JP2001279108A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable composition that can solve the problem that a curable composition having, as a curable component, a vinyl polymer comprising at least one crosslinkable functional group and containing, as in a common case, a general-use limestone powder having a specific surface area on the order of 1 m2/g often fails in providing a cured product having a high level of stretchability, sufficient primerless adhesion and sufficient weather resistant adhesion. SOLUTION: The viscosity ratio of a curable composition, the property of how well it can be cut with a pallet, the strength and elongation at break of a cured product therefrom, and the adhesion and weather resistant adhesion of the cured product to various materials, are improved by using a curable composition comprising a vinyl polymer (I) having at least one crosslinkable functional group and a limestone powder (II) having a specific surface area of <=1.5 m2/g and 50 m2/g<=.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a curable composition. More specifically, the present invention relates to a curable composition containing a vinyl polymer having at least one crosslinkable silyl group and heavy calcium carbonate having a specific surface area of 1.5 m ² / g or more and 50 m ² / g or less.

[0002]

2. Description of the Related Art Among polymers obtained by ionic polymerization or polycondensation, vinyl polymers obtained by radical polymerization and having a functional group, particularly a functional group at a terminal, have not been practically used yet. . Among vinyl polymers, (meth) acrylic polymers have characteristics such as high weather resistance and transparency that cannot be obtained with the above-mentioned polyether polymers, hydrocarbon polymers, or polyester polymers. Those having an alkenyl group or a crosslinkable silyl group in a side chain are used for highly weather-resistant paints and the like. On the other hand, it is not easy to control the polymerization of an acrylic polymer due to its side reaction, and it is very difficult to introduce a functional group into the terminal.

[0003] If a vinyl polymer having an alkenyl group at a molecular chain terminal can be obtained by a simple method, a cured product having excellent physical properties can be obtained as compared with a product having a crosslinkable group in a side chain. it can. Therefore, many researchers have studied the production method, but it is not easy to produce them industrially. For example, JP-A-1-
JP-A-247403 and JP-A-5-255415 disclose a method for synthesizing a (meth) acryl-based polymer having an alkenyl group at a terminal using an alkenyl group-containing disulfide as a chain transfer agent.

Japanese Patent Application Laid-Open No. 5-262808 discloses that a vinyl polymer having a hydroxyl group at both terminals is synthesized using a disulfide having a hydroxyl group, and the vinyl polymer having a hydroxyl group at both ends is further utilized by utilizing the reactivity of the hydroxyl group. A method for synthesizing a (meth) acrylic polymer having an alkenyl group is disclosed.

JP-A-5-212922 discloses that a vinyl polymer having hydroxyl groups at both ends is synthesized by using a polysulfide having a hydroxyl group, and furthermore, by utilizing the reactivity of the hydroxyl group, a vinyl polymer having a hydroxyl group is added to the terminal. A method for synthesizing a (meth) acrylic polymer having a silyl group is disclosed.

In these methods, it is difficult to reliably introduce functional groups at both ends, and a cured product having satisfactory properties 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 addition, since ordinary radical polymerization is used in these methods, 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.

[0007] In contrast to such conventional techniques, the present inventors have made numerous inventions on vinyl polymers having various crosslinkable functional groups at their terminals, their production methods, curable compositions, and uses. (Japanese Patent Laid-Open No. 11-08024)
9, JP-A-11-080250, JP-A-11-0058
15, JP-A-11-116617, JP-A-11-116
606, JP-A-11-080571, JP-A-11-08
0570, JP-A-11-130931, JP-A-11-1
00433, JP-A-11-116763, JP-A-9-2
No. 72714, JP-A-9-272715, etc.).

For example, a vinyl polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having a silicon-containing group capable of being crosslinked by forming a siloxane bond (hereinafter also referred to as “crosslinkable silyl group”). The coalesced product, or a cured product obtained from the composition, has excellent heat resistance or weather resistance, and is not limited, but sealing materials such as an elastic sealing material for building and a sealing material for double glazing,
Electric and electronic parts materials such as encapsulants for solar cells
Electrical insulation materials such as cable insulation coating materials, adhesives, adhesives, elastic adhesives, paints, powder paints, coating materials,
Used for various applications such as foams, potting agents for electric and electronic devices, films, gaskets, casting materials, various molding materials, netted glass and sealing materials for rust prevention and waterproofing of laminated glass end faces (cut sections). It is possible.

Of these, general-purpose heavy calcium carbonate having a specific surface area of about 1 m ² / g is often blended with the elastic sealant for construction. This is for the purpose of reducing the cost of the compound, improving the resilience of the cured product, and the like. However, when this general-purpose heavy calcium carbonate is used for the above-mentioned vinyl polymer having a crosslinkable functional group, there is a problem that it is difficult to obtain a high elongation hardened product required for an elastic sealant for building. Was. In addition, the curable composition tends to be easily stringed, and an improvement in the viscosity ratio and an improvement in spatula cutting properties are sometimes required.

On the other hand, as a demand from the market, not only a sealing material for a double-glazed glass but also an elastic sealant for construction (particularly, a one-component elastic sealant) is strongly applied to various adherends without applying a primer. , That is, it is required to have excellent non-primer adhesion. Furthermore, a sealing material used around glass, such as a sealing material for double-glazed glass, is required to have particularly excellent weather resistance. However, when the above-mentioned general-purpose heavy calcium carbonate was used for the above-mentioned vinyl polymer having a crosslinkable functional group, the adhesion with a non-primer and the weather resistance were insufficient. In particular, there is a problem that the weather-resistant adhesiveness to a heat-insulating glass having a high heat insulating property coated with a metal oxide or the like is insufficient.

[0011]

SUMMARY OF THE INVENTION The present invention relates to a curable composition containing a vinyl polymer having at least one crosslinkable functional group as a main component, which improves the viscosity ratio and the spatability of the curable composition. An object of the present invention is to improve the breaking strength, the breaking elongation, the adhesion to various adherends, and the weather resistance to various types of glass, particularly heat ray reflective glass.

[0012]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned situation, and as a result of intensive studies, it has been found that the addition of a specific filler to this polymer can reduce adverse effects such as a decrease in the curing rate of the composition. Without affecting, the viscosity ratio and the spatula cutting property are improved, and the breaking strength, breaking elongation, and
The inventors have found that the adhesiveness to various adherends and the weather-resistant adhesiveness can be improved, thereby solving the above problems, and have reached the present invention.

That is, the present invention provides the following two components: a vinyl polymer (I) having at least one crosslinkable functional group,
And a curable composition containing heavy calcium carbonate (II) having a specific surface area of 1.5 m ² / g or more and 50 m ² / g or less.

The main chain of the vinyl polymer (I) is not particularly limited, but comprises a (meth) acrylic monomer, an acrylonitrile monomer, an aromatic vinyl monomer, a fluorine-containing vinyl monomer and a silicon-containing vinyl monomer. It is preferably produced by mainly polymerizing monomers selected from the group, more preferably (meth) acrylic monomers, further preferably acrylic monomers, more preferably acrylic ester monomers, most preferably butyl acrylate monomers. It is preferably produced by polymerization using a monomer.

The vinyl polymer (I) is not particularly limited, but the value of the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography is 1. Preferably it is less than 8.

The main chain of the vinyl polymer (I) is not particularly limited, but is preferably produced by a living radical polymerization method, more preferably by an atom transfer radical polymerization method. At this time, the catalyst for the atom transfer radical polymerization method is not particularly limited, but is preferably a metal complex selected from the group consisting of copper, nickel, ruthenium, and iron, and more preferably a copper complex.

The crosslinkable functional group of the vinyl polymer (I) is not limited, but may be a crosslinkable silyl group, alkenyl group, hydroxyl group, amino group, polymerizable carbon-carbon double bond,
Epoxy groups and the like are preferred.

The position of the crosslinkable functional group of the vinyl polymer (I) is not limited, but is preferably at the terminal. In addition, a similar functional group may be provided inside the main chain, but it is preferable to have a functional group only at the terminal when a crosslinked cured product requires rubber elasticity.

The number of the crosslinkable functional groups of the vinyl polymer (I) is not particularly limited, but in order to obtain a cured product having a higher crosslinkability, one or more, preferably 1.2, on average. The number is more preferably 1.5 or more.

The vinyl polymer (I) is preferably, but not limited to, produced by living radical polymerization, more preferably atom transfer radical polymerization. In addition, atom transfer radical polymerization can be, but is not limited to, group 7, 8, 9, 10, or 11 of the periodic table.
Preferably, the catalyst is a complex selected from transition metal complexes having a group metal as the central metal, more preferably a complex selected from the group consisting of copper, nickel, ruthenium, and iron complexes, and particularly preferably a copper complex. .

On the other hand, the specific surface area is not less than 1.5 m ² / g and 50
Heavy calcium carbonate (II) having a m ² / g or less is not particularly limited, but is preferably surface-treated heavy calcium carbonate, and the mixing ratio thereof is not particularly limited. It is more preferable to contain 5-500 parts by weight of heavy calcium carbonate (II) based on parts by weight. Although not particularly limited, a silane coupling agent is further added as a component (C) in an amount of from 0.1 to 2 in order to improve the adhesiveness and the glass weathering adhesiveness.
It is preferable to use 0 parts by weight together.

[0022]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a vinyl polymer (I) having at least one crosslinkable functional group and heavy calcium carbonate having a specific surface area of 1.5 m ² / g or more and 50 m ² / g or less. Curing composition characterized by containing II), in which the curable composition has improved viscosity ratio and spatula cutting property, cured product with improved breaking strength, breaking elongation, and adhesion to various adherends and weather resistance. The curable composition of the present invention will be described in detail below. <<< Vinyl Polymer (I) >>><MainChain> The vinyl monomer constituting the main chain of the vinyl polymer (I) of the present invention is not particularly limited, and various types can be used. . For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, -n (meth) acrylate
-Butyl, isobutyl (meth) acrylate, -tert-butyl (meth) acrylate, -n- (meth) acrylate
-Pentyl, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid-
n-heptyl, n-octyl (meth) acrylate,
2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, (meth)
Dodecyl acrylate, phenyl (meth) acrylate,
Toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) Acrylic acid-2
-Hydroxypropyl, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, an ethylene oxide adduct of (meth) acrylic acid, Trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutyl (meth) acrylate Ethyl, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate , (Meth) acrylic acid 2-perfluorohe Shiruechiru, (meth) acrylate, 2-perfluoro decyl ethyl, (meth) acrylic acid 2
(Meth) acrylic acid monomers such as perfluorohexadecylethyl; styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; perfluoroethylene, perfluoropropylene, and fluorine. Fluorine-containing vinyl monomers such as vinylidene fluoride; vinyltrimethoxysilane,
Silicon-containing vinyl monomers such as vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid,
Monoalkyl esters and dialkyl esters of fumaric acid; maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; acrylonitrile, methacrylic acid Vinyl monomers containing nitrile groups such as lonitrile; vinyl monomers containing amide groups such as acrylamide and methacrylamide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate,
Vinyl esters such as vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride;
Allyl alcohol and the like can be mentioned. These may be used alone or a plurality of them may be copolymerized. Among them, styrene-based monomers and (meth) acrylic-acid-based monomers are preferred from the viewpoint of the physical properties of the product. More preferred are acrylate monomers and methacrylate monomers, particularly preferred are acrylate monomers, and still more preferred is butyl acrylate. In the present invention, these preferred monomers may be copolymerized with other monomers, or further, may be subjected to block copolymerization. In this case, it is preferable that these preferred monomers are contained in a weight ratio of 40%. In the above expression format, for example, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

The molecular weight distribution of the polymer (I) of the present invention, 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 and 1.01. That ’s it,
It is preferably 1.7 or less and 1.01 or more, more preferably 1.6 or less and 1.01 or more, further preferably 1.5 or less and 1.01 or more, and particularly preferably 1.4.
It is 1.01 or more below, most preferably 1.3 or less and 1.01 or more. In the GPC measurement in the present invention, chloroform is usually used as a mobile phase, the measurement is performed using 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 of the present invention 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 synthesis method of the vinyl polymer (I) of the present invention is not limited, but controlled radical polymerization is preferable, living radical polymerization is more preferable, and atom transfer radical polymerization is particularly preferable. These will be described below. Controlled radical polymerization The radical polymerization method is a `` general radical polymerization method '' in which a monomer having a specific functional group and a vinyl monomer are simply copolymerized using an azo compound, a peroxide, or the like as a polymerization initiator. It can be classified as a "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, but in this method, a monomer having a specific functional group is introduced into the polymer only stochastically, so that a polymer having a high functionalization rate is used. If it is intended to obtain such a monomer, it is necessary to use this monomer in a considerably large amount. Conversely, if the monomer is used in a small amount, there is a problem that the proportion of the polymer into which this specific functional group is not introduced becomes large. In addition, since it is free radical polymerization, there is 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 polymerization is carried out using a chain transfer agent having a specific functional group to obtain a vinyl polymer having a functional group at a terminal. The term "living radical polymerization method" can be classified into a "living radical polymerization method" in which a polymer having a molecular weight almost as designed can be obtained by growing a polymer growth terminal without causing a termination reaction or the like.

The "chain transfer agent method" can obtain a polymer having a high degree of functionalization, but requires a considerably large amount of a chain transfer agent having a specific functional group with respect to the initiator, and requires a treatment. There is a problem in the economy, including that. Further, similarly to the above-mentioned "general radical polymerization method", there is also a problem that since it is a free radical polymerization, only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.

Unlike these polymerization methods, the “living radical polymerization method” is a radical polymerization which is difficult to control because the polymerization rate is high and a termination reaction is likely to occur due to coupling between radicals. The reaction hardly occurs and the molecular weight distribution is narrow (Mw / Mn is 1.
(Approximately 1 to 1.5) 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 can introduce a monomer having a specific functional group into almost any position of the polymer. Therefore, the method for producing a vinyl polymer having the specific functional group is more preferable.

In the narrow sense of living polymerization,
This refers to polymerization in which the molecular chain grows while the terminal always keeps activity.In general, the pseudo-polymer in which the terminal is inactivated and the terminal that is activated grows in an equilibrium state. Living polymerization is also included. The definition in the present invention is also the latter.

The "living radical polymerization method" has been actively studied by various groups in recent years. Examples thereof include, for example, Journal of American Chemical Society (J. Am. Chem. Soc.), 19
1994, Vol. 116, p. 7943, using a cobalt porphyrin complex, Macromolecules, 1994, 2
7, “Atom Transfer Radical Polymerization” using a radical scavenger such as a nitroxide compound as shown in page 7228, and using an organic halide or the like as an initiator and a transition metal complex as a catalyst.
cal Polymerization (ATRP).

Among the "living radical polymerization methods", the "atom transfer radical polymerization method" in which a vinyl monomer is polymerized using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above-mentioned "living radical polymerization method". In addition to the features of the `` radical polymerization method, '' vinyl-based polymers having specific functional groups have halogens at the terminals that are relatively advantageous for the functional group conversion reaction, and have a high degree of freedom in designing initiators and catalysts. It is more preferable as a method for producing a united product. As this atom transfer radical polymerization method, for example, Mat
yjaszewski et al., Journal of American Chemical Society (J. Am. Chem. So
c. 1995, 117, 5614, Macromolecules 1995.
Year, Volume 28, 7901, Science
e) 1996, 272, 866, WO 96/30
No. 421, WO97 / 18247, WO98
/ 01480, WO98 / 40415, or Sawamoto et al., Macromolecules (M
acromolecules) 1995, volume 28, 1
721 page, JP-A-9-208616, JP-A-8-208
41117 and the like.

In the present invention, any of these living radical polymerization methods is not particularly limited, but an atom transfer radical polymerization method is preferred.

The living radical polymerization will be described below in detail. Before that, one of the controlled radical polymerizations, which can be used for the production of the polymer (I) described later, is a chain transfer agent. The polymerization will be described. The radical polymerization using a chain transfer agent (telomer) is not particularly limited, but the following two methods are exemplified as a method for obtaining a vinyl polymer having a terminal structure suitable for the present invention.

A method for obtaining a halogen-terminated polymer by using a halogenated hydrocarbon as a chain transfer agent as disclosed in JP-A-4-132706 and JP-A-61-2
No. 71306, Japanese Patent No. 2594402, and Japanese Patent Application Laid-Open No. 54-47782 discloses a method of obtaining a hydroxyl-terminated polymer using a hydroxyl group-containing mercaptan or a hydroxyl group-containing polysulfide as a chain transfer agent.

The living radical polymerization will be described below.

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 used as a radical capping agent. Such compounds include, but are not limited to, 2, 2,
6,6-substituted-1-piperidinyloxy radicals and 2,
Preferred are nitroxy free radicals from cyclic hydroxyamines, such as 2,5,5-substituted-1-pyrrolidinyloxy radicals. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group and 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, 1,1,3,3-tetramethyl-2-isoindolinyloxy radical,
N, N-di-t-butylamineoxy radical and the like can be mentioned. Instead of the nitroxy free radical, a stable free radical such as galvinoxyl free radical may be used.

The above 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 the two is not particularly limited, but 0.1 to 10 mol of the radical initiator is appropriate for 1 mol of the radical capping agent.

As the radical generator, various compounds can be used, but a peroxide capable of generating a radical under polymerization temperature conditions is preferable. 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; Peroxycarbonates such as (4-t-butylcyclohexyl) peroxydicarbonate, t-butyl peroxyoctoate, t-
There are alkyl peresters such as butyl peroxybenzoate. Particularly, benzoyl peroxide is preferred. Further, a radical generator such as a radical-generating azo compound such as azobisisobutyronitrile may be used instead of the peroxide.

Macromolecules 199
5, 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.

[0041]

Embedded image When an alkoxyamine compound is used as the 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 a terminal can be obtained.

The polymerization conditions such as the monomer, solvent and polymerization temperature used in the polymerization using a radical scavenger such as the above-mentioned nitroxide compound are not limited, but may be the same as those used for the atom transfer radical polymerization described below. . Atom transfer radical polymerization Next, a more preferable atom transfer radical polymerization method as the living radical polymerization of the present invention will be described.

In this atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl position), Alternatively, a sulfonyl halide compound or the like is used as an initiator. For example, C ₆ H ₅ —CH ₂ X, C ₆ H ₅ —C (H) (X) CH ₃ , C ₆
H ₅ -C (X) (CH ₃ ) ₂ (where C ₆ H ₅ is a phenyl group, X is chlorine, bromine or iodine) R ¹ -C (H) (X) -CO ₂ R ² , R ¹ -C (CH ₃ )
^{_{(X) -CO 2 R 2,}} R 1 -C (H) (X) -C (O)
R ² , R ¹ -C (CH ₃ ) (X) -C (O) R ² , wherein,
R ¹ and R ² are a hydrogen atom or an alkyl group, an aryl group, or an aralkyl group having 1 to 20 carbon atoms, X is chlorine, bromine, or iodine. R ¹ -C ₆ H ₄ -SO ₂ X (each of the above formulas) In the formula, R ¹ is a hydrogen atom or a carbon atom 1
To 20 alkyl groups, aryl groups, or aralkyl groups, and X is chlorine, bromine, or iodine).

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

The organic halide having an alkenyl group is not limited, and examples thereof include those having a structure represented by the general formula 1. R ⁴ R ⁵ C (X) -R ⁶ -R ⁷ -C (R ³ ) = CH ₂ (1) (wherein, R ³ is hydrogen or a methyl group, and R ⁴ and R ⁵ are hydrogen or carbon A monovalent alkyl group, an aryl group, or an aralkyl of the formulas 1 to 20, or those mutually linked at the other end, R ⁶ is —C (O) O— (ester group), —C (O) — ( Keto group), or o-, m-, p
A phenylene group, R ⁷ is a direct bond, or has 1 to 2 carbon atoms;
0 is a divalent organic group which may contain one or more ether bonds. X is chlorine, bromine, or iodine. Specific examples of the substituents R ⁴ and R ⁵ include hydrogen, methyl, and ethyl. , N-propyl group, isopropyl group, butyl group,
Examples include a pentyl group and a hexyl group. R ⁴ and R ⁵ may be linked at the other end to form a cyclic skeleton.

Specific examples of the organic halide having an alkenyl group represented by the general formula 1 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 ,

[0047]

Embedded image (In each formula mentioned above, X is chlorine, bromine or iodine, n represents an integer of _{0~20,) XCH 2 C (O} ) O (CH 2) n O (CH 2) m CH = C
H ₂ , H ₃ CC (H) (X) C (O) O (CH ₂ ) _n O (C
H 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 ,

[0048]

Embedded image(In each of the above formulas, X represents chlorine, bromine, or iodine.
Prime, n is an integer of 1 to 20, m is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four− (CH_Two)_n-CH = C
H_Two, O, m, p-CH_ThreeC (H) (X) -C₆H_Four− (C
H_Two)_n-CH = CH_Two, O, m, p-CH_ThreeCH_TwoC
(H) (X) -C₆H_Four− (CH_Two)_n-CH = CH_Two,
(In each of the above formulas, X represents chlorine, bromine, or iodine.
Prime, n is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four− (CH_Two)_n-O- (C
H_Two)_m-CH = CH_Two, O, m, p-CH_ThreeC (H)
(X) -C₆H_Four− (CH_Two)_n-O- (CH_Two)_m-CH =
CH_Two, O, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H
_Four− (CH_Two)_n-O- (CH_Two)_mCH = CH_Two,(above
In each formula, X is chlorine, bromine, or iodine, and n is 1
O, m, p-XCH_Two-C₆H_Four-O- (CH_Two)_n-CH
= CH_Two, O, m, p-CH_ThreeC (H) (X) -C₆H_Four−
O- (CH_Two)_n-CH = CH_Two, O, m, p-CH _ThreeCH
_TwoC (H) (X) -C₆H_Four-O- (CH_Two)_n-CH = C
H_Two, (In each of the above formulas, X is chlorine, bromine, or
Iodine, n is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four-O- (CH_Two)_n-O-
(CH_Two)_m-CH = CH_Two, O, m, p-CH_ThreeC (H)
(X) -C₆H_Four-O- (CH_Two)_n-O- (CH_Two) _m-C
H = CH_Two, O, m, p-CH_ThreeCH_TwoC (H) (X)-
C₆H_Four-O- (CH _Two)_n-O- (CH_Two)_m-CH = CH
_Two(In the above formulas, X represents chlorine, bromine, or iodine.
, N is an integer of 1 to 20, m is an integer of 0 to 20) As an organic halide having an alkenyl group,
The compound represented by the general formula 2 is exemplified. H_TwoC = C (R^Three) -R⁷-C (R^Four) (X) -R⁸-R^Five (2) (where R^Three, R^Four, R^Five, R⁷, X is the same as above, R
⁸Is a direct bond, -C (O) O- (ester group), -C
(O)-(keto group) or o-, m-, p-phenyl
R which represents a len group)⁶Is a direct bond or has 1 to 20 carbon atoms
A divalent organic group (containing one or more ether bonds,
Is good, but if it is a direct bond,
A vinyl group is bonded to the bonded carbon, and halogen
Allylic compound. In this case, the adjacent vinyl groups
The carbon-halogen bond is activated,⁸When
It is necessary to have C (O) O group or phenylene group
Alternatively, it may be a direct bond. R⁷Is a direct bond
If not, to activate the carbon-halogen bond,
R⁸Are C (O) O group, C (O) group, phenylene group
Is preferred.

If the compound of the general formula 2 is specifically exemplified, CH ₂ ＝ CHCH ₂ X, CH ₂ ＣC (CH ₃ ) CH
₂ X, CH ₂ ＣＨCHC (H) (X) CH ₃ , CH ₂ ＣC (C
H ₃ ) C (H) (X) CH ₃ , CH ₂ ＣＨCHC (X) (C
H ₃ ) ₂ , CH ₂ （CHC (H) (X) C ₂ H ₅ , CH ₂ ＣC
HC (H) (X) CH (CH 3) 2, CH 2 = CHC
(H) (X) C ₆ H ₅ , CH ₂ ＣＨCHC (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 = CH
_{CH 2 C (H) (X} ) -C 6 H 5, CH 2 = CH (CH 2) 2
C (H) (X) -C 6 H 5, CH 2 = CH (CH 2) 3 C
_{(H) (X) -C 6} H 5, ( in each formula above, X is chlorine, bromine or iodine, R represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group,) and the like, etc. it can.

Specific examples of the sulfonyl halide compound having an alkenyl group include o-, m-, p-C
_{H 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 each of the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20).

Organic halogen having crosslinkable silyl group
The compound is not particularly limited.
One having a structure is exemplified. R^FourR^FiveC (X) -R⁶-R⁷-C (H) (R^Three) CH_Two− [Si (R⁹)_2-b(Y)_b O]_m-Si (R^Ten)_3-a(Y)_a (3) (where R^Three, R^Four, R^Five, R⁶, R⁷, X is the same as above,
R⁹, R^TenIs an alkyl group having 1 to 20 carbon atoms,
Aryl group, aralkyl group, or (R ′)_ThreeSiO-
(R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms,
The three R's may be the same or different
I) represents a triorganosiloxy group represented by⁹Ma
Or R^TenWhen two or more exist, they are the same.
Or may be different. Y is a hydroxyl group or water
A decomposable group, and when two or more Y
They may be one or different. a is 0, 1,
2, or 3, and b represents 0, 1, or 2.
m is an integer of 0-19. Where a + mb ≧ 1
To specifically exemplify the compound of the general formula 3, XCH_Two
C (O) O (CH_Two)_nSi (OCH_Three)_Three, CH_ThreeC
(H) (X) C (O) O (CH_Two)_nSi (OCH_Three)_Three,
(CH_Three)_TwoC (X) C (O) O (CH_Two)_nSi (OCH
_Three)_Three, XCH_TwoC (O) O (CH_Two)_nSi (CH_Three) (O
CH_Three)_Two, CH _ThreeC (H) (X) C (O) O (CH_Two)_n
Si (CH_Three) (OCH_Three)_Two, (CH_Three)_TwoC (X) C
(O) O (CH_Two)_nSi (CH_Three) (OCH_Three)_Two,(Up
In each of the above formulas, X is chlorine, bromine, iodine, and n is 0 to
An integer of 20, XCH_TwoC (O) O (CH_Two)_nO (CH_Two)_mSi (OC
H_Three)_Three, H_ThreeCC (H) (X) C (O) O (CH_Two)_nO
(CH_Two)_mSi (OCH_Three)_Three, (H_ThreeC)_TwoC (X) C
(O) O (CH_Two)_nO (CH_Two)_mSi (OCH_Three)_Three, C
H_ThreeCH_TwoC (H) (X) C (O) O (CH_Two)_nO (CH
_Two)_mSi (OCH_Three)_Three, XCH_TwoC (O) O (CH_Two)_n
O (CH_Two)_mSi (CH_Three) (OCH_Three)_Two, H_ThreeCC
(H) (X) C (O) O (CH_Two)_nO (CH_Two)_m-Si
(CH_Three) (OCH_Three)_Two, (H_ThreeC)_TwoC (X) C (O)
O (CH_Two)_nO (CH_Two)_m-Si (CH_Three) (OCH_Three)
_Two, CH_ThreeCH _TwoC (H) (X) C (O) O (CH_Two)_nO
(CH_Two)_m-Si (CH_Three) (OCH_Three)_Two, (Each of the above
In the formula, X is chlorine, bromine, iodine, and n is 1-20.
An integer, m is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four− (CH_Two)_TwoSi (OC
H_Three)_Three, O, m, p-CH_ThreeC (H) (X) -C₆H_Four−
(CH_Two)_TwoSi (OCH_Three)_Three, O, m, p-CH_ThreeCH_Two
C (H) (X) -C₆H_Four− (CH_Two)_TwoSi (OC
H_Three)_Three, O, m, p-XCH_Two-C₆H_Four− (CH_Two)_ThreeS
i (OCH_Three)_Three, O, m, p-CH_ThreeC (H) (X)-
C₆H_Four− (CH_Two)_ThreeSi (OCH_Three)_Three, O, m, p-C
H_ThreeCH_TwoC (H) (X) -C₆H_Four− (CH_Two)_ThreeSi (O
CH_Three)_Three, O, m, p-XCH_Two-C₆H_Four− (CH_Two)_Two
-O- (CH_Two)_ThreeSi (OCH_Three)_Three, O, m, p-CH
_ThreeC (H) (X) -C₆H_Four− (CH_Two)_Two-O- (CH_Two)
_ThreeSi (OCH_Three)_Three, O, m, p-CH_ThreeCH_TwoC (H)
(X) -C₆H_Four− (CH_Two)_Two-O- (CH_Two)_ThreeSi (O
CH_Three)_Three, O, m, p-XCH_Two-C₆H_Four-O- (C
H_Two)_ThreeSi (OCH_Three)_Three, O, m, p-CH_ThreeC (H)
(X) -C₆H_Four-O- (CH_Two)_ThreeSi (OCH_Three)_Three,
o, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H_Four-O-
(CH_Two)_Three-Si (OCH_Three)_Three, O, m, p-XCH_Two
-C₆H_Four-O- (CH_Two)_Two-O- (CH_Two)_Three-Si (O
CH_Three)_Three, O, m, p-CH_ThreeC (H) (X) -C₆H_Four
-O- (CH_Two)_Two-O- (CH_Two)_ThreeSi (OCH_Three)_Three,
o, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H_Four-O-
(CH_Two)_Two-O- (CH_Two)_ThreeSi (OCH_Three)_Three,(the above
In each formula, X is chlorine, bromine, or iodine).

As the organic halide having a crosslinkable silyl group, those having a structure represented by the following general formula 4 are further exemplified. ^{_{(R 10) 3-a (}} Y) a Si- [OSi (R 9) 2-b (Y) b] m -CH 2 -C (H) (R 3) -R 7 -C (R 4) ( ^{X) 8 -R 5 (4)} ( wherein ^{-R, R 3, R 4,} R 5, R 7, R 8, R 9, R 10, a,
b, m, X, and Y are the same as described above. If such a compound is specifically exemplified, (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) -C
O 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 S
_{i (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 (C
_{H 3) Si (CH 2)} 4 C (H) (X) -C 6 H 5, ( in each formula above, X is chlorine, bromine or iodine, R represents an alkyl group having 1 to 20 carbon atoms, aryl Group, aralkyl group) 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₎ in _{n -OC (O) C (H} ) (R) (X) ( the formulas above, X is chlorine, bromine or iodine, R represents a hydrogen atom or an alkyl having 1 to 20 carbon atoms, Group,
(Aryl group, aralkyl group, n is an integer of 1 to 20) The organic halide having the amino group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following. H ₂ N- (CH ₂₎ in _{n -OC (O) C (H} ) (R) (X) ( the formulas above, X is chlorine, bromine or iodine, R represents a hydrogen atom or 1 to 20 carbon atoms, An alkyl group of
(Aryl group, aralkyl group, 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.

[0054]

Embedded image (In each of 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 in one molecule of the present invention, an organic halide having two or more starting points or halogen Preferably, a sulfonyl halide compound is used as the initiator. To give a concrete example,

[0055]

Embedded image

[0056]

Embedded image And the like.

The vinyl monomer used in this polymerization is not particularly limited, and any of those already exemplified can be suitably used.

The transition metal complex used as the polymerization catalyst is not particularly limited, but is preferably 7 in the periodic table.
It is a metal complex complex having a Group 7, 8, 9, 10 or 11 element as a central metal. More preferably,
Examples thereof include complexes of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, and divalent nickel. Among them, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, and the like. 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 and the like for enhancing the catalytic activity A ligand such as a polyamine is added. Tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ )
Are also suitable as catalysts. When a ruthenium compound is used as a catalyst, aluminum alkoxides are added as an activator. Furthermore, bis (triphenylphosphine) complex of divalent iron (FeCl ₂ (PPh ₃ ) ₂ ) and bistriphenylphosphine complex of divalent nickel (NiCl
₂ (PPh ₃ ) ₂ ) and bistributylphosphine complex of divalent nickel (NiBr ₂ (PBu ₃ ) ₂ ) are also suitable as the catalyst.

The polymerization can be carried out without solvent or in various solvents. Examples of the solvent 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 ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone. Solvent, methanol, ethanol, propanol, isopropanol, n-butyl alcohol, alcohol solvents such as tert-butyl alcohol, acetonitrile, propionitrile, nitrile solvents such as benzonitrile, ethyl acetate, ester solvents such as butyl acetate, Examples thereof include carbonate solvents such as ethylene carbonate and propylene carbonate, which may be used alone or in combination of two or more. Also, although not limited, polymerization is 0
C. to 200.degree. C., preferably 5 to 200.degree.
0-150 ° C. <Functional group> The crosslinkable functional group of the vinyl polymer (I) is not limited, but may be a crosslinkable silyl group, an alkenyl group, a hydroxyl group, an amino group, a polymerizable carbon-carbon double bond,
Epoxy groups and the like are preferred.

All of these crosslinkable functional groups are used / purposes
Can be used properly. Number of crosslinkable functional groups The number of crosslinkable functional groups of the vinyl polymer (I) is particularly limited.
Not to be obtained, but in order to obtain a cured product with higher crosslinkability,
On average one or more, preferably 1.2 or more, more preferably
Or 1.5 or more.Location of crosslinkable functional group Foamed and cured foam of the curable composition of the present invention
When rubber-like properties are particularly required, rubber elasticity is large.
The molecular weight between cross-linking points that gives
At least one of the crosslinkable functional groups must be at the end of the molecular chain.
Is preferred. More preferably, all crosslinkable functional groups are
It has one at the molecular chain end.

A method for producing a vinyl polymer having at least one crosslinkable functional group at a molecular terminal, in particular, a (meth) acrylic polymer is disclosed in JP-B-3-14068 and JP-B-4-55444. JP-A-6-2119
No. 22, for example. However, since these methods are free radical polymerization methods using the above “chain transfer agent method”, the resulting polymer has a relatively high ratio of crosslinkable functional groups at the molecular chain terminals, while Mw / Mn
Has a problem that the value of the molecular weight distribution represented by is generally as large as 2 or more, and the viscosity becomes high. Therefore, in order to obtain a vinyl polymer having a narrow molecular weight distribution and a low viscosity and having a high proportion of a crosslinkable functional group at a molecular chain terminal, the above-mentioned "living radical polymerization method" is used. Is preferred.

Hereinafter, these functional groups will be described. The crosslinkable silyl group crosslinkable silyl group of the present invention, the general formula ^{5; - [Si (R 9} ) 2-b (Y) b O] m -Si (R 10) 3-a (Y) a (5 Wherein R ⁹ and R ¹⁰ are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms.
An aralkyl group, 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), and R ⁹ or R ¹⁰ is 2
When there are more than one, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Ys are present, they may be the same or different. a is 0, 1, 2, or 3
And b represents 0, 1, or 2. m is 0 to 19
Is an integer. However, it is assumed that a + mb ≧ 1 is satisfied. And a group represented by｝.

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. Can be Among these, an alkoxy group, an amide group, and an aminooxy group are preferred, but an alkoxy group is particularly preferred because of its mild hydrolyzability and easy handling.

A hydrolyzable group or a hydroxyl group can be bonded to one silicon atom in the range of 1 to 3 and (a + Σ
b) 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 a crosslinkable silyl group is one or more. In the case of silicon atoms linked by a siloxane bond or the like, the number is preferably 20 or less. In particular, a crosslinkable silyl group represented by the general formula 6-Si (R ¹⁰ ) _3-a (Y) _a (6) (wherein R ¹⁰ , Y and a are the same as above) is easily available. Is preferred. Alkenyl group for the alkenyl group present invention include, but are not limited, it is preferable that the general formula 7. H ₂ C ＝ C (R ¹¹ )-(7) (wherein, R ¹¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms) In the general formula 7, R ¹¹ is a hydrogen atom or a carbon atom having 1 to 20 carbon atoms.
There are 20 hydrocarbon groups, specifically, 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 -C
_{H 3, -C 6 H 5,} -C 6 H 5 (CH 3), - C 6 H 5 (C
_{H 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 of each group is 20 or less) Among these, a hydrogen atom is preferable.

Further, although not limited, the polymer (I)
Is preferably not activated by a carbonyl group, alkenyl group or aromatic ring conjugated to the carbon-carbon double bond.

The form of bonding between the alkenyl group and the main chain of the polymer is not particularly limited. preferable.
The amino group at the amino group present invention, but are not limited to, -NR ¹² ₂ (R ¹² is a hydrogen or a monovalent organic group having 1 to 20 carbon atoms, two R ¹² are different may be the same with each other even if well, also connected to each other at the other end, but may form a cyclic structure) and the _{^{like, -. (NR 12 3)}} + X - (R 12 is the same .X as above ^- Is a counter anion.

In the above formula, R ¹² is hydrogen or a group having 1 to 2 carbon atoms.
0 is a monovalent organic group, for example, hydrogen, 1-2 carbon atoms
Examples include an alkyl group having 0, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Two R ¹² may be the same or different. Further, they may be connected to each other at the other end to form an annular structure. Polymerizable carbon-carbon double bond The group having a polymerizable carbon-carbon double bond is preferably a group represented by the following general formula 8: —OC (O) C (R ¹³ ) = CH ₂ (8) R ¹³ is hydrogen or a monovalent organic group having 1 to 20 carbon atoms.), And more preferably, R ¹³ is hydrogen or a methyl group.

In the general formula 8, R¹³As a specific example of
There is no particular limitation, for example, -H, -CH_Three, -CH_TwoCH
_Three,-(CH_Two)_nCH_Three(N represents an integer of 2 to 19),
-C ₆H_Five, -CH_TwoOH, -CN and the like.
Preferably -H, -CH_ThreeIt is. <Functional group introduction method> The following describes the vinyl polymer of the present invention.
The method for introducing a functional group into (I) will be described.
It is not specified.

First, a method for introducing a crosslinkable silyl group, alkenyl group and hydroxyl group by conversion of a terminal functional group will be described. Since these functional groups can be precursors to each other, they are described in the order starting from the crosslinkable silyl group.

As a method for synthesizing a vinyl polymer having at least one crosslinkable silyl group, (A) a vinyl polymer having at least one alkenyl group and a hydrosilane compound having a crosslinkable silyl group may be used as a catalyst for hydrosilylation. (B) Method of reacting a vinyl polymer having at least one hydroxyl group with a compound having a group capable of reacting with a hydroxyl group such as a crosslinkable silyl group and an isocyanate group in one molecule (C) When a vinyl polymer is synthesized by radical polymerization, a method of reacting a compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule (D) When synthesizing a vinyl polymer by radical polymerization, Method using a chain transfer agent having a crosslinkable silyl group (E) Vinyl having at least one highly reactive carbon-halogen bond A method of reacting a compound having a stable carbanion and crosslinkable silyl group in a molecule in the polymer; and the like.

The vinyl polymer having at least one alkenyl group used in the method (A) can be obtained by various methods. The synthesis method is illustrated below, but is not limited thereto.

(Aa) When synthesizing a vinyl polymer by radical polymerization, for example, a polymerizable alkenyl group and a low polymerizable alkenyl group are combined in one molecule as shown in the following general formula 9. A method in which a compound is reacted as a second monomer. ^{_{H 2 C = C (R 14}} ) -R 15 -R 16 -C (R 17) = CH 2 (9) ( wherein, R ¹⁴ represents a hydrogen or a methyl group, R ¹⁵ is -C
(O) O- or an o-, m-, p-phenylene group; R ¹⁶ represents a direct bond or a divalent organic group having 1 to 20 carbon atoms, including one or more ether bonds. It may be. R ¹⁷ is hydrogen or an alkyl group having 1 to 20 carbon atoms;
It represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms.) There is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule. In particular, when a rubbery property is expected in living radical polymerization, it is preferable to react as a second monomer at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer.

(Ab) When a vinyl-based polymer is synthesized by living radical polymerization, for example, 1,5-hexadiene, 1,7-octadiene, A method of reacting a compound having at least two alkenyl groups having low polymerizability such as 9-decadiene.

(Ac) Various organic compounds having an alkenyl group such as an organic tin such as allyltributyltin and allyltrioctyltin may be used as the vinyl polymer having at least one highly reactive carbon-halogen bond. A method in which a halogen is substituted by reacting a metal compound.

(Ad) A vinyl polymer having at least one highly reactive carbon-halogen bond has a general formula 1
A method in which a halogen is substituted by reacting a stabilized carbanion having an alkenyl group as mentioned in the above No. 0. ^{M + C - (R 18)} (R 19) -R 20 -C (R 17) = CH 2 (10) ( wherein, R ¹⁷ is as defined above, R ^18, R ¹⁹ together carbanion C ^- stable Or one of them is the above-mentioned electron-withdrawing group and the other is hydrogen or a carbon atom having 1 to 10 carbon atoms.
Represents an alkyl group or a phenyl group. R ²⁰ represents a direct bond or a divalent organic group having 1 to 10 carbon atoms, and may contain one or more ether bonds. M ⁺ represents an alkali metal ion or a quaternary ammonium ion.) The electron-withdrawing groups for R ¹⁸ and R ¹⁹ include —CO ₂ R and —C
Those having the structure of (O) R and -CN are particularly preferred.

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

(Af) The vinyl polymer having at least one highly reactive carbon-halogen bond may be, for example, an oxyanion or carboxy having an alkenyl group represented by the general formula (11) or (12). A method in which a halogen is substituted by reacting a rate anion. ^{_{H 2 C = C (R 17}} ) -R 21 -O - M + (11) ( wherein, R ^17, M ⁺ is the same .R ²¹ above are 1 to 2 carbon atoms
H ₂ C 有機 C (R ¹⁷ ) -R ²² -C (O) O ⁻ M ⁺ (12) wherein R 2 is a divalent organic group which may contain one or more ether bonds. ¹⁷ , M ⁺ is the same as described above, and R ²² is a direct bond or a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds.

The above-mentioned method for synthesizing a vinyl polymer having at least one highly reactive carbon-halogen bond is based on an atom transfer radical using an organic halide as described above as an initiator and a transition metal complex as a catalyst. Examples include, but are not limited to, polymerization methods.

The vinyl polymer having at least one alkenyl group can also be obtained from a vinyl polymer having at least one hydroxyl group, and the methods exemplified below can be used, but are not limited to these. is not.
(Ag) A method in which a base such as sodium methoxide is allowed to act on a hydroxyl group of a vinyl polymer having at least one hydroxyl group to react with an alkenyl group-containing halide such as allyl chloride.

(Ah) A method of reacting an alkenyl group-containing isocyanate compound such as allyl isocyanate.

(Ai) A method in which an alkenyl group-containing acid halide such as (meth) acrylic acid chloride is reacted in the presence of a base such as pyridine.

(Aj) a method of reacting an alkenyl group-containing carboxylic acid such as acrylic acid in the presence of an acid catalyst.

In the present invention, when a halogen is not directly involved in a method for introducing an alkenyl group such as (Aa) and (Ab), a vinyl polymer is synthesized by using a living radical polymerization method. Is preferred. The method (Ab) is more preferable because the control is easier.

In the case of introducing an alkenyl group by converting a halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halogen having at least one highly reactive carbon-halogen bond may be used. Halide, or a sulfonyl halide compound as an initiator,
Obtained by radical polymerization of a vinyl monomer using a transition metal complex as a catalyst (atom transfer radical polymerization method).
At least one highly reactive carbon-halogen bond at the terminal
It is preferable to use a vinyl polymer having two or more vinyl polymers. The method (Af) is more preferable because the control is easier.

The hydrosilane compound having a crosslinkable silyl group is not particularly limited, but a typical example is a compound represented by the general formula (13). H- [Si (R ⁹ ) _2-b (Y) _b O] _m -Si (R ¹⁰ ) _3-a (Y) _a (13) wherein R ⁹ and R ¹⁰ each have 1 carbon atom Alkyl group having 20 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, 7 to 20 carbon atoms
An aralkyl group, 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), and R ⁹ or R ¹⁰ is 2
When there are more than one, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Ys are present, they may be the same or different. a is 0, 1, 2, or 3
And b represents 0, 1, or 2. m is 0 to 19
Is an integer. However, it is assumed that a + mb ≧ 1 is satisfied.中 で も Among these hydrosilane compounds, particularly, a crosslinkable group represented by the general formula 14 H—Si (R ¹⁰ ) _3-a (Y) _a (14) (wherein R ¹⁰ , Y and a are the same as above) Are preferred from the viewpoint of easy availability.

When adding the above-mentioned hydrosilane compound having a crosslinkable silyl group to an alkenyl group, a transition metal catalyst is usually used. As the transition metal catalyst, for example, platinum alone, alumina, silica, a dispersion of platinum solids on a carrier such as carbon black, chloroplatinic acid, a complex of chloroplatinic acid and alcohol, aldehyde, ketone, etc.
Platinum-olefin complexes and platinum (0) -divinyltetramethyldisiloxane complexes are mentioned. Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ and RhC
l ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ ,
PdCl ₂ .H ₂ O, NiCl ₂ , TiCl _{4 and the} like.

The methods for producing the vinyl polymer having at least one hydroxyl group used in the methods (B) and (Ag) to (Aj) are exemplified by the following methods. However, the present invention is not limited to this.

(Ba) When a vinyl polymer is synthesized by radical polymerization, for example, a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule as shown in the following general formula 15 may be used as a second compound. A method of reacting as a monomer. H ₂ C ＝ C (R ¹⁴ ) -R ¹⁵ -R ¹⁶ -OH (15) (wherein R ¹⁴ , R ¹⁵ and R ¹⁶ are the same as above) wherein a polymerizable alkenyl group and a hydroxyl group are contained in one molecule. There is no limitation on the timing of reacting the compound having both of the above. Particularly, in the case of living radical polymerization, when a rubber-like property is expected, the reaction is carried out as the second monomer at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer. Is preferred.

(Bb) When synthesizing a vinyl polymer by living radical polymerization, at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer, for example, alkenyl such as 10-undecenol, 5-hexenol and allyl alcohol is used. A method of reacting alcohol.

(Bc) For example, JP-A-5-262808
A radical polymerization of a vinyl monomer using a large amount of a hydroxyl group-containing chain transfer agent such as a hydroxyl group-containing polysulfide shown in (1).

(Bd) For example, JP-A-6-23991
2. A method of radically polymerizing a vinyl monomer using hydrogen peroxide or a hydroxyl group-containing initiator as described in JP-A-8-283310.

(Be) For example, Japanese Unexamined Patent Publication No.
A method of radically polymerizing a vinyl monomer by using an excess of alcohols as described in (1).

(Bf) For example, JP-A-4-132706
A method of introducing a hydroxyl group into a terminal by hydrolyzing or reacting a halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond with a hydroxyl group-containing compound by a method such as that described in US Pat.

(Bg) A vinyl polymer having at least one carbon-halogen bond having high reactivity has a general formula 1
6. A method in which a stabilized carbanion having a hydroxyl group as described in 6 is reacted to replace halogen. ^{M + C - (R 18)} (R 19) -R 20 -OH (16) as an electron withdrawing group ^{(wherein, R 18, R 19, R} 20, are the same) R ^18, R ¹⁹ are, -CO ₂ R, -C
Those having the structure of (O) R and -CN are particularly preferred.

(Bh) An enolate anion is prepared by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a simple metal such as zinc or an organometallic compound. A method of reacting aldehydes or ketones later.

(Bi) A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with, for example, a hydroxyl group-containing oxyanion or carboxylate anion represented by the general formula 17 or 18. Substituting halogen. ^{HO-R 21 -O - M +} (17) ( wherein, R ²¹ and M ⁺ are the ^{same) HO-R 22 -C (O} ) O - M + (18) ( wherein, R ²² and M ⁽⁺ Is the same as above.) (Bj) When a vinyl polymer is synthesized by living radical polymerization, at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer, as a second monomer, polymerizable A compound having a low alkenyl group and a hydroxyl group.

The compound is not particularly limited, and examples thereof include a compound represented by the general formula 19. ^{_{H 2 C = C (R 14}} ) -R 21 -OH (19) ( wherein, R ¹⁴ and R ²¹ are the same as those described above.) It is not particularly restricted but includes compounds represented by the general formula 19 Alkenyl alcohols such as 10-undecenol, 5-hexenol and allyl alcohol are preferable because they are easily available. And the like.

In the present invention, when a halogen is not directly involved in a method for introducing a hydroxyl group such as (Ba) to (Be) and (Bj), a vinyl radical is produced by a living radical polymerization method. Preferably, a polymer is synthesized. The method (Bb) is more preferable because the control is easier.

When a hydroxyl group is introduced by converting a halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halide,
Alternatively, a vinyl-based compound having at least one highly reactive carbon-halogen bond at a terminal obtained by radically polymerizing a vinyl-based monomer using a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst (atom transfer radical polymerization method). Preferably, a polymer is used. The method (B-i) is more preferable because the control is easier.

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

Examples of the compound having a polymerizable alkenyl group and a crosslinkable silyl group in one molecule used in the method (C) include, for example, trimethoxysilylpropyl (meth) acrylate and methyldimethoxysilylpropyl (meth) acrylate. Such a compound represented by the following general formula 20 is exemplified. ^{_{H 2 C = C (R 14}} ) -R 15 -R 23 - [Si (R 9) 2-b (Y) b O] m -Si (R 10) 3-a (Y) a (20) ( Formula Wherein R ⁹ , R ¹⁰ , R ¹⁴ , R ¹⁵ , Y, a, b, and m are the same as those described above, and R ²³ is a direct bond or a divalent organic group having 1 to 20 carbon atoms, and There may be an ether bond.) There is no particular limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule, but rubbery properties are expected especially in living radical polymerization. In this case, it is preferable to react as the second monomer at the end of the polymerization reaction or after the completion of the reaction of a predetermined monomer.

As the chain transfer agent having a crosslinkable silyl group used in the chain transfer agent method (D), for example,
And mercaptans having a crosslinkable silyl group, hydrosilanes having a crosslinkable silyl group, and the like, which are described in JP-B-14068 and JP-B-4-55444.

In the method for synthesizing the vinyl polymer having at least one highly reactive carbon-halogen bond used in the method (E), the above-mentioned organic halide or the like is used as an initiator, Examples include, but are not limited to, atom transfer radical polymerization using a metal complex as a catalyst. Compounds having both a crosslinkable silyl group and a stabilized carbanion in one molecule include those represented by the general formula 21. ^{M + C - (R 18)} (R 19) -R 24 -C (H) (R 25) -CH 2 - [Si (R 9) 2-b (Y) b O] m -Si (R 10) _3-a (Y) _a (21) (wherein, R ⁹ , R ¹⁰ , R ¹⁸ , R ¹⁹ , Y, a, b, and m are the same as those described above. R ²⁴ is a direct bond or a group having 1 to 1 carbon atoms. R ²⁵ may be hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or 7 to 10 carbon atoms, which may contain one or more ether bonds in the divalent organic group of 10.
Represents an aralkyl group. ) The electron-withdrawing groups for R ¹⁸ and R ¹⁹ include —CO ₂ R and —C
Those having the structure of (O) R and -CN are particularly preferred. Vinyl polymer having a terminal reactive functional group in the epoxy group present invention include, but are not limited to, the following steps: (1) producing a vinyl polymer by polymerizing a vinyl monomer to living radical polymerization (2) subsequently reacting a compound having both a reactive functional group and an ethylenically unsaturated group;

Further, in the atom transfer radical polymerization, there is also a method in which allyl alcohol is reacted at the end of polymerization and then epoxy cyclization is performed with a hydroxyl group and a halogen group. The method for producing a vinyl polymer having at least one amino group at the terminal of the main chain includes the following steps. (1) producing a vinyl polymer having at least one halogen group at the terminal of the main chain; and (2) converting the terminal halogen to a substituent having an amino group using an amino group-containing compound.

The substituent having an amino group is not particularly limited, and examples thereof include a group represented by the general formula 22. _{^{-O-R 26 -NR 12 2 (}} 22) ( wherein, R ²⁶ represents one or more ether bonds or ester bonds carbon atoms which may contain 1 to 20 divalent organic group .R ¹² is hydrogen or a monovalent organic group having 1 to 20 carbon atoms. The two R ^{12 s} may be the same or different from each other, and are connected to each other at the other end to form a cyclic structure. In the general formula 22, R ²⁶ has 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, an arylene group having 6 to 20 carbon atoms, and a 7 to 2 carbon atoms
0 aralkylene group, etc., wherein —C ₆ H ₄ —R ²⁷ — (wherein C ₆ H ₄ is a phenylene group, and R ²⁷ is a group containing a direct bond or one or more ether bonds or ester bonds. Or a divalent organic group having 1 to 14 carbon atoms, or —C (O) —R ²⁸ — (wherein R ²⁸ represents a direct bond or one or more ether bonds or ester bonds) 1 to 19 carbon atoms which may be contained
Represents a divalent organic group. Is preferred.

Conversion of terminal halogen of vinyl polymer
As a result, it is possible to introduce an amino group into the polymer terminal.
Wear. Although the substitution method is not particularly limited, the reaction is controlled.
Amino group-containing compounds are considered nucleophiles because they are easy to control.
Is preferred. As such a nucleophile
For example, a hydroxyl group and an amino group represented by the general formula 23 are combined.
Compounds. HO-R²⁶-NR¹² _Two (23) (wherein, R²⁶Represents one or more ether bonds or esters
Divalent organic group having 1 to 20 carbon atoms which may contain a bond
Represents R¹²Is hydrogen or a monovalent organic compound having 1 to 20 carbon atoms
Group, two R¹²Are the same or different
May also be interconnected at the other end to form an annular structure
May be formed. In the above general formula 23, R²⁶Is one or more ether bonds
1 to 20 carbon atoms which may contain a bond or an ester bond
Is a divalent organic group, for example, an alkyl having 1 to 20 carbon atoms.
Rene group, arylene group having 6 to 20 carbon atoms, 7 to 2 carbon atoms
And an aralkylene group of 0. These hydroxyl groups
Among compounds having both an amino group and ²⁶Is -C₆H_Four-R²⁷− (Where C₆H_FourIs a phenylene group, R²⁷Is a direct bond or
Contains one or more ether or ester bonds
Which may represent a divalent organic group having 1 to 14 carbon atoms)
Aminophenols; -C (O) -R²⁸-Where R²⁸Is a direct bond or one or more ether bonds
1 to 19 carbon atoms which may contain a bond or an ester bond
Which represents a divalent organic group).
New

As specific compounds, for example, ethanolamine; o, m, p-aminophenol; o, m, p-
_{NH 2 -C 6 H 4 -CO 2} H; glycine, alanine, etc. aminobutanoic acid.

A compound having both an amino group and an oxyanion can be used as a nucleophile. Such a compound is not particularly limited, and examples thereof include a compound represented by the general formula 24. ^{M + O - -R 26 -NR 12} 2 (24) ( wherein, R ²⁶ represents a divalent organic group having one or more ether bonds or carbon atoms, which may contain an ester bond 20 .R ¹² is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, two R ¹² may be different may be the same each other, connected to each other at the other end, to form a cyclic structure M ⁺ represents an alkali metal ion or a quaternary ammonium ion.) In the general formula 24, M ⁺ is a counter cation of an oxyanion and represents an alkali metal ion or a quaternary ammonium ion. As the alkali metal ion,
Examples thereof include a lithium ion, a sodium ion, and a potassium ion, and a sodium ion or a potassium ion is preferable. Examples of the quaternary ammonium ion include a tetramethylammonium ion, a tetraethylammonium ion, a trimethylbenzylammonium ion, a trimethyldodecylammonium ion, a tetrabutylammonium ion, and a dimethylpiperidinium ion.

Among the above compounds having both an amino group and an oxyanion, the salts of aminophenols represented by the general formula 25 or the salts represented by the general formula 26 are preferred because the substitution reaction is easily controlled and the compound is easily available. Salts of amino acids are preferred. ^{_{M + O - -C 6 H 4}} -R 27 -NR 12 2 (25) M + O - -C (O) -R 28 -NR 12 2 (26) ( 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, and R ³ is a direct bond or one or more ether bonds or ester bonds. represents a divalent organic group comprise also good to 19 carbon atoms and .R ¹² is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, two R ¹² are different may be the same with each other And M ⁺ may be mutually connected at the other end to form a cyclic structure. M ⁺ is the same as described above.) The compound having an oxyanion represented by any one of the general formulas 24 to 26 has the general formula It can be easily obtained by reacting the compound represented by No. 23 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 hydrogen carbonate Sodium, sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, methyllithium, ethyllithium, n-butyllithium, ter
t-butyllithium, lithium diisopropylamide,
Lithium hexamethyldisilazide and the like. The amount of the base used is not particularly limited, but is 0.5 to 5 equivalents, preferably 0.8 to 1.2 equivalents, based on the precursor.

Examples of the solvent used for reacting the precursor with the base include: hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; and halogenated solvents such as methylene chloride and chloroform. Hydrocarbon solvents; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone;
Alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; ester solvents such as ethyl acetate and butyl acetate; ethylene carbonate Carbonate solvents such as propylene carbonate; amide solvents such as dimethylformamide and dimethylacetamide; and sulfoxide solvents such as dimethylsulfoxide. These can be used alone or in combination of two or more.

The 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 reacting the compound with a quaternary ammonium halide. 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 terminal halogen of the polymer. For example, hydrocarbon solvents such as benzene and toluene; diethyl ether;
Ether solvents such as tetrahydrofuran; halogenated hydrocarbon solvents such as methylene chloride and chloroform; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methanol, ethanol, propanol, isopropanol, n-butyl alcohol, ter
alcohol solvents such as t-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile, benzonitrile; ester solvents such as ethyl acetate and butyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate; dimethylformamide, dimethyl Amide solvents such as acetamide; sulfoxide solvents such as dimethyl sulfoxide; They are,
They can be used alone or in combination of two or more.

The reaction can be carried out at a temperature of 0 to 150 ° C. The amount of the amino group-containing compound to be used is not particularly limited, but is 1 to 5 equivalents, preferably 1 to 1.2 equivalents, relative to the terminal halogen of the polymer.

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 in the nucleophilic substitution reaction affects the nucleophilic substitution reaction, it is preferable to protect the amino group with an appropriate substituent. Such substituents include a benzyloxycarbonyl group,
Examples thereof include a tert-butoxycarbonyl group and a 9-fluorenylmethoxycarbonyl group.

Further, there is a method in which the halogen terminal of the vinyl polymer is substituted with an azide anion and then reduced with LAH or the like. Polymerizable carbon-carbon double bond A method for introducing a polymerizable carbon-carbon double bond into the polymer (I) of the present invention is not limited, but includes the following methods. A method for producing a vinyl polymer by substituting a halogen group of a vinyl polymer with a radical polymerizable compound having a carbon-carbon double bond. As a specific example, a method in which a vinyl polymer having a structure represented by the general formula 27 is reacted with a compound represented by the general formula 28. ²⁹ R ³⁰ X (27) (wherein, R ^29, R ³⁰ is a group .X bonded to an ethylenically unsaturated group of a vinyl monomer represents chlorine, bromine, or iodine.) -CR M ^{+ - OC (O) C (R} 13) = CH 2 (28) ( wherein, R ¹³ is hydrogen, or, .M ⁺ is an alkali metal represents an organic group having 1 to 20 carbon atoms, or a quaternary ammonium ion Represented by a reaction between a vinyl polymer having a hydroxyl group and a compound represented by the general formula 29. XC (O) C (R ¹³ ) ＝ CH ₂ (29) (wherein, R ¹³ represents hydrogen or an organic group having 1 to 20 carbon atoms. X represents chlorine, bromine, or a hydroxyl group.) A diisocyanate compound is reacted with a vinyl polymer having the general formula 30
By reacting with a compound represented by the formula: ^{HO-R 31 -OC (O)} C (R 13) = CH 2 (30) ( wherein, R ¹³ is hydrogen or,, .R ³¹ 2 to 20 carbon atoms represents an organic group having 1 to 20 carbon atoms These methods are described in detail below.

The above method will be described. A method wherein a vinyl polymer having a terminal structure represented by the general formula 27 is reacted with a compound represented by the general formula 28. ²⁹ R ³⁰ X (27) (wherein, R ^29, R ³⁰ is a group .X bonded to an ethylenically unsaturated group of a vinyl monomer represents chlorine, bromine, or iodine.) -CR M ^{+ - OC (O) C (R} 13) = CH 2 (28) ( wherein, R ¹³ is hydrogen, or, .M ⁺ is an alkali metal represents an organic group having 1 to 20 carbon atoms, or a quaternary ammonium ion The vinyl polymer having a terminal structure represented by the general formula 27 is obtained by polymerizing a vinyl monomer using the above-mentioned organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or It is produced by a method of polymerizing a vinyl monomer using a halogen compound as a chain transfer agent, and the former is preferred.

The compound represented by the general formula 28 is not particularly limited. Specific examples of R ¹³ include, for example,-
_{H, -CH 3, -CH 2 CH} 3, - (CH 2) n CH 3 (n 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 the oxyanion, and examples of M ⁺ include an alkali metal ion, specifically, a lithium ion, a sodium ion, a potassium ion, and a quaternary ammonium ion. Examples of the quaternary ammonium ion include a tetramethylammonium ion, a tetraethylammonium ion, a tetrabenzylammonium ion, a trimethyldodecylammonium ion, a tetrabutylammonium ion, and a dimethylpiperidinium ion, and a sodium ion and a potassium ion are preferable. The amount of the oxyanion of the general formula 28 to be used is preferably 1 to 5 equivalents, more preferably 1.0 to 1.2 equivalents, to the halogen group of the general formula 27. The solvent for carrying out this reaction is not particularly limited, but a polar solvent is preferred because it is a nucleophilic substitution reaction.For example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphonic Triamide, acetonitrile, and the like are used. The temperature at which the reaction is carried out is not limited, but is generally from 0 to
The reaction is preferably carried out at a temperature of from 150 ° C to a temperature of from 100 ° C to 100 ° C in order to maintain a polymerizable terminal group.

The above method will be described. A method in which a vinyl polymer having a hydroxyl group is reacted with a compound represented by the general formula 29. ^{XC (O) C (R 13} ) = CH 2 (29) ( wherein, R ¹³ is hydrogen or,, .X represents an organic group having 1 to 20 carbon atoms represents a chlorine, bromine or a hydroxyl group.) General The compound represented by the formula 29 is not particularly limited, and specific examples of R ¹³ include, for example, -H, -CH ₃ ,
_{-CH 2 CH 3, - (CH} 2) n CH 3 (n represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -CN, and the like are exemplified, preferably -H, —CH ₃ .

The vinyl polymer having a hydroxyl group at the terminal, preferably at the terminal, is prepared by a method of polymerizing a vinyl monomer using the above-mentioned organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or a method of polymerizing a hydroxyl group. Is produced by a method in which a vinyl monomer is polymerized using a compound having the formula (I) as a chain transfer agent, but 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 represented by the following general formula 31 or the like having both a polymerizable alkenyl group and a hydroxyl group in one molecule is reacted as a second monomer. How to let. ^{_{H 2 C = C (R 32}} ) -R 33 -R 34 -OH (31) ( wherein, R ³² is preferably a hydrogen or a methyl group with an organic group having 1 to 20 carbon atoms, being the same or different R ³³ represents —C (O) O— (ester group) or an o-, m- or p-phenylene group, and R ³⁴ has a direct bond or one or more ether bonds. Represents a divalent organic group having 1 to 20 carbon atoms, wherein R ³³ is an ester group, a (meth) acrylate compound, and R ³³ is a phenylene group, a styrene compound. There is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule.However, if rubbery properties are expected, the polymerization is terminated at the end of the polymerization reaction or after the reaction of a predetermined monomer. It is preferred to react as monomer 2 There.

(B) When synthesizing a vinyl polymer by living radical polymerization, at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer, an alkenyl group having a low polymerizability in one molecule as a second monomer is used. A method of reacting a compound having a hydroxyl group.

The compound is not particularly limited, and examples thereof include a compound represented by the general formula 32. ^{_{H 2 C = C (R 32}} ) -R 35 -OH (32) ( wherein, R ³² are the same as those described above .R ³⁵ number of 1 or more which may contain an ether bond carbons 1 ~ 20
Represents a divalent organic group. The compound represented by the general formula 32 is not particularly limited, but alkenyl alcohols such as 10-undecenol, 5-hexenol, and allyl alcohol are preferable because they are easily available.

(C) Vinyl having at least one carbon-halogen bond represented by the general formula 27 obtained by atom transfer radical polymerization according to the method disclosed in JP-A-4-132706 and the like. A method of introducing a hydroxyl group into a terminal by hydrolyzing or reacting a halogen of a system polymer with a hydroxyl group-containing compound.

(D) Stabilization of a vinyl polymer having at least one carbon-halogen bond represented by the general formula 27 obtained by atom transfer radical polymerization and having a hydroxyl group represented by the general formula 33 A method in which a halogen is substituted by reacting a carbanion. ^{M + C - (R 36)} (R 37) 35 -OH (33) ( wherein -R, R ³⁵ are the same as those described above .R ³⁶ and R ³⁷ together carbanion C ^- electrons stabilize The attraction group, or one of them, represents the above-mentioned electron withdrawing group and the other represents hydrogen or an alkyl group having 1 to 10 carbon atoms or a phenyl group.
^Examples of the electron withdrawing group for R ³⁶ and R ³⁷ include —CO ₂ R (ester group), —C (O) R (keto group), and —CON
(R ₂ ) (amide group), —COSR (thioester group), —CN (nitrile group), —NO ₂ (nitro group) and the like. The substituent R is 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 preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group. As R ³⁶ and R ³⁷ , —CO ₂ R, —C (O) R and —CN are particularly preferred. (E) General formula 27 obtained by atom transfer radical polymerization
A vinyl polymer having at least one carbon-halogen bond represented by is reacted with a metal simple substance such as zinc or an organometallic compound to prepare an enolate anion, and then an aldehyde or ketone is prepared. How to react.

(F) A vinyl-containing polymer having at least one halogen at the terminal of the polymer, preferably represented by the general formula 27, is added to a hydroxyl group-containing oxyanion represented by the following general formula 34 or the like; A method of reacting a hydroxyl group-containing carboxylate anion represented by 35 or the like to replace the halogen with a hydroxyl group-containing substituent. ^{HO-R 35 -O - M +} (34) ( wherein, R ³⁵ and M ⁺ are the same as those described ^{above.) HO-R 35 -C (} O) O - M + (35) ( in the formula , R ³⁵ and M ⁺ are the same as those described above.) In the present invention, when a halogen is not directly involved in the method for introducing a hydroxyl group as in (a) to (b), control is easier. The method (b) is more preferred.

In the case where a hydroxyl group is introduced by converting a halogen of a vinyl polymer having at least one carbon-halogen bond as shown in (c) to (f), control is easier because The method f) is more preferred.

The above method will be described. The vinyl polymer having a hydroxyl group is reacted with a diisocyanate compound, and the remaining isocyanate group is reacted with a compound of the general formula 36.
By reacting with a compound represented by the formula: ^{HO-R 31 -OC (O)} C (R 13) = CH 2 (36) ( wherein, R ¹³ is hydrogen or,, .R ³¹ 2 to 20 carbon atoms represents an organic group having 1 to 20 carbon atoms The compound represented by the general formula 36 is not particularly limited. Specific examples of R ¹³ include, for example, —H, —CH ₃ ,
_{-CH 2 CH 3, - (CH} 2) n CH 3 (n represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -CN, and the like are exemplified, preferably -H, —CH ₃ . Specific compounds include 2-hydroxypropyl methacrylate.

The vinyl polymer having a hydroxyl group at the terminal is
As above.

The diisocyanate compound is not particularly limited, and any conventionally known diisocyanate compound can be used. For example, tolylene diisocyanate, 4,4'-
Diphenylmethane diisocyanate, hexamethyl diisocyanate, xylylene diisocyanate, meta-xylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate,
Isocyanate compounds such as hydrogenated toluylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate; These can be used alone or in combination of two or more. Further, a blocked isocyanate may be used.

In order to make better use of weather resistance, it is preferable to use a diisocyanate compound having no aromatic ring, such as hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate. << About heavy calcium carbonate (II) of component (B) >> The heavy calcium carbonate (II) used in the present invention is:
Natural chalk (chalk), marble, limestone, etc. are mechanically crushed and processed. The pulverization method includes a dry method and a wet method, but a wet pulverized product is not preferable because it often deteriorates the storage stability of the curable composition of the present invention. Heavy calcium carbonate is a product having various average particle diameters depending on the classification. Heavy calcium carbonate (II) used in the present invention has a specific surface area of 1.5 m ² / g.
Not less than 50 m ² / g. The value of the specific surface area of the heavy calcium carbonate (II) of the present invention is defined as JI as a measuring method.
Air permeation method performed according to SK5101 (method of determining specific surface area from permeability of air to powder packed bed)
Means the value measured by As a measuring instrument, it is preferable to use a specific surface area measuring device SS-100 manufactured by Shimadzu Corporation.

The heavy calcium carbonate (I) used in the present invention
The value of the specific surface area of I) is less than 1.5 m ² / g or more 50 m ² / g, but preferably 2m ² / g or more 50 m ² / g or less, 2.4 m ² / g or more 50 m ² / g or less It is more preferably from 3 m ² / g to 50 m ² / g. If the specific surface area is less than 1.5 m ² / g, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product may not be sufficient. As the value of the specific surface area is larger, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product becomes larger. Incidentally, the specific surface area is preferably 50 m ² / g or less. <Surface treatment> Heavy calcium carbonate (I) used in the present invention
I) is more preferably heavy calcium carbonate subjected to a surface treatment using a surface treatment agent. When the surface-treated calcium carbonate is used as the component (B), it is considered that the workability of the composition of the present invention is improved, and the effect of improving the adhesiveness and weather resistance of the curable composition is further improved. As the surface treatment agent, organic substances such as fatty acids, fatty acid soaps and fatty acid esters and various surfactants, and various coupling agents such as silane coupling agents and titanate coupling agents are used. Specific examples include, but are not limited to, fatty acids such as caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid. And salts of the fatty acids such as sodium and potassium, and alkyl esters of the fatty acids. Specific examples of the surfactant include polyoxyethylene alkyl ether sulfates and long-chain alcohol sulfates, and sulfate-type anionic surfactants such as sodium salts and potassium salts thereof, and alkylbenzenesulfonic acid and alkylnaphthalene. Sulfonic acid, paraffin sulfonic acid, α-olefin sulfonic acid, alkyl sulfosuccinic acid and the like, and sulfonic acid type anionic surfactants such as a sodium salt and a potassium salt thereof, and the like.

The amount of the surface treatment agent to be treated is preferably in the range of 0.1 to 20% by weight, more preferably in the range of 1 to 5% by weight, based on heavy calcium carbonate. preferable. If the treatment amount is less than 0.1% by weight, the effect of improving workability, adhesiveness and weather resistance may not be sufficient, and if it exceeds 20% by weight, the storage stability of the curable composition is reduced. May be. <Addition amount> Heavy calcium carbonate (II) used in the present invention
Is preferably used in a range of 5 to 500 parts by weight, and more preferably in a range of 20 to 350 parts by weight, based on 100 parts by weight of the vinyl polymer (I). More preferably, it is particularly preferably used in the range of 40 to 200 parts by weight. If the amount is less than 5 parts by weight, the effect of improving the breaking strength, breaking elongation, adhesiveness and weather resistance of the cured product may not be sufficient.
If the amount is more than 10 parts by weight, the workability of the curable composition may decrease. The heavy calcium carbonate (II) of the present invention may be used alone or in combination of two or more.

Further, heavy calcium carbonate having a specific surface area of less than 1.5 m ² / g is used in combination with the curable composition to such an extent that the cured product of the curable composition does not deteriorate the breaking strength, breaking elongation, adhesiveness and weather resistance. May be. The composition of the present invention can be further modified by blending various fillers as fillers other than heavy calcium carbonate (II). Specific examples of such fillers include, for example, wood flour, pulp, cotton chips, asbestos, glass fiber, carbon fiber,
Reinforcing fillers such as mica, walnut husk powder, rice husk powder, graphite, diatomaceous earth, terra alba, fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid, carbon black Materials: Colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, active zinc white, zinc powder and white powder Fillers such as balloons; fibrous fillers such as asbestos, glass fibers and filaments, but are not limited thereto. These fillers may be used alone or in combination with the above-mentioned heavy calcium carbonate (II). << Curable Composition >> Some curable compositions of the present invention require a curing catalyst or a curing agent depending on each crosslinkable functional group. Further, various compounding agents may be added according to the desired physical properties. <Curing Catalyst / 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. As the properties of the cured product, a wide range from rubbery to resinous can be prepared according to the molecular weight of the polymer and the main chain skeleton.

Examples of such a condensation catalyst include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutylmalate, and the like. Dibutyltin diisooctyl malate, dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, dioctyltin diisooctyl Tetravalent tin compounds such as malate; divalent tin compounds such as tin octylate, tin naphthenate and tin stearate; titanates such as tetrabutyl titanate and tetrapropyl titanate; Organoaluminum compounds such as ammonium trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; chelate compounds such as zirconium tetraacetylacetonate, titanium tetraacetylacetonate; lead octylate; butylamine, octyl Amine, 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) undecene -7 (DBU)
And the like; or salts of these amine compounds with carboxylic acids and the like; reactants and mixtures of amine compounds and organotin compounds such as reactants or mixtures of laurylamine and tin octylate; Low molecular weight polyamide resin obtained from polyamine and polybasic acid; reaction product of excess polyamine and epoxy compound; amino such as γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane Silanol condensation catalysts such as silane coupling agents having groups; and other known silanol condensation catalysts such as other acidic catalysts and basic catalysts.

These catalysts may be used alone.
Two or more kinds may be used in combination. The amount of the condensation catalyst is from 0.1 to 100 parts by weight (hereinafter the same) with respect to 100 parts (parts by weight, hereinafter the same) of the vinyl polymer (I) having at least one crosslinkable silyl group.
About 20 parts are preferable, and 1 to 10 parts is more preferable. If the amount of the silanol condensation catalyst falls below this range, the curing speed may be slow, and the curing reaction may be difficult to proceed sufficiently. On the other hand, when the amount of the silanol condensation catalyst exceeds this range, local heat generation and foaming occur during curing, and it becomes difficult to obtain a good cured product, and the pot life becomes too short, which is preferable from the viewpoint of workability. Absent.

In the curable composition of the present invention, in order to further increase the activity of the condensation catalyst, the general formula 37 R ⁴⁹ _a Si (OR ⁵⁰ ) _4-a (37) (where R ⁴⁹ and R ⁵⁰ are , Each independently having 1 carbon atom
To 20 substituted or unsubstituted hydrocarbon groups. A is 0, 1, 2, or 3. ), A silicon compound having no silanol group may be added.

Examples of the silicon compound include, but are not limited to, those represented by general formula (1) such as phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and triphenylmethoxysilane. R ⁴⁹ is preferably an aryl group having 6 to 20 carbon atoms, since the effect of accelerating the curing reaction of the composition is large. In particular, diphenyldimethoxysilane and diphenyldiethoxysilane are most preferable because they are inexpensive and easily available.

The compounding amount of the silicon compound is determined by the amount of the vinyl polymer (I) 10 having at least one crosslinkable silyl group.
About 0.01 to 20 parts is preferable with respect to 0 parts, and 0.1
-10 parts is more preferred. If the amount of the silicon compound falls below this range, the effect of accelerating the curing reaction may be reduced. On the other hand, if the 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, in the case of cross-linking using an alkenyl group, it is not limited, but it is preferable to use a hydrosilyl group-containing compound as a curing agent and cross-link by a hydrosilylation reaction using a hydrosilylation catalyst.

Examples of the hydrosilyl group-containing compound include al
Hydrocarbons that can be cured by crosslinking with polymers having kenyl groups
There is no particular limitation as long as it is a silyl group-containing compound.
Can be used. For example, general formula 38 or 3
A chain polysiloxane represented by 9; R⁵¹ _ThreeSiO- [Si (R⁵¹)_TwoO]_a− [Si (H) (R⁵²) O]_b− [Si (R ⁵² ) (R⁵³) O]_c-SiR⁵¹ _Three (38) HR⁵¹ _TwoSiO- [Si (R⁵¹)_TwoO]_a− [Si (H) (R⁵²) O]_b− [Si (R⁵²) (R⁵³) O]_c-SiR⁵¹ _TwoH (39) (wherein, R⁵¹And R⁵²Is an alkyl group having 1 to 6 carbon atoms,
Or a phenyl group, R ⁵³Is an alkyl having 1 to 10 carbons
Group or aralkyl group. a is 0 ≦ a ≦ 100, b
Is an integer satisfying 2 ≦ b ≦ 100 and c is an integer satisfying 0 ≦ c ≦ 100
Show. A) a cyclic siloxane represented by the general formula 40;

[0142]

Embedded image(Where R⁵⁴And R⁵⁵Is an alkyl group having 1 to 6 carbon atoms,
Or a phenyl group, R ⁵⁶Is an alkyl having 1 to 10 carbons
Group or aralkyl group. d is 0 ≦ d ≦ 8, e is 2
≦ e ≦ 10, f represents an integer of 0 ≦ f ≦ 8, and 3 ≦ d
+ E + f ≦ 10 is satisfied. ))
it can.

These may be used alone or in combination of two or more. Among these siloxanes, from the viewpoint of compatibility with the (meth) acrylic polymer, chain siloxanes having a phenyl group represented by the following general formulas 41 and 42 and cyclic siloxanes represented by the general formulas 43 and 44 Is preferred. _{(CH 3) 3 SiO- [Si} (H) (CH 3) O] g - [Si (C 6 H 5) 2 O] h -S i (CH 3) 3 (41) (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 (42) In the formula, R ⁵⁷ represents hydrogen or a methyl group, and g is 2 ≦ g.
≦ 100, h represents an integer of 0 ≦ h ≦ 100. C ₆ H ₅ represents a phenyl group. )

[0144]

Embedded image (Wherein, R ⁵⁷ represents hydrogen or a methyl group.
i ≦ 10 and j are integers satisfying 0 ≦ j ≦ 8 and 3 ≦ i + j ≦ 10. C ₆ H ₅ represents a phenyl group. ) Hydrosilyl group-containing compounds further include 2
A compound obtained by subjecting a hydrosilyl group-containing compound represented by any of the general formulas 38 to 44 to an addition reaction with a low-molecular compound having at least two alkenyl groups so that some hydrosilyl groups remain even after the reaction is used. You can also.
Various compounds can be used as the compound having two or more alkenyl groups in the molecule. For example, 1,4-pentadiene, 1,5-hexadiene,
1,6-heptadiene, 1,7-octadiene, 1,8
Hydrocarbon compounds such as nonadiene and 1,9-decadiene, O, O'-diallylbisphenol A, 3,3'-
Examples thereof include ether compounds such as diallyl bisphenol A, ester compounds such as diallyl phthalate, diallyl isophthalate, triallyl trimellitate and tetraallyl pyromellitate, and carbonate compounds such as diethylene glycol diallyl carbonate.

The above-mentioned alkenyl group-containing compound can be slowly added dropwise to an excess amount of the hydrosilyl group-containing compound represented by the above general formulas 38 to 44 in the presence of a hydrosilylation catalyst to obtain the compound. . Among these compounds, the following compounds are preferred in consideration of the availability of raw materials, the ease of removal of excess siloxane, and the compatibility of the component (A) with the polymer.

[0146]

Embedded image The polymer and the curing agent can be mixed in any 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 more preferably 2.5 to 0.2. It is particularly preferred that the value be 0.4. When the molar ratio is 5 or more, only a cured product with insufficient curing and insufficient tackiness is obtained, and when it is less than 0.2, a large amount of active hydrosilyl groups remains 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 accelerate the reaction more quickly. Such a hydrosilylation catalyst is not particularly limited, and examples thereof include a radical initiator such as an organic peroxide and an azo compound, and a transition metal catalyst.

The radical initiator is not particularly limited.
For example, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane,
Such as 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, dicumyl peroxide, t-butylcumyl peroxide, α, α′-bis (t-butylperoxy) isopropylbenzene Dialkyl peroxides such as dialkyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diacyl peroxides such as lauroyl peroxide, peracid esters such as t-butyl perbenzoate; Peroxydicarbonates such as diisopropyl carbonate, di-2-ethylhexyl percarbonate, 1,1-di (t-butylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -3,3,5-trimethyl Peroxyke such as cyclohexane It can be mentioned Lumpur and the like.

The transition metal catalyst is not particularly limited, and may be, for example, platinum alone, a dispersion of platinum solid in a carrier such as alumina, silica or carbon black, chloroplatinic acid, chloroplatinic acid and an alcohol, an aldehyde, or the like. Examples include a complex with a ketone, a platinum-olefin complex, and a platinum (0) -divinyltetramethyldisiloxane complex. Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , R
hCl 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. The amount of the catalyst is not particularly limited, but 1 mol of the alkenyl group of the vinyl polymer (I).
On the other hand, the amount is preferably in the range of 10 ^-1 to 10 ^-8 mol, and more preferably in the range of 10 ^-3 to 10 ^-6 mol. If the amount is less than 10 ^-8 mol, the curing does not proceed sufficiently. In addition, since the hydrosilylation catalyst is expensive, it is 10 ^-1.
It is preferable not to use more than mol.

The curing temperature is not particularly limited, but it is generally preferable to cure at 0 ° C. to 200 ° C., preferably at 30 ° C. to 150 ° C., more preferably at 80 ° C. to 150 ° C. In the case of a hydroxyl group, the polymer having a hydroxyl group of the present invention is uniformly cured by using a compound having two or more functional groups capable of reacting with the hydroxyl group as a curing agent. As specific examples of the curing agent,
For example, a polyvalent isocyanate compound having two or more isocyanate groups in one molecule, an aminoplast resin such as methylolated melamine and its alkyl ether compound or a low condensation product, a polyfunctional carboxylic acid and its halide, and the like can be mentioned. When preparing a cured product using these curing agents, an appropriate curing catalyst can be used. In the case of an amino group, the polymer having an amino group of the present invention 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 polyvalent isocyanate compound having two or more isocyanate groups in one molecule, an aminoplast resin such as a methylolated melamine and an alkyl etherified product or a low condensed product thereof, a polyfunctional carboxylic acid and And halides thereof. When preparing 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 the polymer having an epoxy group of the present invention is not particularly limited. For example, aliphatic amines, alicyclic amines, aromatic amines; acid anhydrides; polyamides; imidazoles; Amine imides; Ureas; Melamines and derivatives thereof; Polyamine salts; Phenolic resins; Polymer captans, polysulfides; . 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.

As a crosslinking method, a method of curing with an active energy ray or a method of curing with heat can be used. In the active energy ray-curable composition, the photopolymerization initiator is preferably a photoradical initiator or a photoanion initiator. In the thermosetting composition,
Thermal polymerization initiator, azo-based initiator, peroxide, persulfate,
And a redox initiator.

The crosslinking reaction will be described in detail below.

When a polymer having a polymerizable carbon-carbon double bond is crosslinked, a polymerizable monomer and / or oligomer and 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 is preferable. Examples of the radical polymerizable group include an acrylic functional group such as a (meth) acryl group, a styrene group, an acrylonitrile group, a vinyl ester group, an N-vinylpyrrolidone group, an acrylamide group, a conjugated diene group, a vinyl ketone group, and a vinyl chloride group. Is mentioned. Among them, those having a (meth) acryl group similar to the polymer of the present invention are 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,
Examples include a conjugated diene group and a vinyl ketone group. Among them, those having an acrylic functional group are preferred.

Specific examples of the above monomers include (meth) acrylate monomers, cyclic acrylates, N-
Examples include vinylpyrrolidone, styrene-based monomers, acrylonitrile, N-vinylpyrrolidone, acrylamide-based monomers, conjugated diene-based monomers, and vinyl ketone-based monomers. 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 formulas. it can.

[0155]

Embedded image

[0156]

Embedded image

[0157]

Embedded image

[0158]

Embedded image

[0159]

Embedded image (In the formula, n represents an integer of 0 to 20) Styrene-based monomers include styrene, α-methylstyrene, and the like, acrylamide-based monomers include acrylamide, N, N-dimethylacrylamide, and the like, and conjugated diene-based monomers include Butadiene, isoprene, etc.
Examples of the vinyl ketone-based monomer include methyl vinyl ketone.

Examples of the polyfunctional monomer include neopentyl glycol polypropoxy diacrylate, trimethylolpropane polyethoxy triacrylate, bisphenol F polyethoxy diacrylate, and bisphenol A
Polyethoxydiacrylate, dipentaerythritol polyhexanolide hexaacrylate, tris (hydroxyethyl) isocyanurate polyhexanolide triacrylate, tricyclodecane dimethylol diacrylate 2- (2-acryloyloxy-1,1-dimethyl) )
-5-ethyl-5-acryloyloxymethyl-1,3
-Dioxane, tetrabromobisphenol A diethoxy diacrylate, 4,4-dimercaptodiphenyl sulfide dimethacrylate, polytetraethylene glycol diacrylate, 1,9-nonanediol diacrylate, ditrimethylolpropane tetraacrylate and the like. As the oligomer, epoxy acrylate resins such as bisphenol A type epoxy acrylate resin, phenol novolak type epoxy acrylate resin, cresol novolak type epoxy acrylate resin, COOH group-modified epoxy acrylate resin,
Polyols (polytetramethylene glycol, polyester diol of ethylene glycol and adipic acid, 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, xylene) Diisocyanate, etc.) to obtain a hydroxy group-containing (meth) acrylate メ タ hydroxyethyl (meth) acrylate, hydroxypropyl (meth)
Urethane acrylate resin obtained by reacting acrylate, hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, etc., resin in which (meth) acryl group is introduced into the above polyol via ester bond, polyester acrylate resin, etc. Is mentioned.

[0161] These monomers and oligomers are selected depending on the initiator and curing conditions used.

The number average molecular weight of the monomer and / or oligomer having an acrylic functional group is preferably 2,000 or less, and more preferably 1,000 or less, because of good compatibility.

As a method for crosslinking a polymer having a polymerizable carbon-carbon double bond, it is preferable to use active energy rays such as UV rays and electron beams.

In the case of crosslinking by active energy rays, it is preferable to contain a photopolymerization initiator.

The photopolymerization initiator used in the present invention is not particularly limited, but a photoradical initiator and a photoanion initiator are preferable, and a photoradical initiator is particularly preferable. For example, acetophenone, propiophenone, benzophenone, xanthol, fluorein, benzaldehyde,
Anthraquinone, triphenylamine, carbazole,
3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophen, 3-bromoacetophenone, 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-nonyl xanthone, benzoyl, benzoin methyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzyl methoxy ketal, 2-chlorothioxanthone and the like. These initiators may be used alone or in combination with other compounds. Specific examples include a combination with an amine such as diethanolmethylamine, dimethylethanolamine, and triethanolamine, further combined with an iodonium salt such as diphenyliodonium chloride, and a combination with a dye and an amine such as methylene blue. Can be

Further, as a near-infrared light polymerization initiator, a near-infrared light absorbing cationic dye may be used. As a near-infrared light-absorbing cationic dye, it is excited by light energy in the range of 650 to 1500 nm, for example, as disclosed in JP-A-3-11.
It is preferable to use a near-infrared light-absorbing cationic dye-borate anion complex or the like disclosed in JP-A-1402 and JP-A-5-194609, and it is more preferable to use a boron sensitizer in combination.

The amount of the photopolymerization initiator to be added is not particularly limited, since it is only necessary to slightly photofunctionalize the system. However, 0.001 to 10 parts by weight based on 100 parts of the polymer of this composition is used. preferable.

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

As a method of crosslinking a polymer having a polymerizable carbon-carbon double bond, heat is preferably used.

When crosslinking by active energy rays, it is preferable to contain a thermal polymerization initiator.

The thermal polymerization initiator used in the present invention is not particularly limited, and includes an azo-based initiator, a peroxide, a persulfate, and a redox initiator.

Suitable azo initiators include, but are not limited to, 2,2'-azobis (4-methoxy-
2,4-dimethylvaleronitrile) (VAZO 3
3), 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) and 2,2'-azobis (methylisobutyl
G) (V-601) (available from Wako Pure Chemical Industries).

Suitable peroxide initiators include, but are not limited to, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetylperoxydicarbonate, di (4-t- Butylcyclohexyl) peroxydicarbonate (Perkadox)
16S) (available from Akzo Nobel), di (2-ethylhexyl) peroxydicarbonate, t
-Butyl peroxypivalate (Luppersol 1
1) (available from Elf Atochem), t-butylperoxy-2-ethylhexanoate (Trig
onox 21-C50) (available from Akzo Nobel), and dicumyl peroxide.

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

Suitable redox (redox) initiators include, but are not limited to, combinations of the above persulfate initiators with reducing agents such as sodium metabisulfite and sodium bisulfite; And 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, pinacols such as tetraphenyl 1,1,2,2-ethanediol.

The preferred thermal radical initiator is selected from the group consisting of an azo initiator and a peroxide initiator. More preferred are 2,2'-azobis (methylisobutyrate), t-butylperoxypivalate,
And di (4-tert-butylcyclohexyl) peroxydicarbonate, and mixtures thereof.

The thermal initiator used in the present invention is present in a catalytically effective amount, and such amount is not limited,
Typically, about 0.01 to 5 parts by weight based on 100 parts by weight of the polymer of the present invention having at least one terminal acrylic functional group and the monomer and oligomer mixture added to the other. , More preferably about 0.025
~ 2 parts by weight. If a mixture of initiators is used, the total amount of the mixture of initiators is as if only one initiator was used.

The method for curing the thermosetting composition of the present invention is not particularly limited. The temperature varies depending on the type of the thermal initiator, the polymer (I) and the compound to be used. C. to 250.degree. C. are preferred,
The temperature is more preferably in the range of 70C to 200C. The curing time varies depending on the used polymerization initiator, monomer, solvent, reaction temperature and the like, but is usually in the range of 1 minute to 10 hours. <Adhesiveness-imparting agent> A silane coupling agent or an adhesiveness-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) aminopropyl Methyldiethoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-
Amino group-containing silanes such as γ-aminopropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-
Mercapto group-containing silanes such as mercaptopropylmethyldimethoxysilane and γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxy Epoxy group-containing silanes such as silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β
Carboxysilanes such as -carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyl Vinyl-type unsaturated group-containing silanes such as oxypropylmethyldimethoxysilane and γ-acroyloxypropylmethyltriethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; tris (trimethoxysilyl) isocyanurate And the like isocyanurate silanes. Amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, and the like, which are derivatives thereof, can also be used as the silane coupling agent. .

The silane coupling agent used in the present invention is
Usually, 0.1 part with respect to 100 parts of the crosslinkable functional group-containing polymer.
Used in the range of ~ 20 parts. In particular, it is preferable to use it 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 include various adherends, namely, glass, aluminum, stainless steel, zinc, copper, inorganic bases such as mortar, PVC, acrylic,
When used for an organic substrate such as polyester, polyethylene, polypropylene, and polycarbonate, it exhibits a remarkable effect of improving adhesiveness 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 significant.

Specific examples other than the silane coupling agent are not particularly restricted but include, for example, epoxy resins, phenolic resins, sulfur, alkyl titanates, aromatic polyisocyanates and the like.

The above-mentioned adhesiveness-imparting agents may be used alone or in combination of two or more. The addition of these adhesion-imparting agents can improve the adhesion to the adherend. <Plasticizer> In the curable composition of the present invention, various plasticizers are used as needed. The plasticizer is not particularly limited. For example, phthalate esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate and butyl benzyl phthalate; Non-aromatic dibasic acid esters such as dioctyl sebacate, dibutyl sebacate and isodecyl succinate; aliphatic esters such as butyl oleate and methyl acetyl ricinoleate; diethylene glycol dibenzoate;
Esters of polyalkylene glycol such as triethylene glycol dibenzoate and pentaerythritol ester; Phosphates such as tricresyl phosphate and tributyl phosphate; Trimellitic esters; Polystyrenes such as polystyrene and poly-α-methylstyrene Polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene; chlorinated paraffins; hydrocarbon-based oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; polyethylene glycol, polypropylene glycol, polytetramethylene glycol Polyether polyols such as polyether polyols and derivatives obtained by converting hydroxyl groups of these polyether polyols into ester groups, ether groups, etc .; Epoxy plasticizers such as soybean oil and benzyl epoxy stearate; dibasic acids such as sebacic acid, adipic acid, azelaic acid, and phthalic acid; and 2 such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol. Polyester plasticizers obtained from polyhydric alcohols; vinyl polymers obtained by polymerizing vinyl monomers such as acrylic plasticizers by various methods, or a mixture of two or more vinyl polymers. Can be
It is not necessary. In addition, these plasticizers can be blended at the time of polymer production.

The amount of the plasticizer used is not limited, but may be 5 to 100 parts by weight of the vinyl polymer (I).
The amount is from 150 to 150 parts by weight, preferably from 10 to 120 parts by weight, more preferably from 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. <Physical property adjuster> The curable composition of the present invention may optionally contain a physical property adjuster for adjusting the tensile properties of the resulting cured product.

The physical property modifier is not particularly limited,
For example, alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, γ-glycidoxypropylmethyldisilane Alkylisopropenoxysilanes such as isopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane, N- (β
-Aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Alkoxysilanes having a functional group such as mercaptopropylmethyldimethoxysilane; silicone varnishes; and polysiloxanes. By using the physical property modifier, the hardness of the composition of the present invention when it is cured can be increased, or the hardness can be decreased, and elongation can be obtained. The physical property modifiers may be used alone or in combination of two or more. <Thixotropic agent (anti-sagging agent)> A thixotropic agent (anti-sagging agent) is added to the curable composition of the present invention to prevent sagging and improve workability, if necessary. Is also good.

The anti-sagging agent is not particularly restricted but includes, for example, 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 needed 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, antioxidants, radical inhibitors, ultraviolet absorbers, metal deactivators, ozone deterioration inhibitors, light stabilizers, phosphorus-based additives. Examples include an oxide decomposing agent, a lubricant, a pigment, a foaming agent, and a photocurable resin. These various additives may be used alone or in combination of two or more.

Specific examples of such additives include, for example,
Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-1088928,
JP-A-63-254149, JP-A-64-22904
It is described in each specification of the issue.

The curable composition of the present invention can be prepared as a one-component type in which all the components are pre-mixed, sealed and stored, and then cured by the moisture in the air after application. Ingredients such as a filler, a plasticizer, and water may be blended in advance, and the blended material and the polymer composition may be mixed before use to prepare a two-component type. <Uses> The curable composition of the present invention is not limited, but it is not limited, but is used as a sealing material such as an elastic sealing material for buildings or a sealing material for double-layered glass; Electrical insulation materials such as insulation coating materials for cables,
Adhesives, adhesives, elastic adhesives, paints, powder coatings, coating materials, foams, potting agents for electric and electronic devices, films, gaskets, casting materials, various molding materials, and end faces of netted glass and laminated glass ( It can be used for various purposes such as rust prevention and waterproofing sealing material for the cut part).

[0188]

EXAMPLES Hereinafter, specific examples of the present invention will be described 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)"
Is a gel permeation chromatography (GP
Calculated by standard polystyrene conversion method using C).
However, a GPC column filled with a polystyrene cross-linked gel (shodex GPC K-804; manufactured by Showa Denko KK) was used, and chloroform was used as a GPC solvent. (Production Example 1) (Synthesis of carboxylate having alkenyl group) 10-undecenoic acid (150 g,
0.814 mol) and potassium-tert-butoxide (91.3 g, 0.814 mol), and the mixture was stirred at 0 ° C. Volatile components were distilled off under heating under reduced pressure to obtain potassium undecenoate represented by the following formula. CH ₂ ＣＨCH— (CH ₂ ) ₈ —CO ₂ ^{− +} K (BA semi-batch polymerization—5 kg) In a 10 L glass reaction vessel, under a nitrogen atmosphere, cuprous bromide (35.3 g, 0.246 mol), acetonitrile ( 470 mL) and heated at 70 ° C. for 60 minutes.
To this, butyl acrylate (940 mL, 6.56 mo
l) was added and the mixture was further stirred for 60 minutes. Add pentamethyldiethylenetriamine (2.00 mL, 9.58 mm
ol) was added to initiate polymerization. After 55 minutes, butyl acrylate (3.76 L, 26.2 mol) was added over 260 minutes. During this time, pentamethyldiethylenetriamine (5.00 mL, 24.0 mmol) was added little by little while sampling the reaction solution to monitor the reaction. Heating was continued for an additional 90 minutes after the addition of the butyl acrylate. At this time, the consumption rate of butyl acrylate was 97.1% from the GC measurement. After diluting the mixture with toluene and treating with activated alumina, the volatile components were distilled off by heating under reduced pressure to obtain a colorless transparent polymer [1]. The number average molecular weight of the obtained polymer [1] was 10,800, and the molecular weight distribution was 1.15.

The above polymer (2.0 kg), the above potassium undecenoate (89 g) and 2 L of dimethylacetamide
Was added to a glass container, and heated and stirred at 70 ° C. for 3 hours under a nitrogen atmosphere. After removing the volatile components of the reaction solution under heating under reduced pressure, the reaction solution was diluted with toluene and filtered. The volatiles were distilled off from the filtrate under heating under reduced pressure, and the solution was concentrated. 20 wt% of aluminum silicate (Kyowa Chemical Co., Ltd., Kyoward 700 PEL) was added to the polymer, and the mixture was heated and stirred at 100 ° C. for 3 hours. The reaction solution was diluted with toluene and filtered, and volatiles were distilled off from the filtrate under reduced pressure and heating to obtain an alkenyl group-terminated polymer (polymer [2]). ^{According to 1} H-NMR measurement, the number of alkenyl groups introduced per polymer molecule was 1.8.

The polymer [2] (589) was placed in a 1 L pressure-resistant reaction vessel.
g), dimethoxymethylhydrosilane (24.3 mL,
0.20 mol), methyl orthoformate (10.8 mL,
0.098 mmol), and 1,1,3,
A 3-tetramethyl-1,3-divinyldisiloxane complex was charged. However, the amount of the platinum catalyst used was 5 × 10 ⁻⁴ equivalent in molar ratio to the alkenyl group of the polymer. The reaction mixture was heated at 100 C for 1 hour. Thereafter, 12.1 ml of dimethoxymethyl was added, and the mixture was further heated at 100 ° C. for 3 hours. By distilling off the volatile components of the mixture under reduced pressure,
A silyl group-terminated polymer (polymer [3]) was obtained. The number average molecular weight of the obtained polymer was 14,200, and the molecular weight distribution was 1.
It was 6. When the average number of silyl groups introduced per molecule of the polymer was determined by ¹ H NMR analysis,
It was 1.9. (Production Example 2) In a 2 L separable flask equipped with a reflux tube and a stirrer, CuBr (8.39 g, 0.0585 m
ol), and the inside of the reaction vessel was purged with nitrogen. Add acetonitrile (112 mL) and add 3 at 70 ° C in an oil bath.
Stirred for 0 minutes. Add butyl acrylate (224m
L) Diethyl 2,5-dibromoadipate (23.4)
g, 0.0650 mol) and pentamethyldiethylenetriamine (0.500 mL, 0.244 mmol) (hereinafter triamine) were added to initiate the reaction. 7
While stirring with heating at 0 ° C., butyl acrylate (895 m
L) was continuously dropped over 150 minutes. During the dropping of butyl acrylate, triamine (2.50 mL, 12.0 mL
mmol) was added. 310 minutes after the start of the reaction, 1,7-octadiene (288 mL, 1.95 mol
l), triamine (4.0 mL, 0.0195 mol)
Was added and the mixture was heated and stirred at 70 ° C. for 240 minutes. After diluting the reaction mixture with hexane and passing through an activated alumina column, volatile components were distilled off under reduced pressure to obtain an alkenyl group-terminated polymer (polymer [4]). The number average molecular weight of the polymer [4] was 20,000, and the molecular weight distribution was 1.3.
Polymer [4] was placed in a 2 L separable flask with a reflux tube.
(1.0 kg), potassium benzoate (34.8 g),
N, N-dimethylacetamide (1 L) was charged and heated and stirred at 70 ° C. for 15 hours under a nitrogen stream. N,
After removing N-dimethylacetic acid amide, the mixture was diluted with toluene. Solids insoluble in toluene (KBr and excess potassium benzoate were filtered through an activated alumina column. The volatiles in the filtrate were distilled off under reduced pressure to obtain a polymer [5].

In a 2 L round bottom flask equipped with a reflux tube, polymer [5] (1 kg), aluminum silicate (200 g, Kyoward 700PEL, manufactured by Kyowa Chemical Co., Ltd.) and toluene (1 L) were charged, and the mixture was heated at 100 ° C. under a nitrogen stream at 100 ° C. The mixture was heated and stirred for 5 hours. After removing the aluminum silicate by filtration, toluene of the filtrate was distilled off under reduced pressure to obtain a polymer [6].

The polymer [6] (71) was placed in a 1 L pressure-resistant reaction vessel.
8.80 g), dimethoxymethylhydrosilane (27.
55 mL, 0.223 mol), methyl orthoformate (8.14 mL, 0.074 mmol), and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zero-valent platinum were charged. However, the amount of the platinum catalyst used was 5 × 10 5 in molar ratio with respect to the alkenyl group of the polymer.
^-4 equivalents. The reaction mixture was heated at 100 C for 5 hours. The volatile component of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated polymer (polymer [7]). The number average molecular weight of the obtained polymer was 23,000 by GPC measurement (in terms of polystyrene), and the molecular weight distribution was 1.4. Polymer 1
The average number of silyl groups introduced per molecule is ¹ H N
1.7 pieces were obtained by MR analysis. (Production Example 3) (Synthesis of carboxylate having alkenyl group) 10-undecenoic acid (150 g,
0.814 mol) and potassium-tert-butoxide (91.3 g, 0.814 mol), and the mixture was stirred at 0 ° C. Volatile components were distilled off under heating under reduced pressure to obtain potassium undecenoate represented by the following formula. CH ₂ ＣＨCH— (CH ₂ ) ₈ —CO ₂ ^{− +} K (BA semi-batch polymerization—1 kg) Cuprous bromide (8.39 g, 0.0585 mol), acetonitrile ( ₂ kg) in a 2 L glass reaction vessel under a nitrogen atmosphere. 112 mL) and heated at 70 ° C. for 60 minutes.
To this, butyl acrylate (224 mL, 1.56 mo
l) was added and the mixture was further stirred for 30 minutes. Add pentamethyldiethylenetriamine (0.41 mL, 1.95 mm
ol) was added to initiate polymerization. Thereafter, the reaction solution was sampled to monitor the reaction while monitoring the reaction with pentamethyldiethylenetriamine (5.66 mL, 27.1 mmol).
l) was added, and butyl acrylate (895 mL, 6.24 mol) was added over 140 minutes 55 minutes after the start of the reaction. Heating was continued for another 170 minutes after the addition of the butyl acrylate. At this time, the consumption rate of butyl acrylate was 92.9% according to GC measurement. After the mixture was diluted with toluene and treated with activated alumina, the volatiles were distilled off by heating under reduced pressure to obtain a colorless and transparent polymer [8]. The number average molecular weight of the obtained polymer [8] was 21,000, and the molecular weight distribution was 1.1.

The above-mentioned polymer [8] (0.35 kg), the above-mentioned potassium undecenoate (8.85 g) and 350 mL of dimethylacetamide were added to a glass container, and heated and stirred at 70 ° C. for 3 hours in a nitrogen atmosphere. After removing the volatile components of the reaction solution under heating under reduced pressure, the reaction solution was diluted with toluene and filtered. The volatiles were distilled off from the filtrate under heating under reduced pressure, and the solution was concentrated.
This is made of aluminum silicate (Kyowa Chemical, Kyoward 700P
EL) was added to the polymer in an amount of 20 wt%, and the mixture was heated and stirred at 100 ° C. for 3 hours. The reaction solution was diluted with toluene and filtered, and volatiles were distilled off from the filtrate under reduced pressure and heating to obtain an alkenyl group-terminated polymer (polymer [9]).
^{According to 1} H-NMR measurement, 1.9 alkenyl groups were introduced per polymer molecule.

The polymer [9] (350) was placed in a 1 L pressure-resistant reaction vessel.
g), dimethoxymethylhydrosilane (12.3 mL,
0.20 mol), methyl orthoformate (3.65 mL,
0.033 mmol), and 1,1,3,
A 3-tetramethyl-1,3-divinyldisiloxane complex was charged. However, the amount of the platinum catalyst used was 5 × 10 ⁻⁴ equivalent in molar ratio to the alkenyl group of the polymer. The reaction mixture was heated at 100 C for 90 minutes. The volatile component 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 26,000, and the molecular weight distribution was 1.2. The average number of silyl groups introduced per molecule of polymer was ¹ H NM
When determined by R analysis, the number was 1.4. (Production Example 4) CuBr (251.82 g, 1.76 mol) was charged into a 50 L polymerization machine equipped with a reflux tower and a stirrer, and the inside of the reaction vessel was purged with nitrogen. Acetonitrile (3
(360 mL) and stirred at 68 ° C. for 20 minutes. To this, butyl acrylate (6.80 L), diethyl 2,5-dibromoadipate (526.70 g, 1.46 mo)
l), pentamethyldiethylenetriamine (12.0 m
L, 0.0585 mmol) (hereinafter triamine) was added to start the reaction. With heating and stirring at 70 ° C., butyl acrylate (26.80 L) was continuously added dropwise over 204 minutes. Triamine (36.0 mL, 0.176 mmol) was added during the dropping of butyl acrylate. After 397 minutes from the start of the reaction, 1,7-octadiene (8640 mL, 58.5 mol) and triamine (120 mL, 0.585 mol) were added.
The mixture was heated and stirred for 40 minutes. Then triamine (80 mL,
(0.390 mol) and heated and stirred at 90 ° C. for 240 minutes.

The reaction mixture was diluted with toluene, the insoluble copper complex was removed using a centrifugal separator, and the mixture was passed through an activated alumina column. (Polymer [11]) was obtained. The number average molecular weight of the polymer [11] was 24,000, and the molecular weight distribution was 1.21. In a 10 L separable flask equipped with a reflux tube, polymer [11] (3.0 kg), potassium benzoate (69.9 g), N, N-dimethylacetamide (3
L) and heated and stirred at 100 ° C. for 10 hours under a nitrogen stream. After removing N, N-dimethylacetic acid amide under reduced pressure by heating, the mixture was diluted with toluene. Solids insoluble in toluene (KBr and excess potassium benzoate were filtered through an activated alumina column. The volatiles in the filtrate were distilled off under reduced pressure to obtain a polymer [12].

In a 10 L round bottom flask equipped with a reflux tube, polymer [12] (3 kg), hydrotalcite (450 g,
Kyowa Chemical, Kyoword 500SH, Kyoword 7
00SL) and xylene (0.6 L), and heated and stirred at 130 ° C. for 5.0 hours under a nitrogen stream. After removing the aluminum silicate by filtration, the filtrate was distilled off under reduced pressure to obtain a polymer [13].

In a 2 L reaction vessel, polymer [13] (1000
g), dimethoxymethylhydrosilane (45 mL, 0.1 mL).
365 mol), methyl orthoformate (13.3 mL,
0.122 mmol), and 1,1,3,
A 3-tetramethyl-1,3-divinyldisiloxane complex was charged (30 ppm as platinum). 1 reaction mixture
The mixture was heated and stirred at 00 ° C. for 10 hours. During the reaction, a platinum catalyst,
Dimethoxymethylsilane was added. The added amount of the platinum catalyst was 120 ppm as platinum, and the added amount of dimethoxymethylsilane was 15 mL. The volatile component of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated polymer (polymer [1
4]) was obtained. The number average molecular weight of the obtained polymer was determined by GPC.
As a result of measurement (in terms of polystyrene), it was 28500, 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 to be 2.5. Example 1 100 parts of the polymer [3] obtained in Production Example 1 was mixed with heavy calcium carbonate having a specific surface area of 3.2 m ² / g (particle diameter 0.7 μm) (Softon 3200: Bihoku Powder Chemical Industry) 100 parts), and cured at 50 ° C. for 2 days in a room using a tetravalent Sn catalyst (dibutyltin diacetylacetonate) to obtain a cured product. Tensile test was performed on 2
(1/3) No. type dumbbell test pieces were punched out, and the test was performed using an autograph manufactured by Shimadzu (measurement conditions: 23 ° C., 200
mm / min). (Example 2) Instead of the heavy calcium carbonate used in Example 1, 100 parts of heavy calcium carbonate (PO320B: made of Shiraishi calcium) having the same specific surface area and treated with a fatty acid-based surface treatment agent was used. A cured product was prepared and subjected to a tensile test in the same manner as in Example 1 except for the difference. Comparative Example 1 Instead of the heavy calcium carbonate used in Example 1, the specific surface area was 1.2 m ² / g (particle size 1.8 μm).
A cured product was prepared in the same manner as in Example 1 except that 100 parts of heavy calcium carbonate (Whiteton SB: manufactured by Shiraishi calcium) was used, and a tensile test was performed. (Comparative Example 2) Instead of the heavy calcium carbonate used in Comparative Example 1, heavy calcium carbonate (Ryton A: manufactured by Bihoku Powder Chemical Industry) having an equivalent specific surface area and treated with a fatty acid-based surface treatment agent was used. A cured product was prepared in the same manner as in Example 1 except that 100 parts were used, and a tensile test was performed.

Table 1 shows the results of the tensile test of each cured product.
It was shown to.

[0201]

[Table 1] Example 3 100 parts of the polymer [7] obtained in Production Example 2 was mixed with heavy calcium carbonate having a specific surface area of 3.2 m ² / g (particle diameter 0.7 μm) (Softon 3200: Bihoku Powder Chemical Industry) 100 parts), and cured at 50 ° C. for 2 days in a room using a tetravalent Sn catalyst (dibutyltin diacetylacetonate) to obtain a cured product. (Example 4) Instead of the heavy calcium carbonate used in Example 3, the specific surface area was 2.5 m ² / g (particle diameter 0.9 μm).
A cured product was prepared in the same manner as in Example 3 except that 100 parts of the above heavy calcium carbonate (Nanox # 25: manufactured by Maruo Calcium) was used. Comparative Example 3 Instead of the heavy calcium carbonate used in Example 3, the specific surface area was 1.2 m ² / g (particle size 1.8 μm).
A cured product was produced in the same manner as in Example 3 except that 100 parts of heavy calcium carbonate (Whiteton SB: manufactured by Shiraishi calcium) was used.

Each of the cured products was subjected to a tensile test. In the tensile test, the sheet-shaped cured product was subjected to 2 (1/1)
3) A dumbbell test piece was punched out, and the test was performed using an autograph manufactured by Shimadzu (measurement conditions: 23 ° C., 200 mm /
min). The results are shown in Table 2.

[0203]

[Table 2] (Example 5) Polymer [10] 100 obtained in Production Example 3
And 100 parts of heavy calcium carbonate having a specific surface area of 3.2 m ² / g (particle size 0.7 μm) (Softon 3200: manufactured by Bihoku Powder Chemical Industry), and a tetravalent Sn catalyst (dibutyltin diacetylacetonate) And cured at 50 ° C. for 2 days in a room to obtain a cured product. (Example 6) For 100 parts of heavy calcium carbonate (PO320B: made of Shiroishi calcium) having the same specific surface area and treated with a fatty acid-based surface treatment agent, instead of the heavy calcium carbonate used in Example 5 A cured product was prepared in the same manner as in Example 5 except for the presence of the cured product. (Comparative Example 4) Instead of the heavy calcium carbonate used in Example 5, the specific surface area was 1.2 m ² / g (particle size: 1.8 μm).
A cured product was prepared in the same manner as in Example 5 except that 100 parts of heavy calcium carbonate (Whiteton SB: manufactured by Shiraishi calcium) was used.

[0204] Each of the cured products was subjected to a tensile test. In the tensile test, the sheet-shaped cured product was subjected to 2 (1/1)
3) A dumbbell test piece was punched out, and the test was performed using an autograph manufactured by Shimadzu (measurement conditions: 23 ° C., 200 mm /
min). The results are shown in Table 3.

[0205]

[Table 3] In addition, a glass plate (for JIS A 5758: 50 × 50
× 5 mm) and Examples 1 and 2 and Comparative Example 1
The cured products of (1) and (2) were irradiated with a light of 500 h or the like from the glass surface side with a xenon weather meter (Suga tester SX120 type, radiation intensity 180 W, black panel temperature 63 ° C., rainfall during irradiation for 2 hours 18 minutes) . After the irradiation, a hand peeling test was performed to check the state of destruction. The results are shown in Table 4.

[0206]

[Table 4]In the table, ○ indicates cohesive failure, × indicates interfacial failure, and Δ indicates cohesive failure.
Where both the damaged part and the interfacial fracture part are mixed
You. (Example 7) Polymer [14] 100 obtained in Production Example 4
Part, 50 parts of DIDP (manufactured by Kyowa Hakko) and specific surface area
3.2m^Two/ G (particle diameter 0.7μm) heavy calcium carbonate
200 units (Softon 3200: manufactured by Bihoku Powder Chemical Industry)
After mixing, mix well using 3 paint rolls and harden.
A curable composition was obtained. Use a BS viscometer (low
Tar No. 7, measurement environment 23 ° C). The result
The results are shown in Table 5. (Example 8) Substitute for heavy calcium carbonate used in Example 1
Instead, the specific surface area is 2.3 m ^Two/ G (particle size 1.2
μm) of heavy calcium carbonate (Nanox # 25:
Example 7 except that 200 parts of Maruo Calcium) were used.
A curable composition was prepared in the same manner. Formulation viscosity B
With an S-type viscometer (rotor No. 7, measurement environment 23 ° C)
It was measured. Table 5 shows the results. (Comparative Example 5) Substitute for heavy calcium carbonate used in Example 1
Instead, the specific surface area is 1.2m^Two/ G (1.8 μm particle size)
Heavy Calcium Carbonate (Whiteton SB: Shiraishi Calcium)
Hardened in the same manner as in Example 7 except that 200 parts of
A curable composition was prepared. Use a BS viscometer to measure the viscosity of the compound
(Rotor No. 7, measurement environment 23 ° C.).
Table 5 shows the results.

[0207]

[Table 5] From the results in Table 5, it can be seen that the viscosity ratios of the blends of Example 7 and Example 8 are larger than Comparative Example 5. The viscosity ratio is a value obtained by comparing the viscosity at low shear (1 to 2 rpm) with the viscosity at high shear (10 rpm).
The viscosity at low shear is close to the viscosity at rest, and the viscosity at high shear is close to the viscosity during construction work. Therefore, a large viscosity ratio means that the viscosity at rest is relatively high and the viscosity at the time of construction is low.If the viscosity ratio is large, the viscosity is low at the time of work and the spatula sharpness is also improved. Work becomes easier, and sagging hardly occurs after construction.

[0208]

When the curable composition of the crosslinkable functional group-containing vinyl polymer of the present invention is used, the viscosity ratio of the curable composition is increased, the spatula cutting property is improved, and the cured product is obtained. The mechanical properties and adhesiveness of are improved. By using the curable composition of the present invention, a cured product having a large elongation (EB or the like) can be obtained without lowering the strength (M50, Tmax or the like).

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Yoshiki Nakagawa 1-2-80 Yoshida-cho, Hyogo-ku, Kobe-shi, Hyogo Kanebuchi Chemical Industry Co., Ltd. Functional Materials RD Research Center Kobe Research Laboratory F-term (reference) 4J002 BC001 BD121 BG021 BG101 DE236 FD016

Claims (21)

[Claims] 1. The following two components: (A) a vinyl polymer (I) having at least one crosslinkable functional group, and
(B) A curable composition containing heavy calcium carbonate (II) having a specific surface area of 1.5 m ² / g or more and 50 m ² / g or less. 2. The curable composition according to claim 1, wherein the molecular weight distribution of the vinyl polymer (I) is less than 1.8. 3. The main chain of the vinyl polymer (I) is selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers and silicon-containing vinyl monomers. The curable composition according to claim 1, wherein the curable composition is produced by mainly polymerizing a monomer to be produced. 4. The curable composition according to claim 1, wherein the vinyl polymer (I) is a (meth) acrylic polymer. 5. The curable composition according to claim 1, wherein the vinyl polymer (I) is an acrylic polymer. 6. The curable composition according to claim 5, wherein the vinyl polymer (I) is an acrylate polymer. 7. The curable composition according to claim 6, wherein the vinyl polymer (I) is a butyl acrylate polymer. 8. The crosslinkable functional group of the vinyl polymer (I) is a crosslinkable silyl group.
8. The curable composition according to any one of items 7 to 7. 9. The crosslinkable functional group of the vinyl polymer (I) is an alkenyl group.
The curable composition according to any one of the above. 10. The curable composition according to claim 1, wherein the crosslinkable functional group of the vinyl polymer (I) is a hydroxyl group. 11. The curable composition according to claim 1, wherein the crosslinkable functional group of the vinyl polymer (I) is an amino group. 12. The method according to claim 1, wherein the crosslinkable functional group of the vinyl polymer (I) is a group having a polymerizable carbon-carbon double bond. Curable composition. 13. The curable composition according to claim 1, wherein the crosslinkable functional group of the vinyl polymer (I) is an epoxy group. 14. The curable composition according to claim 1, wherein the main chain of the vinyl polymer (I) is produced by a living radical polymerization method. . 15. The curable composition according to claim 14, wherein the living radical polymerization is atom transfer radical polymerization. 16. The atom transfer radical polymerization is characterized by using a complex selected from transition metal complexes having a central metal of Group 7, 8, 9, 10 or 11 of the periodic table as a catalyst. The curable composition according to claim 15, wherein 17. The metal complex used as a catalyst is copper, nickel,
The curable composition according to claim 16, which is a complex selected from the group consisting of ruthenium and iron complexes. 18. The curable composition according to claim 17, wherein the metal complex used as a catalyst is a copper complex. 19. The curable composition according to claim 1, wherein the heavy calcium carbonate (II) is a surface-treated heavy calcium carbonate. 20. The method according to claim 1, wherein 5 to 500 parts by weight of heavy calcium carbonate (II) is contained based on 100 parts by weight of the vinyl polymer (I). 3. The curable composition according to item 1. 21. The curable composition according to claim 1, further comprising, as a component (C), 0.1 to 20 parts by weight of a silane coupling agent. object.