxyl group. It is. A vinyl polymer having a highly reactive carbon-halogen bond only at one molecular chain end can be obtained by the production method [Ka] described later, but is not limited thereto. Absent.

[Hd] A vinyl polymer having a highly reactive carbon-halogen bond only at one molecular chain end is reacted with a stabilized carbanion having a hydroxyl group represented by the general formula (14) or the like. And replacing the halogen with a hydroxyl group-containing substituent.

[He] An aldehyde is prepared by reacting a vinyl polymer having a highly reactive carbon-halogen bond only at one molecular chain terminal with a metal alone or an organometallic compound such as zinc. Or a method of reacting ketones.

[Hf] A hydroxyl group-containing oxyanion represented by the above general formula (15) or the like or the above general formula is added to a vinyl polymer having a highly reactive carbon-halogen bond only at one molecular chain end. (16) A method of reacting a hydroxyl group-containing carboxylate anion represented by the above formula and substituting the halogen with a hydroxyl group-containing substituent.

In the method of converting the halogen into a hydroxyl group of the vinyl polymer having a carbon-halogen bond having high reactivity only at one molecular chain end, the above-described production methods [Ha] to [Hc] are used. In the case of a production method in which a halogen atom is not directly involved when a hydroxyl group is introduced, it is preferable to use a living radical polymerization method. In this case, the method [Hb] is more preferable because control is easier. Among the living radical polymerization methods, the atom transfer radical polymerization method is more preferable.

In the case of a production method in which a hydroxyl group is introduced by converting a highly reactive carbon-halogen bond, such as the production methods [Hd] to [Hf] described above, an organic halide or halogenation described later is used. A vinyl polymer having a highly reactive carbon-halogen bond only at one molecular chain end, obtained by radical polymerization (atom transfer radical polymerization method) using a sulfonyl compound as an initiator and a transition metal complex as a catalyst Is preferably used. In this case, the method [Hf] is more preferable because control is easier.

Carbon-halogen having high reactivity only at one molecular chain end used in the above production methods [K], [Gc] to [Gf], and [Hd] to [Hf]. The production method [Ka] of the vinyl polymer having a bond will be described below.

[Ka] A method of polymerizing a vinyl monomer by an atom transfer radical polymerization method using an initiator having one highly reactive carbon-halogen bond.

Examples of the initiator used in the above production method [Ka] include organic halides having one highly reactive carbon-halogen bond shown below, or halogenated sulfonyl compounds. It is not limited.
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 (wherein C ₆ H ₅ is Represents a phenyl group, and X represents chlorine, bromine or iodine.)
R—C (H) (X) —CO ₂ R, R—C (CH ₃ ) (X) —CO ₂ R, R—C (H) (X) —C (O) R, R—C (CH ₃ ) (X) -C (O) R, wherein R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group. The plurality of R may be the same, X may represent chlorine, bromine or iodine.
R—C ₆ H ₄ —SO ₂ X (wherein, R represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group; X represents chlorine, bromine, or iodine)
These may be used alone or in combination of two or more.

The initiator having one starting point used for the above-mentioned living radical polymerization differs depending on the polymerization method used. In the case of atom transfer radical polymerization, the organic halide having one highly reactive carbon-halogen bond described in [Ka], a sulfonyl halide compound, or the like can be used as an initiator. In the case of living radical polymerization using radical scavengers such as nitroxide compounds or living radical polymerization using cobalt porphyrin complexes, peroxides such as benzoyl peroxide, azobisisobutyronitrile, azobisisovaleronitrile, etc. Examples of the azo compound are as initiators.

A vinyl polymer having a crosslinkable silyl group only at one molecular chain end was obtained by a method using an organic halide having a crosslinkable silyl group, which is the production method [F] of the component (A1). A vinyl polymer having a crosslinkable silyl group at one end and a highly reactive carbon-halogen bond at the other end is obtained as it is or by converting this halogen to a group other than the crosslinkable silyl group. It is also possible.

Similarly, a vinyl polymer obtained by a method using an organic halide having an alkenyl group, having an alkenyl group at one end and a highly reactive carbon-halogen bond at the other end, It is possible to obtain a vinyl polymer having a crosslinkable silyl group only at one molecular chain end by converting this alkenyl group into a crosslinkable silyl group by the above-described method.

As described above, for example, one molecule obtained via the production method [I] or the method such as [Ga], [Gb], [Ha], [Hb], etc. The crosslinkable silyl group of a vinyl polymer having a crosslinkable silyl group only at the chain end does not always exist at the end in a strict sense, and may exist only near the end. However, the effect of addition of these polymers is essentially the same as that of polymers existing at the molecular chain ends. Accordingly, these polymers are crosslinkable silyl groups represented by the general formula (1) only at one molecular chain terminal, which is the main component of the reactive plasticizer as the component (E) according to the fourth invention. It is included in the vinyl polymer having

The vinyl polymer having a crosslinkable silyl group only at one molecular chain terminal, which is the reactive plasticizer of the above component (E), can be obtained by combining the above-described production methods as needed. As a typical manufacturing process, the manufacturing process similar to the synthetic | combination processes A and B of (A1) component mentioned above can be mentioned.

The amount of the reactive plasticizer added as the component (E) is 100 parts by weight of a vinyl polymer having an average of 1.1 or more crosslinkable silyl groups represented by the general formula (1) of the component (A4). The amount is 5 to 150 parts by weight, preferably 10 to 120 parts by weight, more preferably 20 to 100 parts by weight. 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.

To the curable composition of the fourth aspect of the present invention, optional components similar to those described above for the first aspect of the present invention can be added.

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

The curable composition of the fourth aspect 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 multi-layer glass, and electric / electronic component materials such as a solar cell back surface sealing material, electric wires, Electrical insulation materials such as insulation coating materials for cables, 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 rust-proof and waterproof sealing materials for meshed glass and laminated glass end faces (cut parts).

<About the fifth invention>
Next, the curable composition of 5th this invention is explained in full detail. The curable composition of 5th this invention contains the vinyl polymer which has a crosslinkable silyl group which is (A5) component, and the silanol containing compound which is (F) component.

[Vinyl polymer of component (A5)] The component (A5) in the fifth aspect of the present invention has an average of at least one crosslinkable silyl group represented by the general formula (1). The chain is a vinyl polymer obtained by a living polymerization method, and is crosslinked and cured by forming a siloxane bond.

In general formula (1) representing the crosslinkable silyl group in component (A5), R ¹ and R ² are the same or different, and an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, Or it is the same as that of General formula (1) showing the crosslinkable silyl group in the (A1) component used by 1st this invention except showing a C7-C20 aralkyl group.

The crosslinkable silyl group represented by the general formula (1) has at least one crosslinkable silyl group in one molecule. If the crosslinkable silyl group is less than 1 on average in one molecule, a sufficient cured product cannot be obtained. The number of crosslinkable silyl groups represented by the general formula (1) necessary for obtaining a sufficient cured product is usually 1.1 to 5 on average in one molecule, and 1. What has 2-4 pieces is preferable, and what has 1.3-3 pieces on average is more preferable.

The monomer constituting the main chain is not particularly limited as long as it is a vinyl monomer, and examples thereof include those exemplified in the first aspect of the present invention. From the viewpoint of physical properties, the vinyl polymer having 1.1 or more crosslinkable silyl groups on average is obtained by synthesizing using 40% by weight or more of the (meth) acrylic acid monomer among the above monomers. Preferred is a (meth) acrylic polymer. Furthermore, an acrylic polymer obtained by synthesizing using 30% by weight or more of an acrylic acid monomer among the above monomers is more preferable.

The number average molecular weight of the vinyl polymer having 1.1 or more crosslinkable silyl groups on average is not particularly limited, but is preferably in the range of 500 to 100,000. When the molecular weight is 500 or less, the original characteristics of the vinyl polymer are hardly expressed, and when it is 100,000 or more, handling becomes difficult.

The molecular weight distribution of the vinyl polymer having 1.1 or more crosslinkable silyl groups on average, that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is not particularly limited. However, it is preferable that the molecular weight distribution is narrow in order to make the curable composition low in viscosity and facilitate handling, and to obtain sufficient cured product properties. The molecular weight distribution is preferably less than 1.8, more preferably 1.7 or less, still more preferably 1.6 or less, still more preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1. 3 or less. The molecular weight distribution is most commonly measured by gel permeation chromatography (GPC). Chloroform or THF is used as the mobile phase, and a polystyrene gel column is used as the column, and the number average molecular weight and the like can be determined by a value in terms of polystyrene.

The vinyl polymer of component (A5) used in the fifth aspect of the present invention is produced by a living polymerization method, so that it is possible to control with high accuracy for the introduction of a crosslinkable silyl group, unlike the case of free radical polymerization. is there. In other words, because of the characteristics of the living polymerization method, a crosslinkable silyl group can be introduced at or near the end of the molecular chain with a very high probability for each molecule. Can also be improved. Further, by using the living polymerization method, it is possible to reduce the molecular weight distribution that greatly affects the viscosity of the polymer, thereby making it possible to reduce the viscosity of the polymer and the curable composition.

However, there is a limit to reducing the modulus only with the crosslinkable silyl group-containing vinyl polymer (A5) whose main chain is produced by the living polymerization method. In the fifth aspect of the present invention, the vinyl polymer having at least one crosslinkable silyl group whose main chain as component (A5) is produced by a living polymerization method, and a silanol-containing compound as component (F) described later are used in combination. By doing so, the effect of lower modulus is greater than when using a vinyl polymer having a main chain produced by a conventional free radical polymerization method.

The living polymerization method includes a living anion polymerization method, a living cation polymerization method, a living radical polymerization method, and the like, but is not particularly limited in the fifth aspect of the present invention, and any method can be used. Moreover, the method for introducing the crosslinkable silyl group into the vinyl polymer is not particularly limited, and various methods can be used.

However, from the point of versatility of the monomer and ease of control, a method of directly introducing a crosslinkable silyl group into the main chain by a living radical polymerization method, and conversion into a crosslinkable silyl group by one or several steps of reaction A method of converting the specific functional group into a crosslinkable silyl group after obtaining a vinyl polymer having the specific functional group is preferable. Of these, the atom transfer radical polymerization method is more preferable.

The living radical polymerization method is a radical polymerization that is difficult to control because it has a high polymerization rate and is likely to cause a termination reaction due to coupling between radicals. However, the termination reaction is difficult to occur and the molecular weight distribution is narrow (Mw / Mn). Is about 1.1 to 1.5), and a polymer can be obtained, and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

Therefore, 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. It is more preferable as a method for producing a vinyl polymer having the above functional group.

As a specific method for producing the component (A5), various methods as described above in the first aspect of the present invention can be used, but a synthesis method using a polymerization method other than the living polymerization method is excluded. As a typical manufacturing process, the manufacturing process similar to the synthesis | combining process A and B of (A1) component mentioned above can be mentioned.

When the cured product obtained from the curable composition of the fifth aspect of the present invention is particularly required to have rubber-like properties, the molecular weight between crosslinking points that greatly affects rubber elasticity can be increased. At least one is preferably at the end of the molecular chain. Those having a crosslinkable silyl group at two molecular chain terminals are more preferred. What all the crosslinkable silyl groups have at the molecular chain end is further preferred.

[Silanol-containing compound of component (F)] The silanol-containing compound of component (F) used in the fifth aspect of the present invention is the compound (I) having one silanol group in the molecule and / or moisture. The compound (II) which can produce | generate the compound which has one silanol group in a molecule | numerator by reacting. Only one of these may be used, or both compounds may be used simultaneously.

The compound (I) having one silanol group in the molecule, which is one of the components (F) used in the present invention, 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, the formula _C 6 _{H 5} is a phenyl _{group, C} 10 _{H 7} represents a naphthyl group.) Such as _(R ") 3 SiOH (provided that Shikichu R" is substituted or unsubstituted, identical or different A compound represented by an alkyl group or an aryl group of

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 (48) is preferable.
(R ²⁶ ) ₃ SiOH
(48)
(In the formula, R ²⁶ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. The plurality of R ²⁶ may be the same or different.)

R ²⁶ 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 (I) having one silanol group in the molecule reacts with the crosslinkable silyl group of the vinyl polymer (A5) or the siloxane bond formed by crosslinking, thereby reducing the number of crosslinking points. It is presumed that the cured product is given flexibility.

In addition, compound (II) that can generate a compound having one silanol group in the molecule by reacting with moisture, which is one of the components (F), is not particularly limited, but is produced by reacting with moisture. The compound (hydrolysis product) having one silanol group in the molecule is preferably a compound represented by the general formula (48). For example, although not particularly limited, the following compounds may be mentioned in addition to the compound represented by the general formula (49) 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, trimethylsilyl phenoxide, 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 (II) that can form a compound having one silanol group in the molecule by reacting with moisture, which is one of the components (F), is not particularly limited. A compound represented by formula (49) is preferred.
((R ²⁶ ) ₃ SiO) _n R ²⁷ (49)
(Wherein R ²⁶ is the same as described above, n is a positive number, and R ²⁷ is a group obtained by removing some or all of the active hydrogen from the active hydrogen-containing compound.)

R ²⁶ 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 ²⁶ ) ₃ Si group is particularly preferably a trimethylsilyl group in which all three R ²⁶ are methyl groups. N is preferably 1 to 5.

No particular limitation is imposed on the origin become active hydrogen-containing compounds of the above ^{R 27,} for example, methanol, ethanol, n- butanol, i- butanol, t-butanol, n- octanol, 2-ethylhexanol, benzyl alcohol, 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 (II) capable of generating a compound having one silanol group in the molecule by reacting with the water represented by the general formula (49) is, for example, trimethylsilyl chloride, Although 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 ²⁶ ) ₃ Si group, which is also called a silylating agent such as dimethyl (t-butyl) chloride. (However, R ²⁶ is the same as described above.)

Specific examples of the compound represented by the general formula (49) include allyloxytrimethylsilane, N, O-bis (trimethylsilyl) acetamide, N- (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, N- Methyl-N-trimethylsilyltrifluoroacetamide, bistrimethylsilylurea, N- (t-butyldimethylsilyl) N-methyltrifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (N, N-diethylamino) trimethylsilane, Hexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, N- (trimethylsilyl) imidazole, trimethylsilyltrifluoromethanesulfonate, trimethylsilylphenoxide, n-octanol trimethyl Silylated, 2-ethylhexanol trimethylsilylated, glycerol tris (trimethylsilyl), trimethylolpropane tris (trimethylsilyl), pentaerythritol tris (trimethylsilyl), pentaerythritol tetra (trimethylsilyl) 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 ²⁸ ) ₃ SiO) (R ²⁹ O) _s ) _t Z, CH ₃ O (CH ₂ CH (CH ₃ ) O) ₅ Si (CH ₃ ) ₃ , CH ₂ ═CHCH ₂ (CH ₂ CH (CH ₃ ) O) ₅ Si (CH ₃ ) ₃ , (CH ₃ ) ₃ SiO (CH ₂ CH (CH ₃ ) O) ₅ Si (CH ₃ ) ₃ , ( CH ₃ ) ₃ SiO (CH ₂ CH (CH ₃ ) O) ₇ Si (CH ₃ ) ₃ (wherein R ²⁸ is the same or different substituted or unsubstituted monovalent hydrocarbon group or hydrogen atom, R ²⁹ Is preferably a divalent hydrocarbon group having 1 to 8 carbon atoms, s and t are positive integers, s is 1 to 6, s × t is 5 or more, and Z is a 1 to 6 valent organic group). Can be used. These may be used alone or in combination of two or more.

Among the compounds (II) that can generate a compound having one silanol group in the molecule by reacting with moisture, the activity generated after hydrolysis in that it does not adversely affect storage stability, weather resistance, etc. The hydrogen compounds are preferably phenols, acid amides and alcohols, more preferably phenols and alcohols whose active hydrogen compounds are hydroxyl groups.

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.

Compound (II), which can generate a compound having one silanol group in the molecule by reacting with this moisture, reacts with moisture at the time of storage, at the time of curing or after curing, so that one silanol in the molecule is obtained. A compound having a group is produced. The compound having one silanol group in the molecule thus produced reacts with the crosslinkable silyl group of the vinyl polymer (A5) or the siloxane bond formed by the crosslinking, as described above, thereby forming a crosslinking point. It is presumed that the number of the above is reduced, and the cured product is given flexibility.

The amount of the component (F) silanol-containing compound added can be appropriately adjusted according to the expected physical properties of the cured product. The silanol-containing compound as component (F) is 0.1 to 50 parts by weight, preferably 0.3 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the vinyl polymer (A5). Can be added. If the amount is less than 0.1 parts by weight, the effect of adding the component (F) 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 the silanol containing compound of (F) component to a vinyl type polymer (A5) is not specifically limited, You may add at the time of manufacture of a vinyl type polymer (A5), and at the time of preparation of a curable composition It may be added.

To the curable composition of the fifth invention, optional components similar to those described above for the first invention can be added.

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

The curable composition of the fifth aspect 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 multi-layer glass, and electric / electronic component materials such as a solar cell back surface sealing material, Electrical insulation materials such as insulation coating materials for cables, 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 rust-proof and waterproof sealing materials for meshed glass and laminated glass end faces (cut parts).

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 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 and chloroform as a GPC solvent were used.

Example of the first invention (Production Example 1) CuBr (28.0 g, 0.195 mol) was charged into a 10 L separable flask equipped with a reflux tube and a stirrer, and the inside of the reaction vessel was purged with nitrogen. Acetonitrile (559 mL) was added, and the mixture was stirred in an oil bath at 70 ° C. for 15 minutes. To this, butyl acrylate (1.00 kg), diethyl 2,5-dibromoadipate (117 g, 0.325 mol), pentamethyldiethylenetriamine (1.70 mL, 1.41 g, 8.14 mmol) (hereinafter referred to as triamine) Was added to start the reaction. While heating and stirring at 70 ° C., butyl acrylate (4.00 kg) was continuously added dropwise over 175 minutes. Triamine (8.50 mL, 7.06 g, 40.7 mmol) was added during the dropwise addition of butyl acrylate. After 370 minutes from the start of the reaction, 1,7-octadiene (1.57 L, 1.17 kg, 7.10 mol) and triamine (20.4 mL, 16.9 g, 97.7 mmol) were added, followed by heating at 70 ° C. for 220 minutes. Stir. 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 [1]). The number average molecular weight of the polymer [1] was 21,300, and the molecular weight distribution was 1.3.

A 2 L separable flask equipped with a reflux tube was charged with the polymer [1] (0.73 kg), potassium benzoate (25 g), and N, N-dimethylacetamide (0.7 L), and the nitrogen stream was maintained at 70 ° C. for 12 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 content of the filtrate was distilled off under reduced pressure to obtain a polymer [2].

A 2 L round bottom flask with a reflux tube was charged with polymer [2] (0.73 kg), aluminum silicate (150 g, manufactured by Kyowa Chemical Co., Ltd., Kyoward 700 PEL), toluene (4.0 L), and 5 ° C. at 100 ° C. under a nitrogen stream. Stir for hours. After removing the aluminum silicate by filtration, the toluene in the filtrate was distilled off under reduced pressure to obtain a polymer [3].

In a 1 L pressure-resistant reaction vessel, polymer [3] (390 g), dimethoxymethylhydrosilane (36.0 mL, 0.292 mol), methyl orthoformate (7.10 mL, 0.065 mol), and 1,1, 3,3-tetramethyl-1,3-divinyldisiloxane complex was charged. However, the platinum catalyst was used in an amount of 10 ⁻² equivalent in terms of molar ratio to the alkenyl group of the polymer. The reaction mixture was heated at 100 ° C. for 400 minutes. The volatile component of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated polymer (polymer [4]). The number average molecular weight of the obtained polymer was 246000 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.5. The average number of silyl groups introduced per molecule of the polymer was determined by ¹ H NMR analysis and found to be 3.0.

Production Example 2 CuBr (22.4 g, 0.156 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, butyl acrylate (0.20 kg), methyl 2-bromopropionate (86.9 g, 0.520 mol), pentamethyldiethylenetriamine (0.19 mL, 0.18 g, 1.04 mmol) (hereinafter referred to as triamine) Was added to start the reaction. While heating and stirring at 70 ° C., butyl acrylate (0.80 kg) was continuously added dropwise over 150 minutes. Triamine (1.81 mL, 1.71 g, 9.88 mmol) was added during the dropwise addition of butyl acrylate. Subsequently, the mixture was heated and stirred at 70 ° C. for 230 minutes. The reaction mixture was diluted with toluene, 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 [5]). The number average molecular weight of the polymer [5] was 2600, and the molecular weight distribution was 1.18.

A 2 L separable flask equipped with a reflux tube was charged with the polymer [5] (0.937 kg), potassium acetate (73.5 g), and N, N-dimethylacetamide (0.8 L). 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 benzoate were filtered through an activated alumina column. The volatile content of the filtrate was distilled off under reduced pressure to obtain a polymer [6].

(Example 1) To 100 parts of the polymer [4] obtained in Production Example 1, 3 parts of pentaerythritol triacrylate {(CH ₂ = CHCOOCH ₂ ) ₃ CCH ₂ OH}, the polymer [6] as a plasticizer 50 parts and 100 parts of Calfine 100 (manufactured by Maruo Calcium) as a filler are mixed and stirred, and then stirred using 2 parts of γ-glycidoxypropyltrimethoxysilane and 1 part of a tetravalent Sn catalyst (dibutyltin diacetylacetonate). After mixing, defoaming was performed to produce a sheet-like cured product having a thickness of about 2 mm and a mountain-shaped cured product having a maximum thickness of about 5 mm on a glass plate. The curing curing was allowed to stand for 2 days at a position where the sunlight hits the room (near the window) and then at 50 ° C for 3 days. The surface-retained tack (stickiness) of the cured sheet-like product after curing was observed by finger touch and left outdoors. Further, the chevron-shaped cured product is irradiated for 500 hours immediately after curing, and from the glass surface side by a xenon weather meter (Suga Test Instruments SX120 type, irradiance 180 W, black panel temperature 63 ° C., irradiation for 2 hours, rainfall time 18 minutes). Thereafter, a hand peeling test was performed. The results are shown in Table 1.

(Example 2) In the same manner as in Example 1 except that trimethylolpropane triacrylate {(CH ₂ = CHCOOCH ₂ ) ₃ CCH ₂ CH ₃ } was used instead of pentaerythritol triacrylate used in Example 1. A cured product was produced. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 A cured product was produced in the same manner as in Example 1 except that pentaerythritol triacrylate of Example 1 was not used. Evaluation was performed in the same manner. The results are shown in Table 1.

In Table 1, residual tack evaluation: no stickiness ← ◎>○>△> × → Sticky hand peel test: cohesive failure (CF)
← 〇>△> × → Interfacial fracture (AF)

Example (Production Example 3) of Second Invention According to the present invention , CuBr (42.0 g, 0.293 mol) was charged into a 10 L separable flask equipped with a reflux tube and a stirrer, and the inside of the reaction vessel was purged with nitrogen. Acetonitrile (559 mL) was added and stirred in an oil bath at 70 ° C. for 45 minutes. To this, butyl acrylate (1.00 kg), diethyl 2,5-dibromoadipate (176 g, 0.488 mol), pentamethyldiethylenetriamine (2.00 mL, 1.66 g, 9.58 mmol) (hereinafter referred to as triamine) Was added to start the reaction. While heating and stirring at 70 ° C., butyl acrylate (4.00 kg) was continuously added dropwise over 190 minutes. Triamine (6.00 mL, 4.98 g, 28.8 mmol) was added during the dropwise addition of butyl acrylate. After 310 minutes from the start of the reaction, 1,7-octadiene (1.44 L, 1.07 kg, 9.75 mol) and triamine (20.5 mL, 17.0 g, 98.1 mmol) were added, followed by heating at 70 ° C. for 210 minutes. Stir. 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 [7]). The number average molecular weight of the polymer [7] was 14,000, and the molecular weight distribution was 1.3.

A 10 L separable flask equipped with a reflux tube was charged with the polymer [7] (2.7 kg), potassium benzoate (142 g), and N, N-dimethylacetamide (2.7 L), and a nitrogen stream at 70 ° C. for 25 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 [8].

A 2 L round bottom flask equipped with a reflux tube was charged with polymer [8] (2.7 kg), aluminum silicate (540 g, manufactured by Kyowa Chemical Co., Ltd., Kyoward 700 PEL), toluene (2.7 L), and 5% at 100 ° C. under a nitrogen stream. Stir with heating for hours. After removing the aluminum silicate by filtration, the filtrate toluene was distilled off under reduced pressure to obtain a polymer [9].

In a 1 L pressure-resistant reaction vessel, polymer [9] (409 g), dimethoxymethylhydrosilane (27.0 mL, 0.22 mol), methyl orthoformate (8.0 mL, 0.07 mmol), and 1,1, 3,3-tetramethyl-1,3-divinyldisiloxane complex was charged. However, the platinum catalyst was used in an amount of 10 ⁻³ equivalent in terms of molar ratio to the alkenyl group of the polymer. The reaction mixture was heated at 100 ° C. for 1 hour. The volatile content of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated polymer (polymer [10]). The number average molecular weight of the obtained polymer was 13900 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 1.5.

(Example 3) 100 parts of the polymer [10] obtained in Production Example 3 was mixed with 3 parts of tung oil and stirred and mixed with 1 part of a tetravalent Sn catalyst (dibutyltin diacetylacetonate). Foaming was performed to produce a sheet-like cured product having a thickness of 2 mm. Observe the remaining tack on the cured product surface the next day with your finger. Further, the cured product was left outdoors, and the condition of the cured product surface after one month was observed. The results are shown in Table 2.

(Example 4) In Example 3, a cured product was prepared in the same manner as in Example 3 except that 5 parts of tung oil was used instead of 3 parts and evaluated in the same manner. The results are shown in Table 2.

(Comparative Example 2) A cured product was prepared in the same manner as in Example 3 except that the tung oil used in Example 3 was not used, and was similarly evaluated. The results are shown in Table 2.

In Table 2, residual tack evaluation: No stickiness ← ◎>○>△> × → Sticky dirt evaluation: Good ← ◎>○>△>
× → Blackening (many deposits)

(Example 5) A cured product was produced in the same manner as in Example 3. However, the curing curing was allowed to stand at room temperature for 2 days and then at 50 ° C. for 3 days. A 2 (1/3) type dumbbell test piece was punched from the cured sheet-like cured product, and a tensile test was performed using an autograph manufactured by Shimadzu (measurement conditions: 23 ° C., 200 mm / min). The results are shown in Table 3.

(Example 6) Under the same curing conditions as in Example 5, a cured product similar to that in Example 4 was prepared and evaluated in the same manner as in Example 5. The results are shown in Table 3.

(Comparative Example 3) Under the same curing conditions as in Example 5, a cured product similar to Comparative Example 2 was produced and evaluated in the same manner as in Example 5. The results are shown in Table 3.

(Example 7) The sheet-like cured product obtained in Example 3 was coated with various alkyd paints and allowed to stand indoors. The surface coated after a certain period of time was touched with a finger to determine the degree of curing. The results are shown in Table 4.

Example 8 The sheet-like cured product obtained in Example 4 was evaluated in the same manner as in Example 7. The results are shown in Table 4.

(Comparative Example 4) Using the sheet-like cured product obtained in Comparative Example 2, evaluation was made in the same manner as in Example 7. The results are shown in Table 4.

In Table 4, the result after 1 day / 7 days is shown.
◯: Completely cured Δ: Tack (sticky) present ×: Uncured alkyd paint is Schakerverf: SIGMA Rubbol AZ: Akzo Sigmasolid semisig: SIGMA

Third embodiment concerning the present invention (Production Example 4) separable flask 10L equipped with a reflux tube and a stirrer was charged with CuBr (42.0 g, 0.293 mol), and the reactor was purged with nitrogen. Acetonitrile (559 mL) was added and stirred in an oil bath at 70 ° C. for 45 minutes. To this, butyl acrylate (1.00 kg), diethyl 2,5-dibromoadipate (176 g, 0.488 mol), pentamethyldiethylenetriamine (4.00 mL, 3.32 g, 19.2 mmol) (hereinafter referred to as triamine) Was added to start the reaction. While heating and stirring at 70 ° C., butyl acrylate (4.00 kg) was continuously added dropwise over 190 minutes. Triamine (4.00 mL, 3.32 g, 0.0192 mol) was added during the dropwise addition of butyl acrylate. After 310 minutes from the start of the reaction, 1,7-octadiene (1.44 L, 1.07 kg, 9.75 mol) and triamine (20.5 mL, 17.0 g, 98.1 mol) were added, followed by heating at 70 ° C. for 210 minutes. Stir. 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 [11]). The number average molecular weight of the polymer [11] was 14,000, and the molecular weight distribution was 1.3.

A 10 L separable flask equipped with a reflux tube was charged with the polymer [11] (2.7 kg), potassium benzoate (142 g), and N, N-dimethylacetamide (2.7 L), and a nitrogen stream at 70 ° C. for 25 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 content of the filtrate was distilled off under reduced pressure to obtain a polymer [12].

A 2 L round bottom flask equipped with a reflux tube was charged with polymer [12] (2.7 kg), aluminum silicate (540 g, manufactured by Kyowa Chemical Co., Ltd., Kyoward 700 PEL), toluene (2.7 L), and 5% at 100 ° C. under a nitrogen stream. Stir for hours. After removing the aluminum silicate by filtration, the filtrate toluene was distilled off under reduced pressure to obtain a polymer [13].

In a 1 L pressure-resistant reaction vessel, polymer [13] (760 g), dimethoxymethylhydrosilane (46.3 mL, 0.38 mol), methyl orthoformate (13.7 mL, 0.13 mmol), and 1,1, 3,3-tetramethyl-1,3-divinyldisiloxane complex was charged. However, the platinum catalyst was used in an amount of 10 ⁻³ equivalent in terms of molar ratio to the alkenyl group of the polymer. The reaction mixture was heated at 100 ° C. for 1 hour. The volatile content of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated polymer (polymer [14]). The number average molecular weight of the obtained polymer was 15000 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.4. 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.

(Production Example 5) CuBr (22.4 g, 0.156 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, butyl acrylate (0.20 kg), methyl 2-bromopropionate (86.9 g, 0.520 mol), pentamethyldiethylenetriamine (0.19 mL, 0.18 g, 1.04 mmol) (hereinafter referred to as triamine) Was added to start the reaction. While heating and stirring at 70 ° C., butyl acrylate (0.80 kg) was continuously added dropwise over 150 minutes. Triamine (1.81 mL, 1.71 g, 9.88 mmol) was added during the dropwise addition of butyl acrylate. Subsequently, the mixture was heated and stirred at 70 ° C. for 230 minutes. The reaction mixture was diluted with toluene, 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 [15]). The number average molecular weight of the polymer [15] was 2600, and the molecular weight distribution was 1.18.

A 2 L separable flask equipped with a reflux tube was charged with polymer [15] (0.937 kg), potassium acetate (73.5 g), and N, N-dimethylacetamide (0.8 L), and the mixture was stirred at 70 ° C. under a nitrogen stream at 5 ° 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 benzoate were filtered through an activated alumina column. The volatile content of the filtrate was distilled off under reduced pressure to obtain a polymer [16].

(Example 9) 100 parts of the polymer [14] obtained in Production Example 4 was mixed with 50 parts of various polymer plasticizers and stirred and mixed using 1 part of a tetravalent Sn catalyst (dibutyltin diacetylacetonate). Thereafter, degassed under reduced pressure to produce a 2 mm thick sheet-like cured product. The curing curing was allowed to stand indoors for 2 days and then at 50 ° C. for 3 days. A 2 (1/3) type dumbbell test piece was punched from the cured sheet-like cured product, and a tensile test was performed using an autograph manufactured by Shimadzu (measurement conditions: 23 ° C., 200 mm / min). The viscosity was measured at 23 ° C. using an E-type viscometer (using EHD 3 ° cone 28Φ). The results are shown in Table 5.

(Comparative Example 5) The polymer plasticizer of Example 9 was replaced with various low-molecular plasticizers, and the others were prepared in the same manner as in Example 9. Similarly, a tensile test was performed. The viscosity was measured in the same manner as in Example 9. The results are shown in Table 5. In Table 5, the adipate polyester plasticizer is manufactured by Asahi Denka Kogyo Co., Ltd., the polybutene plasticizer is manufactured by Idemitsu Petrochemical Co., and the alkylbenzene plasticizer is manufactured by Nippon Petrochemical Co., Ltd.

(Example 10) Among the sheet-like cured product (dumbbell test piece) obtained in Example 9, several kinds were left to stand in a dryer at 150 ° C. The sample was taken out after a certain period and a tensile test was conducted in the same manner as in Example 9. The results are shown in Table 6.

(Comparative Example 6) Several kinds of cured sheet materials (dumbbell test pieces) obtained in Comparative Example 5 were allowed to stand in a dryer at 150 ° C. as in Example 10. The sample was taken out after a certain period, and a tensile test was conducted in the same manner as in Example 10. The results are shown in Table 6.

(Example 11) Among several kinds of sheet-like cured products (dumbbell test pieces) obtained in Example 9, a sunshine weather meter (WEL-SUN-DC type manufactured by Suga Test Instruments Co., Ltd., black panel temperature 63 ° C, irradiation 2) During the time, it was installed at a rain time of 18 minutes. The sample was taken out after a certain period and a tensile test was conducted in the same manner as in Example 9. The results are shown in Table 7.

(Comparative Example 7) Among several kinds of sheet-like cured products (dumbbell test pieces) obtained in Comparative Example 5, a sunshine weather meter (WEL-SUN-DC type manufactured by Suga Test Instruments Co., Ltd., black panel temperature 63 ° C., irradiation 2) During the time, it was installed at a rain time of 18 minutes. The sample was taken out after a certain period and a tensile test was conducted in the same manner as in Example 11. The results are shown in Table 7.

(Example 12) Various alkyd paints were applied to several kinds of the sheet-like cured product (dumbbell test piece) obtained in Example 9 and allowed to stand indoors. The surface coated after a certain period of time was touched with a finger to determine the degree of curing. The results are shown in Table 8.

(Comparative Example 8) Various alkyd paints were applied from several sheet-like cured products (dumbbell test pieces) obtained in Comparative Example 5 and allowed to stand indoors. Similarly to Example 12, the painted surface was touched after a certain period of time, and the degree of curing was determined. The results are shown in Table 8.

In Table 8, the results after 1 day / 7 days are shown.
◯: Completely cured Δ: Tack (sticky) present ×: Uncured alkyd paint is Schakerverf: SIGMA Rubbol AZ: Akzo Sigmasolid semisig: SIGMA

Example (Production Example 6) separable flask 10L equipped with a reflux tube and stirrer regarding the fourth aspect of the present invention, was charged with CuBr (42.0 g, 0.293 mol), and the reactor was purged with nitrogen. Acetonitrile (559 mL) was added and stirred in an oil bath at 70 ° C. for 45 minutes. To this, butyl acrylate (1.00 kg), diethyl 2,5-dibromoadipate (176 g, 0.488 mol), pentamethyldiethylenetriamine (2.00 mL, 1.66 g, 9.58 mmol) (hereinafter referred to as triamine) Was added to start the reaction. While heating and stirring at 70 ° C., butyl acrylate (4.00 kg) was continuously added dropwise over 190 minutes. Triamine (6.00 mL, 4.98 g, 288 mmol) was added during the dropwise addition of butyl acrylate. After 310 minutes from the start of the reaction, 1,7-octadiene (1.4.4 L, 1.07 kg, 9.75 mol) and triamine (20.5 mL, 17.0 g, 98.1 mmol) were added. The mixture was stirred with heating for a minute. 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 [17]). The number average molecular weight of the polymer [17] was 14,000, and the molecular weight distribution was 1.3.

A 10 L separable flask equipped with a reflux tube was charged with the polymer [17] (2.7 kg), potassium benzoate (142 g), and N, N-dimethylacetamide (2.7 L), and the nitrogen stream was maintained at 70 ° C. for 25 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 content of the filtrate was distilled off under reduced pressure to obtain a polymer [18].

A 2 L round bottom flask equipped with a reflux tube was charged with polymer [18] (2.7 kg), aluminum silicate (540 g, manufactured by Kyowa Chemical Co., Ltd., Kyoward 700PEL), toluene (2.7 L), and 5% at 100 ° C. under a nitrogen stream. Stir for hours. After the aluminum silicate was removed by filtration, the toluene in the filtrate was distilled off under reduced pressure to obtain a polymer [19].

In a 1 L pressure-resistant reaction vessel, polymer [19] (409 g), dimethoxymethylhydrosilane (27.0 mL, 0.22 mol), methyl orthoformate (8.0 mL, 0.07 mmol), and 1,1, 3,3-tetramethyl-1,3-divinyldisiloxane complex was charged. However, the platinum catalyst was used in an amount of 10 ⁻³ equivalent in terms of molar ratio to the alkenyl group of the polymer. The reaction mixture was heated at 100 ° C. for 1 hour. The volatile component of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated polymer (polymer [20]). The number average molecular weight of the obtained polymer was 13900 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 1.5.

(Production example 7) Synthesis example of Br group-terminated poly (butyl acrylate) CuBr (5.54 g, 38.6 mmol) was charged into a 2 L separable flask equipped with a reflux tube and a stirrer, Was replaced with nitrogen. Acetonitrile (73.8 mL) was added, and the mixture was stirred in an oil bath at 70 ° C. for 30 minutes. To this was added butyl acrylate (132 g), methyl 2-bromopropionate (14.4 mL, 0.129 mol) and pentamethyldiethylenetriamine (4.69 mL, 0.022 mol) to initiate the reaction. While heating and stirring at 70 ° C., butyl acrylate (528 g) was continuously added dropwise over 90 minutes, and further heated and stirred for 80 minutes. The reaction mixture was diluted with toluene, passed through an activated alumina column, and then the volatile matter was distilled off under reduced pressure to obtain poly (butyl acrylate) having a Br group at one end (polymer [21]). The number average molecular weight of the polymer [21] was 5800, and the molecular weight distribution was 1.14.

(Production Example 8) Synthesis example of one-terminal alkenyl group poly (butyl acrylate) In a 500 mL flask with a reflux tube, the polymer [21] (150 g) obtained in Production Example 2 and potassium pentenoate (8 .29 g) and dimethylacetamide (150 mL) were added, and the mixture was heated and stirred at 70 ° C. for 6 hours. Dimethylacetamide was distilled off from the reaction mixture, dissolved in toluene, and passed through an activated alumina column. Toluene was distilled off to obtain a polymer.

A polymer (20 g), aluminum silicate (4.0 g, manufactured by Kyowa Chemical, Kyoward 700PEL) and toluene (20 mL) were charged, and the mixture was heated and stirred at 100 ° C. for 1 hour in a nitrogen stream. After filtering the aluminum silicate, the filtrate was concentrated to obtain poly (butyl acrylate) (polymer [22]) having an alkenyl group at one end. The number average molecular weight was 5800, and the molecular weight distribution was 1.13. The viscosity was 11 Pa · s (E-type viscometer: measured 23 ° C.).

(Production Example 9) Synthesis example of single terminal silyl group poly (butyl acrylate) In a 30 mL pressure-resistant reaction vessel, the polymer [22] (9.4 g) obtained in Production Example 7 and dimethoxymethylhydrosilane (0.58 mL) 4.7 mmol), methyl orthoformate (0.17 mL, 1.6 mmol), and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zerovalent platinum. However, the platinum catalyst was used in a molar ratio of 10 ⁻⁴ equivalent to the alkenyl group of the polymer. The reaction mixture was heated at 100 ° C. for 1 hour. Dimethoxymethylhydrosilane (0.58 mL, 4.7 mmol), 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zerovalent platinum (2 × in molar ratio to the alkenyl group of the polymer) 10 ⁻⁴ equivalents) was added, and the mixture was further heated at 100 ° C. for 1 hour. The reaction solution was concentrated to obtain poly (butyl acrylate) having a silyl group at one end (polymer [23]). The number average molecular weight was 6100, the molecular weight distribution was 1.18, and the average number of silyl groups introduced per polymer molecule was 1.0. The viscosity was 13 Pa · s (E-type viscometer: measurement 23 ° C.).

(Example 13) 100 parts of the polymer [20] obtained in Production Example 6 was mixed with 50 parts of the polymer [23] as a reactive plasticizer, and 1 part of a tetravalent Sn catalyst (dibutyltin diacetylacetonate). The mixture was stirred and mixed and then degassed under reduced pressure to prepare a 2 mm thick sheet-like cured product. After standing for 1 day indoors and then at 50 ° C. for 1 day, the gel content was measured. The viscosity of a mixture of 100 parts of the polymer [20] and 50 parts of the polymer [23] was also measured (E-type viscometer: measured at 23 ° C.). The results are shown in Table 9.

(Comparative Example 9) The reactive plasticizer of Example 13 (polymer [23]) was replaced with a non-reactive plasticizer having no silyl group (polymer [22]), and the rest was the same as in Example 13. To produce a cured product. Evaluation was performed in the same manner. The viscosity of a mixture of 100 parts of the polymer [20] and 50 parts of the polymer [22] was also measured (E-type viscometer: measured at 23 ° C.). The results are shown in Table 9.

Reference Example 1 A cured product was prepared in the same manner as in Example 13 except that the reactive plasticizer (polymer [23]) of Example 13 was not added. Evaluation was performed in the same manner. The viscosity of only the polymer [20] was also measured (E-type viscometer: measured at 23 ° C.). The results are shown in Table 9.

Example 14 A cured product was produced in the same manner as in Example 13. However, the curing curing was allowed to stand at room temperature for 2 days and then at 50 ° C. for 3 days. A 2 (1/3) type dumbbell test piece was punched from the cured sheet-like cured product, and a tensile test was performed using an autograph manufactured by Shimadzu (measurement conditions: 23 ° C., 200 mm / min). The results are shown in Table 10.

Comparative Example 10 A cured product was prepared in the same manner as Comparative Example 9. However, the curing curing was performed in the same manner as in Example 14, and a tensile test was performed in the same manner as in Example 14. The results are shown in Table 10.

Example of Example 5 (Production Example 10) CuBr (28.0 g, 0.195 mol) was charged into a 10 L separable flask equipped with a reflux tube and a stirrer, and the inside of the reaction vessel was purged with nitrogen. Acetonitrile (559 mL) was added, and the mixture was stirred in an oil bath at 70 ° C. for 15 minutes. To this, butyl acrylate (1.00 kg), diethyl 2,5-dibromoadipate (117 g, 0.325 mol), pentamethyldiethylenetriamine (1.70 mL, 1.41 g, 8.14 mmol) (hereinafter referred to as triamine) Was added to start the reaction. While heating and stirring at 70 ° C., butyl acrylate (4.00 kg) was continuously added dropwise over 175 minutes. Triamine (8.50 mL, 7.06 g, 40.7 mmol) was added during the dropwise addition of butyl acrylate. After 370 minutes from the start of the reaction, 1,7-octadiene (1.57 L, 1.17 kg, 7.10 mol) and triamine (20.4 mL, 16.9 g, 97.7 mmol) were added, followed by heating at 70 ° C. for 220 minutes. Stir. 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 [24]). The number average molecular weight of the polymer [24] was 21,300, and the molecular weight distribution was 1.3.

A 2 L separable flask equipped with a reflux tube was charged with the polymer [24] (0.73 kg), potassium benzoate (25 g), and N, N-dimethylacetamide (0.7 L), and the nitrogen flow was at 70 ° C. for 12 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 content of the filtrate was distilled off under reduced pressure to obtain a polymer [25].

A 2 L round bottom flask equipped with a reflux tube was charged with polymer [25] (0.73 kg), aluminum silicate (150 g, manufactured by Kyowa Chemical Co., Ltd., Kyoward 700 PEL), toluene (4.0 L), and 5% at 100 ° C. under a nitrogen stream. Stir for hours. After removing the aluminum silicate by filtration, the filtrate toluene was distilled off under reduced pressure to obtain a polymer [26].

In a 1 L pressure-resistant reaction vessel, polymer [26] (390 g), dimethoxymethylhydrosilane (36.0 mL, 0.292 mol), methyl orthoformate (7.10 mL, 0.065 mol), and 1,1, 3,3-tetramethyl-1,3-divinyldisiloxane complex was charged. However, the platinum catalyst was used in an amount of 10 ⁻² equivalent in terms of molar ratio to the alkenyl group of the polymer. The reaction mixture was heated at 100 ° C. for 400 minutes. The volatile content of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated polymer (polymer [27]). The number average molecular weight of the obtained polymer was 246000 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.5. The average number of silyl groups introduced per molecule of the polymer was determined by ¹ H NMR analysis and found to be 3.0.

(Production Example 11) The polymer [26] (300 g) obtained in Production Example 10 in a 1 L pressure-resistant reaction vessel, dimethoxymethylhydrosilane (18.0 mL, 0.146 mol), methyl orthoformate (4.97 mL, 0.8. 045 mol), and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zerovalent platinum. However, the platinum catalyst was used in an amount of 10 ⁻² equivalent in terms of molar ratio to the alkenyl group of the polymer. The reaction mixture was heated at 100 ° C. for 250 minutes. The volatile content of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated polymer (polymer [28]). The number average molecular weight of the obtained polymer was 246000 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.5. When the average number of silyl groups introduced per molecule of the polymer was determined by ¹ H NMR analysis, it was 1.2.

(Example 15) A divalent Sn catalyst (dioctyl) obtained by mixing 1 part of (CH ₃ ) ₃ SiOC ₆ H ₅ as a silanol-containing compound with 100 parts of the polymer [27] obtained in Production Example 10 and stirring and mixing in advance. After stirring and mixing using 4 parts of tin) and laurylamine (mixing ratio 3: 1), the mixture was degassed under reduced pressure to prepare a sheet-like cured product having a thickness of 2 mm. The curing curing was allowed to stand indoors for 2 days and then at 50 ° C. for 3 days. A 2 (1/3) type dumbbell test piece was punched from the cured sheet-like cured product, and a tensile test was performed using an autograph manufactured by Shimadzu (measurement conditions: 23 ° C., 200 mm / min). The results are shown in Table 11.

(Example 16) Instead of 1 part of the silanol-containing compound (CH ₃ ) ₃ SiOC ₆ H ₅ used in Example 15, 1 part of Me ₃ SiO [CH ₂ CH (CH ₃ ) O] ₇ SiMe ₃ was used. Produced a cured product in the same manner as in Example 15 and conducted a tensile test in the same manner. The results are shown in Table 11.

(Example 17) was manufactured and carried silanol-containing compound used in Example _{15 (CH 3) 3 SiOC 6} H 5 1 part _C 12 _H 25 similarly cured as in Example 15 except for using OSiMe ₃ instead of Similarly, a tensile test was performed. The results are shown in Table 11.

Example 18 A cured product was obtained in the same manner as in Example 15 except that 1 part of C ₄ H ₉ OSiMe ₃ was used instead of 1 part of the silanol-containing compound (CH ₃ ) ₃ SiOC ₆ H ₅ used in Example 15. A tensile test was performed in the same manner. The results are shown in Table 11.

Comparative Example 11 A cured product was prepared in the same manner as in Example 15 except that the silanol-containing compound used in Example 15 was not added, and a tensile test was performed in the same manner. The results are shown in Table 11.

(Comparative Example 12) A cured product was prepared in the same manner as in Comparative Example 11 except that the polymer [28] obtained in Production Example 11 was used, and a tensile test was performed in the same manner. The results are shown in Table 11.

In both Examples and Comparative Examples, the surface state of the cured product was observed by finger touch, and the stickiness (residual tack) was evaluated. The results are also shown in Table 11.

In Table 11, residual tack evaluation: no stickiness ← ○> △> × → stickiness

Claims (69)

The following two components:
(A2) A vinyl polymer having an average of at least one crosslinkable silyl group represented by the general formula (1),-[Si (R ¹ ) _2-b (Y) _b O] _m -Si (R ² ) _3-a (Y) _a (1)
(In the formula, R ¹ and R ² are the same or different and each represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO. (In the formula, R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. The plurality of R ′ may be the same or different. When two or more R ¹ or R ² are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and two or more Y are present. , They may be the same or different, a represents 0, 1, 2, or 3. b represents 0, 1, or 2. m represents an integer of 0 to 19. A + mb ≧ 1).
(C) A curable composition comprising an air oxidation curable substance. The curable composition according to claim 1, wherein the vinyl polymer as the component (A2) has a molecular weight distribution of less than 1.8. The curable composition according to claim 1 or 2, wherein the vinyl polymer (A2) is a (meth) acrylic polymer. The curable composition according to claim 3, wherein the vinyl polymer of component (A2) is an acrylic polymer. The curable composition according to any one of claims 1 to 4, wherein a main chain of the vinyl polymer (A2) is produced by a living radical polymerization method. The curable composition according to claim 5, wherein the main chain of the vinyl polymer (A2) is produced by an atom transfer radical polymerization method. The vinyl polymer as the component (A2) has at least one crosslinkable silyl group represented by the general formula (1) at the molecular chain terminal on average. The curable composition according to 1. Component (A2) is a vinyl polymer (1) a step of synthesizing a vinyl polymer having a halogen atom at its terminal by polymerizing a vinyl monomer by an atom transfer radical polymerization method, A step of synthesizing a vinyl polymer having an alkenyl group at the terminal by reacting the vinyl polymer having a terminal halogen atom obtained in 1) with an oxyanion having an alkenyl group to substitute the halogen; and (3) By adding a hydrosilane compound having a crosslinkable silyl group represented by the general formula (1) to the terminal alkenyl group of the vinyl polymer having an alkenyl group at the terminal obtained in the step (2). It is a polymer obtained by the process converted into the substituent containing a crosslinkable silyl group, Curability of any one of Claims 1-7 Narubutsu. The component (A2) vinyl polymer comprises (1) a step of forming a vinyl polymer by polymerizing a vinyl monomer by a living radical polymerization method, and (2) at least a low polymerizable alkenyl group. A step of synthesizing a vinyl polymer having an alkenyl group at the terminal by reacting two compounds, and (3) a terminal of the vinyl polymer having an alkenyl group at the terminal obtained in the step (2). A polymer obtained by a step of converting to a substituent containing a crosslinkable silyl group by adding a hydrosilane compound having a crosslinkable silyl group represented by the general formula (1) to the alkenyl group of The curable composition of any one of 1-7. The oxidative curable substance of component (C) is tung oil or a liquid diene polymer, The curable composition according to any one of claims 1 to 9. The following two components:
(A3) A curable composition comprising a vinyl polymer having an average of at least one crosslinkable functional group, and (D) a polymer plasticizer. The curable composition according to claim 11, wherein the vinyl polymer as the component (A3) has a molecular weight distribution of less than 1.8. The curable composition according to claim 11 or 12, wherein the vinyl polymer (A3) is a (meth) acrylic polymer. The curable composition according to claim 11 or 12, wherein the vinyl polymer (A3) is an acrylic polymer. The curable composition according to any one of claims 11 to 14, wherein the crosslinkable functional group of the vinyl polymer (A3) is a crosslinkable silyl group. The curable composition according to any one of claims 11 to 14, wherein the crosslinkable functional group of the vinyl polymer (A3) is an alkenyl group. The curable composition according to any one of claims 11 to 14, wherein the crosslinkable functional group of the vinyl polymer (A3) is a hydroxyl group. The curable composition according to any one of claims 11 to 14, wherein the crosslinkable functional group of the vinyl polymer (A3) is an amino group. The curable composition according to any one of claims 11 to 14, wherein the crosslinkable functional group of the vinyl polymer (A3) is a group having a polymerizable carbon-carbon double bond. The curable composition according to any one of claims 11 to 14, wherein the crosslinkable functional group of the vinyl polymer (A3) is an epoxy group. The curable composition according to any one of claims 11 to 20, wherein the main chain of the vinyl polymer (A3) is produced by a living radical polymerization method. The curable composition according to claim 21, wherein the main chain of the vinyl polymer (A3) is produced by an atom transfer radical polymerization method. The curable composition according to claim 22, wherein the atom transfer radical polymerization is carried out using a transition metal complex having a central metal of Group 7, Group 8, Group 9, Group 10 or Group 11 of the periodic table as a catalyst. Composition. The curable composition according to claim 23, wherein the transition metal complex is a complex of copper, nickel, ruthenium or iron. The curable composition according to claim 24, wherein the transition metal complex is a copper complex. The curable composition according to any one of claims 11 to 25, wherein the polymer plasticizer as the component (D) has a number average molecular weight of 500 to 15000. 27. The curable composition according to claim 26, wherein the polymer plasticizer of component (D) has a number average molecular weight of 800 to 10,000. 28. The curable composition according to claim 27, wherein the polymer plasticizer of component (D) has a number average molecular weight of 1000 to 8000. The curable composition according to any one of claims 11 to 28, wherein the polymer plasticizer of component (D) is a vinyl polymer. 30. The curable composition according to claim 29, wherein the polymer plasticizer of component (D) has a molecular weight distribution of less than 1.8. The curable composition according to claim 29 or 30, wherein the polymer plasticizer of component (D) is a (meth) acrylic polymer. The curable composition according to claim 29 or 30, wherein the polymer plasticizer of component (D) is an acrylic polymer. The curable composition according to any one of claims 29 to 32, wherein the polymer plasticizer as component (D) is produced by a living radical polymerization method. The curable composition according to claim 33, wherein the polymer plasticizer as component (D) is produced by an atom transfer radical polymerization method. The amount of the component (D) polymer plasticizer used is 5 to 150 parts by weight with respect to 100 parts by weight of the vinyl polymer (A3) having at least one crosslinkable functional group. 2. The curable composition according to item 1. The following two components:
(A4) Vinyl polymer having 1.1 or more crosslinkable silyl groups represented by general formula (1) on average,-[Si (R ¹ ) _{2 -b} (Y) _b O] _m -Si (R ² ) _3-a (Y) _a (1)
(In the formula, R ¹ and R ² are the same or different and each represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO. (In the formula, R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. The plurality of R ′ may be the same or different. When two or more R ¹ or R ² are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and two or more Y are present. , They may be the same or different, a represents 0, 1, 2, or 3. b represents 0, 1, or 2. m represents an integer of 0 to 19. A + mb ≧ 1).
(E) A curable composition comprising, on average, a reactive plasticizer that is a vinyl polymer having a crosslinkable silyl group represented by the general formula (1) of 1 or less. The curable composition according to claim 36, wherein the vinyl polymer as the component (A4) has a molecular weight distribution of less than 1.8. 38. The curable composition according to claim 36 or 37, wherein the vinyl polymer of component (A4) is a (meth) acrylic polymer. The curable composition according to claim 38, wherein the vinyl polymer of component (A4) is an acrylic polymer. The curable composition according to any one of claims 36 to 39, wherein the main chain of the vinyl polymer as the component (A4) is produced by a living radical polymerization method. The curable composition according to claim 40, wherein the main chain of the vinyl polymer (A4) is produced by an atom transfer radical polymerization method. The vinyl polymer as the component (A4) has 1.1 or more crosslinkable silyl groups represented by the general formula (1) on average at the molecular chain terminals. The curable composition according to item 1. The component (A4) vinyl polymer comprises (1) a step of synthesizing a vinyl polymer having a halogen atom at its terminal by polymerizing a vinyl monomer by an atom transfer radical polymerization method, (2) the step ( A step of synthesizing a vinyl polymer having an alkenyl group at the terminal by reacting the vinyl polymer having a terminal halogen atom obtained in 1) with an oxyanion having an alkenyl group to substitute the halogen; and (3) By adding a hydrosilane compound having a crosslinkable silyl group represented by the general formula (1) to the terminal alkenyl group of the vinyl polymer having an alkenyl group at the terminal obtained in the step (2). The polymer obtained by the process of converting into a substituent containing a crosslinkable silyl group, The hard material according to any one of claims 36 to 42. Gender composition. The component (A4) vinyl polymer comprises (1) a step of forming a vinyl polymer by polymerizing a vinyl monomer by a living radical polymerization method, and (2) at least a low polymerizable alkenyl group. A step of synthesizing a vinyl polymer having an alkenyl group at the terminal by reacting two compounds, and (3) a terminal of the vinyl polymer having an alkenyl group at the terminal obtained in the step (2). A polymer obtained by a step of converting to a substituent containing a crosslinkable silyl group by adding a hydrosilane compound having a crosslinkable silyl group represented by the general formula (1) to the alkenyl group of The curable composition according to any one of 36 to 42. 45. The curable composition according to any one of claims 36 to 44, wherein the reactive plasticizer of component (E) has a molecular weight distribution of less than 1.8. 46. The curable composition according to any one of claims 36 to 45, wherein the number average molecular weight of the reactive plasticizer of component (E) is 500 to 15000. 47. The curable composition according to any one of claims 36 to 46, wherein the reactive plasticizer of component (E) has a lower viscosity than the vinyl polymer of component (A4). 48. The curable composition according to any one of claims 36 to 47, wherein the reactive plasticizer of component (E) is a (meth) acrylic polymer. 49. The curable composition according to claim 48, wherein the reactive plasticizer of component (E) is an acrylic polymer. The curable composition according to any one of claims 36 to 49, wherein the reactive plasticizer of component (E) has a polymer main chain produced by a living radical polymerization method. 51. The curable composition according to claim 50, wherein the reactive plasticizer of component (E) has a polymer main chain produced by an atom transfer radical polymerization method. (E) The reactive plasticizer of component (1) is a vinyl heavy polymer having a highly reactive carbon-halogen bond only at one molecular chain end by polymerizing a vinyl monomer by an atom transfer radical polymerization method. (2) reacting a vinyl polymer having a highly reactive carbon-halogen bond only at one molecular chain end obtained in the step (1) with an oxyanion having an alkenyl group. A step of synthesizing a vinyl polymer having an alkenyl group only at the end of one molecular chain by substituting halogen, and (3) only at the end of one molecular chain obtained in the step (2) By adding a hydrosilane compound having a crosslinkable silyl group represented by the general formula (1) to a terminal alkenyl group of a vinyl polymer having an alkenyl group, the terminal is crosslinkable silyl. The curable composition according to any one of claims 36 to 51 the step of converting a polymer obtained by the. (E) The reactive plasticizer of component (1) is a step of forming a vinyl polymer by polymerizing a vinyl monomer by a living radical polymerization method using an initiator having one starting point, (2 And a step of synthesizing a vinyl polymer having an alkenyl group at the terminal by reacting with a compound having at least two alkenyl groups having low polymerizability; and (3) the terminal obtained in the step (2). A hydrosilane compound having a crosslinkable silyl group represented by the general formula (1) is added to the terminal alkenyl group of the vinyl polymer having an alkenyl group to convert to a substituent containing a crosslinkable silyl group. 52. The curable composition according to any one of claims 36 to 51, wherein the curable composition is a polymer obtained by the step of: The following two components:
(A5) A vinyl polymer having a polymer main chain obtained by a living polymerization method having at least one crosslinkable silyl group represented by the general formula (1) on average,-[Si (R ¹ ) _{2 ^{-b (Y) b O] m}} -Si (R 2) 3-a (Y) a (1)
(In the formula, R ¹ and R ² are the same or different and each represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. R ¹ or R ^{when 2} there are two or more, respectively, they may be the same, when good .Y be different existing .Y more than two showing a hydroxyl group or a hydrolyzable group, they had the same A represents 0, 1, 2, or 3. b represents 0, 1, or 2. m represents an integer of 0 to 19. However, a + mb ≧ 1. Satisfied with that.)
(F) containing compound (I) having one silanol group in the molecule and / or compound (II) capable of producing a compound having one silanol group in the molecule by reacting with moisture. A curable composition characterized by the above. 55. The curable composition according to claim 54, wherein the vinyl polymer as the component (A5) has a molecular weight distribution of less than 1.8. 56. The curable composition according to claim 54 or 55, wherein the vinyl polymer of component (A5) is a (meth) acrylic polymer. 57. The curable composition according to claim 56, wherein the vinyl polymer of component (A5) is an acrylic polymer. 58. The curable composition according to any one of claims 54 to 57, wherein the vinyl polymer of component (A5) has a main chain produced by a living radical polymerization method. 59. The curable composition according to claim 58, wherein the vinyl polymer of component (A5) has a main chain produced by an atom transfer radical polymerization method. The vinyl polymer as the component (A5) has at least one crosslinkable silyl group represented by the general formula (1) on average at the molecular chain terminal. The curable composition according to 1. The component (A5) vinyl polymer comprises: (1) a step of synthesizing a vinyl polymer having a halogen atom at its terminal by polymerizing a vinyl monomer by an atom transfer radical polymerization method; A step of synthesizing a vinyl polymer having an alkenyl group at the terminal by reacting the vinyl polymer having a terminal halogen atom obtained in 1) with an oxyanion having an alkenyl group to substitute the halogen; and (3) By adding a hydrosilane compound having a crosslinkable silyl group represented by the general formula (1) to the terminal alkenyl group of the vinyl polymer having an alkenyl group at the terminal obtained in the step (2). The polymer obtained by the process of converting into a substituent containing a crosslinkable silyl group, The hard material according to any one of claims 54 to 60. Gender composition. The component (A5) vinyl polymer comprises (1) a step of forming a vinyl polymer by polymerizing a vinyl monomer by a living radical polymerization method, and (2) at least a low polymerizable alkenyl group. A step of synthesizing a vinyl polymer having an alkenyl group at the terminal by reacting two compounds, and (3) a terminal of the vinyl polymer having an alkenyl group at the terminal obtained in the step (2). A polymer obtained by a step of converting to a substituent containing a crosslinkable silyl group by adding a hydrosilane compound having a crosslinkable silyl group represented by the general formula (1) to the alkenyl group of The curable composition according to any one of 54 to 60. 63. The compound (I) having one silanol group in the molecule, which is one of the components (F), is a compound represented by the general formula (48). Curable composition. (R ²⁶ ) ₃ SiOH (48)
(In the formula, R ²⁶ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. The plurality of R ²⁶ may be the same or different.) Compound (II), which is one of the components (F) and can generate a compound having one silanol group in the molecule by reacting with moisture, is reacted with moisture in the general formula (48). 63. The curable composition according to any one of claims 54 to 62, wherein the curable composition is a compound capable of producing a represented compound.
(R ²⁶ ) ₃ SiOH (48)
(In the formula, R ²⁶ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. The plurality of R ²⁶ may be the same or different.) The compound (II) that can generate a compound having one silanol group in the molecule by reacting with moisture, which is one of the components (F), is (CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ . 65. The curable composition according to claim 64. Compound (II), which is one of the components (F) and can generate a compound having one silanol group in the molecule by reacting with moisture, is a compound represented by the general formula (49). Item 65. The curable composition according to Item 64.
((R ²⁶ ) ₃ SiO) _n R ²⁷ (49)
(In the formula, R ²⁶ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. A plurality of R ²⁶ may be the same or different. N represents a positive number, and R ²⁷ represents (Residues obtained by removing some or all of the active hydrogen from the active hydrogen-containing compound.) In the general formula (48) or a compound represented by (49), at least one ^{R 26} is a methyl group claim 63 or 66 curable composition. The curable composition according to claim 63 or 64, wherein the compound represented by the general formula (48) is trimethylsilanol. 67. The curable composition according to claim 66, wherein in the general formula (49), the active hydrogen-containing compound from which ^R27 is derived is a phenol, an acid amide, or an alcohol.