JP2001011321A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of modifying the surface of a cured product and maintaining high flame retardance and good weather resistance by including a vinylic polymer having at least one cross-linkable silyl group and a compound having siloxane bonds. SOLUTION: This composition comprises (A) a vinylic polymer having at least one cross-linkable silyl group and (B) a compound having siloxane bonds. The component A is preferably a vinylic polymer having the cross-linkable silyl group at the molecular terminal. The cross-linkable silyl group of the component A is preferably a cross-linkable silyl group represented by formula I [R1 and R2 are each a 1-20C alkyl, a 6-20C aryl or the like; Y is hydroxyl group or the like; a is 0-3; b is 0-2; m is 0-19, with the proviso that (a+mb) is >=1] and the component B preferably has 1.1-5 cross-linkable groups on the average in one molecule. The component B is preferably an organopolysiloxane comprising a recurring unit represented by formula II (R3 and R4 are each H or a monovalent hydrocarbon).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a curable composition. More specifically, when it is exposed to moisture, it cures to a rubber-like substance, and the surface of the cured product is modified, with less surface tack, high flame retardancy, and good heat resistance and weather resistance. Curable composition.

[0002]

2. Description of the Related Art Conventionally, a rubber-like cured product which is cured by moisture or the like has been used as an elastic sealant for a building. Recently, a material using a polyoxyalkylene-based polymer as its raw material has been used. Are mainly used because they are inexpensive and have excellent performance. However, its heat resistance / weather resistance / flame retardancy is somewhat lacking due to its molecular structure, and thus its improvement (improvement) has been required. In order to solve this problem, the present inventors have found a rubber using a (meth) acrylic polymer.

[0003] However, a rubber-like cured product using a (meth) acrylic polymer has improved heat resistance / weather resistance / flame retardancy as compared with a conventional one using a polyoxyalkylene-based polymer. Depending on the curing conditions, tackiness (tack: stickiness) may still remain on the surface. If the adhesiveness remains on the surface in this way, dust, dust, earth and sand, etc. adhere to the surface, which is not preferable because the appearance is impaired.

[0004]

SUMMARY OF THE INVENTION In view of the above situation, the present invention cures to a rubber-like substance upon contact with moisture, and the surface of the cured product is modified, the surface is less tacky and flame retardant. It is an object of the present invention to provide a curable composition having high heat resistance and maintaining good heat resistance and weather resistance.

[0005]

Means for Solving the Problems As a result of intensive studies, the inventors have found that a vinyl polymer having at least one crosslinkable silyl group is used as the component (A) and a compound having a siloxane bond as the component (B). The present inventors have found that the use of the compound improves the surface of the cured product, thereby obtaining a curable composition having high flame retardancy and good weather resistance, and arrived at the present invention. That is, the present invention is a curable composition containing the following two components: (A) a vinyl polymer having at least one crosslinkable silyl group, and (B) a compound having a siloxane bond. Here, the vinyl polymer as the component (A) is not particularly limited, but is preferably a vinyl polymer having a crosslinkable silyl group at a molecular terminal, and more preferably a crosslinked polymer represented by the following general formula (1). A vinyl polymer having a hydrophilic silyl group is more preferred. ^{_{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1) ( wherein, ^{R 1} and ^{R 2} are both 1 carbon atoms 20 alkyl groups, aryl groups having 6 to 20 carbon atoms, 7 to 2 carbon atoms
An aralkyl group of 0, or (R ′) ₃ Si— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms;
May be the same or different), and when two or more R ¹ or R ² are present, they may be the same or different. Is also good. Y represents a hydroxyl group or a hydrolyzable group,
When two or more Y are present, they may be the same or different. a represents 0, 1, 2 or 3, and b represents 0, 1 or 2. m is an integer of 0-19. However, it is assumed that a + mb ≧ 1 is satisfied. )

The main chain of the vinyl polymer of the component (A) is not particularly limited, but includes (meth) acrylic acid monomers, nitrile group-containing vinyl monomers, aromatic vinyl monomers, and fluorine-containing vinyl monomers. And a monomer selected from the group consisting of silicon-containing vinyl monomers, and is preferably produced mainly by polymerization, more preferably (meth) acrylic monomers, particularly preferably acrylic monomers, and still more preferably acrylic esters. It is preferably produced by polymerization using a system monomer, most preferably butyl acrylate.

Further, the vinyl polymer of the component (A) has a value of a molecular weight distribution (Mw / Mn) which is a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn) measured by gel permeation chromatography. Is preferably less than 1.8.

The main chain of the component (A) is preferably produced by a living radical polymerization method, and more preferably by an atom transfer radical polymerization method. At that time, the catalyst for the atom transfer radical polymerization method is preferably a metal complex selected from the group consisting of copper, nickel, ruthenium and iron, and more preferably a copper complex.

On the other hand, the compound having a siloxane bond as the component (B) is not particularly limited, but is preferably an organopolysiloxane comprising a repeating unit represented by the following general formula (2), and-[Si (R ³ ) (R ⁴ ) O]-(2) (wherein R ³ and R ⁴ represent hydrogen or a monovalent hydrocarbon group, and they may be the same or different). the is an organopolysiloxane represented by the following general formula ^{_{(3), Z 3-c}} -Si (R 5) c O- [Si (R 5) 2 O] n -Si (R 5) c (Z _3-c (3) (wherein, R ⁵ represents a same or different monovalent hydrocarbon group, n represents a positive integer of 19 or less, and when two or more R ⁵ are present, May be the same or different, and c is 0, 1, 2, or 3. Shows, Z represents a hydroxyl group or a hydrolyzable group, when Z is present two or more, they may be the same or may be different) more R ⁵ is a methyl group in the general formula (3) Or a phenyl group, c = 2, and Z is particularly preferably a hydroxyl group.

In order to enhance the compatibility with the vinyl polymer of the component (A), a copolymer having a siloxane bond of the component (B) with a (meth) acrylic acid monomer may be used.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a cured product surface using a vinyl polymer having at least one crosslinkable silyl group as a component (A) and a compound having a siloxane bond as a component (B). Has been modified, the surface tackiness is low, the flame retardancy is high, and good heat resistance, relates to a curable composition that retains weather resistance, below, the curable composition of the present invention will be described in detail .

[About the vinyl polymer of the component (A)]
The crosslinkable silyl group is a group that is crosslinked and cured by forming a siloxane bond. The vinyl polymer as the component (A) is a vinyl polymer having at least one crosslinkable silyl group. If the number of crosslinkable silyl groups is less than one on average per molecule, a sufficient cured product cannot be obtained.
In order to obtain a sufficient cured product, those having an average of 1.1 to 5 crosslinkable silyl groups represented by the above general formula (1) per molecule are preferable, and an average of 1.2 to 4 crosslinkable silyl groups. Are more preferred.

The vinyl polymer (A) having a crosslinkable silyl group can be obtained as follows. One is a method of polymerizing a monomer having a crosslinkable silyl group and a vinyl group in one molecule, and the other is a method of converting a terminal of a vinyl-based polymer obtained by living polymerization described below. . The vinyl polymer of the component (A) preferably has a crosslinkable silyl group at the molecular terminal as in the latter case. Further, the crosslinkable silyl group is preferably represented by the above general formula (1).

In the above general formula (1), R ¹ and R ²
May be the same or different and have 1 to 2 carbon atoms
It represents an alkyl group having 0, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. When two or more R ¹ or R ² are present, they may be the same or different.

In the general formula (1), Y represents a hydroxyl group or a hydrolyzable group. When there are two or more Y,
They may be the same or different. Y
Is preferably 1 to 5.

The hydrolyzable group is not particularly restricted but includes, for example, hydrogen, halogen atom, alkoxy group, acyloxy group, ketoximate group, amino group, amide group,
Examples include an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, an alkoxy group is preferable because it has a mild hydrolytic property and is easy to handle.

In the general formula (1), a is 0, 1,
Represents 2 or 3, b represents 0, 1 or 2, m represents 0 to 1
Indicates an integer of 9. Y can be bonded to one silicon atom in the range of 1-3. a, b and m are a + mb
Satisfies ≧ 1. That is, the general formula (1) contains at least one Y.

The silicon atom constituting the crosslinkable silyl group represented by the general formula (1) may be present alone,
Two or more may be present. In the case of silicon atoms linked by a siloxane bond, m may be 0 or 1 to 19 since about 20 may be used.

The monomer constituting the main chain of the vinyl polymer is not particularly restricted but includes, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate and (meth) acrylic acid. n-propyl, (meth)
Isopropyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate , (Meta)
Cyclohexyl acrylate, (meth) acrylic acid-n-
Heptyl, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, Toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) Acrylic acid
2-hydroxypropyl, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid , Trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2- (meth) acrylate Perfluorobutylethyl, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2 (meth) acrylate -Perfluoroethylmethyl, (meth) acrylic acid-2-PA Fluorohexyl ethyl, (meth)
2-perfluorodecylethyl acrylate, (meth)
(Meth) acrylic acid monomers such as 2-perfluorohexadecylethyl acrylate; aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; perfluoroethylene , Fluorine-containing vinyl monomers such as perfluoropropylene and vinylidene fluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid,
Monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide,
Maleimide-based monomers such as ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; vinyl monomers containing a nitrile group such as acrylonitrile and methacrylonitrile; acrylamide and methacrylamide Vinyl monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; Vinyl chloride, vinylidene chloride,
Allyl chloride, allyl alcohol and the like can be mentioned.

These may be used alone or in combination of two or more. In the above expression format, for example, (meta)
Acrylic acid refers to acrylic acid and / or methacrylic acid. The same applies to the following.

The main chain of the vinyl polymer of the component (A) is
Using a monomer selected from the group consisting of (meth) acrylic acid-based monomer, nitrile group-containing vinyl monomer, aromatic vinyl-based monomer, fluorine-containing vinyl-based monomer and silicon-containing vinyl-based monomer in an amount of 40% by weight or more based on all monomers. It is preferably obtained by polymerization.

Of these, aromatic vinyl monomers and (meth) acrylic monomers are preferred in view of the physical properties of the product and the like. Further, the reactivity of the functional group introduction reaction of the present invention and the low glass transition point are preferred. In view of the above, acrylate monomers are preferred, and butyl acrylate is particularly preferred.

The vinyl polymer having at least one crosslinkable silyl group can be obtained by synthesizing at least 40% by weight of a (meth) acrylic acid monomer among the above monomers from the viewpoint of physical properties ( (Meth) acrylic polymers are preferred.

Further, an acrylic polymer obtained by synthesizing the above monomer with an acrylic acid monomer in an amount of 30% by weight or more is more preferable.

The molecular weight of the vinyl polymer having at least one crosslinkable silyl group represented by the above general formula (1) in one molecule and having a main chain obtained by a living polymerization method is not particularly limited. However, it is preferably in the range of 500 to 100,000. When the molecular weight is less than 500, the intrinsic properties of the vinyl polymer are hardly exhibited, and
If it exceeds 00000, handling becomes difficult.

The molecular weight distribution of the vinyl polymer having at least one crosslinkable silyl group, that is, the molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is curable. In order to keep the viscosity of the composition low and to facilitate handling, and to obtain sufficient physical properties of the cured product, the composition is preferably narrow. The value of the molecular weight distribution is preferably less than 1.8, more preferably 1.7 or less, still more preferably 1.6 or less, and still more preferably 1.5 or less.
Or less, particularly preferably 1.4 or less, most preferably 1.
3 or less. Most commonly, the molecular weight distribution is measured by gel permeation chromatography (GPC). Chloroform or THF as the mobile phase,
A polystyrene gel column is used as the column, and the number average molecular weight and the like can be determined by values in terms of polystyrene.

[Method for Producing Polymer] <Regarding Living Polymerization Method> As a method for producing the vinyl polymer as the component (A) used in the present invention, a living polymerization method is preferable, and a living radical polymerization method is more preferable. .

Unlike the free radical polymerization method and the like, the living polymerization method can control the introduction of a crosslinkable silyl group with high precision. That is, due to the characteristics of the living polymerization method, it is possible to introduce a crosslinkable silyl group at or near the molecular chain terminal with extremely high probability for each molecule. And the gel fraction can be improved. In addition, by using the living polymerization method, the molecular weight distribution that greatly affects the viscosity of the polymer can be reduced, whereby the viscosity of the polymer and the curable composition can be reduced.

Examples of the above living polymerization method include a living anionic polymerization method, a living cationic polymerization method, a living radical polymerization method, and the like. However, the present invention is not particularly limited, and any method can be used. The method for introducing the crosslinkable silyl group into the vinyl polymer is not particularly limited, and various methods can be used.

However, from the viewpoint of versatility and controllability of the monomer, a living radical polymerization method is preferable, and among them, an atom transfer radical polymerization method is more preferable.

<Regarding the Living Radical Polymerization Method> The “living radical polymerization method” is a radical polymerization which is difficult to control because the polymerization rate is high and a termination reaction due to coupling between radicals is likely to occur. Hardly occur and the molecular weight distribution is narrow (Mw / Mn
(Approximately 1.1 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 above 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 of living polymerization in the present invention is also the latter.

The "living radical polymerization method" has been actively studied in recent years by various groups. For example, Journal of American Chemical Society (J. Am. Chem. Soc.), 1994, 11
6, using a cobalt porphyrin complex as shown on page 7943, Macromolecules (Macr.
omolecules), 1994, 27, 722.
"Atom transfer radical polymerization" using a radical scavenger such as a nitroxide compound as shown on page 8, and using an organic halide or the like as an initiator and a transition metal complex as a catalyst
(Atom Transfer Radical Po
lymerization: ATRP).

<Regarding Atom Transfer Radical Polymerization Method> Among the "living radical polymerization methods", "atom transfer radical polymerization" 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. The `` method '' has the features of the above `` living radical polymerization method '' and has a halogen or the like at the terminal which is relatively advantageous for the functional group conversion reaction, and has a high degree of freedom in designing initiators and catalysts. Is more preferable as a method for producing a vinyl polymer having the above functional group. As this atom transfer radical polymerization method, for example, Matyjaszewsk
i, et al., Journal of American Chemical Society (J. Am. Chem. Soc.), 1995.
Year 117, 5614; Macromolecules (M
acromolecules), 1995, volume 28,
7901; Science, 1996.
Year 272, page 866; WO96 / 30421, WO97 / 18247 or Sawamoto
Et al., Macromolecules
es), 1995, 28, 1721.

In the present invention, the living radical polymerization method is preferably an atom transfer radical polymerization method because of its easy control.

Among these living radical polymerizations,
First, a method using a radical scavenger such as a nitroxide compound will be described. In this polymerization, a stable nitroxy free radical (= NO) is generally used as a radical capping agent. Such compounds are not limited, but include cyclic compounds such as 2,2,6,6-substituted-1-piperidinyloxy radical and 2,2,5,5-substituted-1-pyrrolidinyloxy radical. Preference is given to nitroxy free radicals from hydroxyamines. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group and an ethyl group is suitable. Although a specific nitroxy free radical compound is not limited, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMP
O), 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. it can. Instead of nitroxy free radical, galvinoxyl (galvin
oxyl) Stable free radicals such as free radicals 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. The peroxide is not particularly limited, for example, benzoyl peroxide, diacyl peroxides such as lauroyl peroxide, dicumyl peroxide, dialkyl peroxides such as di-t-butyl peroxide, diisopropyl peroxydicarbonate, Peroxycarbonates such as bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxyoctoate,
Examples thereof include alkyl peresters such as t-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 an initiator, if it has a functional group such as a hydroxyl group represented by the above formula, a polymer having a functional group at a terminal can be obtained. When this is used in the method of the present invention, a star 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 the 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. Good.

Next, a more preferred atom transfer radical polymerization method as the living radical polymerization of the present invention will be described.

[Regarding Atom Transfer Radical Polymerization] <Catalyst> In this atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, an ester having a halogen at the α-position) A compound or a compound having a halogen at the benzyl position) or a sulfonyl halide compound is used as an initiator. As the catalyst, group 7 of the periodic table,
A metal complex having a Group 8, 9, 10, or 11 element as a central metal is used. As the metal species, 0 and monovalent copper, divalent nickel, divalent ruthenium, and divalent iron are preferable. Among them, a copper complex is more preferable. If specifically exemplified, cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous acetate, cuprous perchlorate, etc. will be mentioned. be able to. When a copper compound is used, 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, alkylamines such as tributylamine, tetramethylethylenediamine, pentamethyldiethylenetriamine, and hexamethyltriethylene in order to enhance the catalytic activity A ligand such as a polyamine such as tetraamine is added. In addition, a tristriphenylphosphine complex of divalent ruthenium chloride (RuCl
₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When this catalyst is used, an aluminum compound such as trialkoxyaluminum is added to enhance its activity. Further, a tristriphenylphosphine complex of divalent iron chloride (FeCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst.

<Regarding the Initiator> In this polymerization method, an organic halide or a sulfonyl halide compound is used as an initiator. As a specific 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 , wherein C ₆ H ₅ represents a phenyl group and X represents chlorine, bromine or iodine. R ⁶ -C (H) ( ^{_{X) -CO 2 R 7, R}} 6 -C (C
^{_{H 3) (X) -CO 2}} R 7, R 6 -C (H) (X) -C
_{^{(O) R 7, R 6}} -C (CH 3) (X) -C (O)
R ⁷ , wherein R ⁶ and R ⁷ are a hydrogen atom or a carbon atom
X represents an alkyl group, an aryl group, or an aralkyl group, and X represents chlorine, bromine, or iodine. R ⁶ -C ₆ H ₄ -SO ₂ X (wherein R ⁶ is a hydrogen atom Or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and X represents chlorine, bromine,
Or iodine).

When an organic halide or a sulfonyl halide compound having a functional group other than the one that initiates the polymerization is used, a polymer having a functional group introduced at the terminal can be easily obtained. Examples of such a functional group include an alkenyl group, a hydroxyl group, an epoxy group, an amino group, an amide group, and a silyl group.

The organic halide having an alkenyl group is not particularly restricted but includes, for example, those having a structure represented by the following general formula (4). ^{R 13 R 14 C (X)} -R 15 -R 16 -C (R 8) = CH 2 (4) ( wherein, ^{R 8} is hydrogen or a methyl ^{group, R 13,}
R ¹⁴ represents hydrogen or a monovalent alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, or one linked to each other at the other end, and R ¹⁵ represents —C
(O) O- (ester group), -C (O)-(keto group),
Or, o-, m-, p-phenylene ^{group, R 1 6} is a direct bond, or represents one or more carbon atoms which may contain an ether bond 20 divalent organic group, X is Indicates chlorine, bromine, or iodine. )

In these compounds, the carbon to which the halogen is bonded is bonded to a carbonyl group or a phenyl group, and the carbon-halogen bond is activated to initiate polymerization. As the substituents R ¹³ and R ¹⁴ , for example, hydrogen, a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
Examples thereof include an n-butyl group, a pentyl group, and a hexyl group. R ¹³ and R ¹⁴ may be linked at the other end to form a cyclic skeleton, in which case -R ¹³
-R ¹⁴ - as, for _{example, -CH 2 CH 2 -, -} C
_{H 2 CH 2 CH 2 -,} - CH 2 CH 2 CH 2 CH 2 -,
—CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ — and the like. Specific examples of the organic halide having an alkenyl group represented by the general formula (4) 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 = C
H ₂ , CH ₃ CH ₂ C (H) (X) C (O) O (C
H ₂ ) _n CH = CH ₂ ,

[0050]

Embedded image

(In each of the above formulas, X represents chlorine, bromine,
Or iodine, and n represents an integer of 0 to 20) XCH₂C (O) O (CH₂)_nO (CH₂)_mCH =
CH₂, H₃CC (H) (X) C (O) O (CH₂)_n
O (CH₂)_mCH = CH₂, (H₃C)₂C (X) C
(O) O (CH₂)_nO (CH₂)_mCH = CH₂, C
H₃CH₂C (H) (X) C (O) O (CH₂)_nO
(CH₂)_mCH = CH ₂,

[0052]

Embedded image

(In each of the above formulas, X is chlorine, bromine,
Or iodine, n is an integer of 1 to 20, m is
O, m, p-XCH₂-C₆H₄− (CH₂)_n-CH
= CH₂, O, m, p-CH₃C (H) (X) -C₆H
₄− (CH₂)_n-CH = CH₂, O, m, p-CH₃
CH₂C (H) (X) -C₆H₄− (CH₂)_n-CH
= CH₂, (In each of the above formulas, X is chlorine, bromine, or
Represents iodine, and n represents an integer of 0 to 20) o, m, p-XCH₂-C₆H₄− (CH₂)_n-O-
(CH₂)_m-CH = CH₂, O, m, p-CH₃C
(H) (X) -C₆H₄− (CH₂)_n-O- (C
H₂) _m-CH = CH₂, O, m, p-CH₃CH₂C
(H) (X) -C₆H₄− (CH₂)_n-O- (C
H₂)_mCH = CH₂, (In the above formulas, X is a salt
Represents fluorine, bromine, or iodine, and n is an integer of 1 to 20
And m represents an integer of 0 to 20) o, m, p-XCH₂-C₆H₄-O- (CH₂)_n−
CH = CH₂, O, m, p-CH₃C (H) (X) -C
₆H₄-O- (CH₂)_n-CH = CH ₂, O, m, p
-CH₃CH₂C (H) (X) -C₆H₄-O- (CH
₂)_n-CH = CH₂, (In each of the above formulas, X is a salt
Represents nitrogen, bromine, or iodine, and n is an integer of 0 to 20
O), m, p-XCH₂-C₆H₄-O- (CH₂)_n−
O- (CH₂)_m-CH = CH₂, O, m, p-CH₃
C (H) (X) -C₆H₄-O- (CH₂)_n-O-
(CH ₂)_m-CH = CH₂, O, m, p-CH₃CH
₂C (H) (X) -C₆H₄-O- (CH₂)_n-O-
(CH₂)_m-CH = CH₂, (In each of the above equations,
X represents chlorine, bromine or iodine, and n is 1 to 20
Represents an integer, and m represents an integer of 0 to 20)

The organic halide having an alkenyl group further includes a compound represented by the following general formula (5). _{^{H 2 C = C (R 8}} ) -R 16 -C (R 13) (X) -R 17 -R 14 (5) ( ^{wherein, R 8, R 13, R} 14, R 16, X is the R ¹⁷ is a direct bond, —C (O) O— (ester group), —C (O) — (keto group), or o—, m
-Represents a p-phenylene group. )

R ¹⁶ is a direct bond or has 1 to 20 carbon atoms.
A divalent organic group (which may contain one or more ether bonds). In the case of a direct bond, a vinyl group is bonded to the carbon to which the halogen is bonded, and The compound represented by (5) is an allyl halide compound. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, R ¹⁷ does not have to be a C (O) O group or a phenylene group, and may be a direct bond. When R ¹⁶ is not a direct bond, R ¹⁷ is C (O) O in order to activate a carbon-halogen bond.
Groups, C (O) groups and phenylene groups are preferred.

As the compound represented by the above general formula (5)
Is, for example, CH₂= CHCH₂X, CH₂= C (CH
₃) CH₂X, CH₂= CHC (H) (X) CH₃, C
H₂= C (CH₃) C (H) (X) CH ₃, CH₂= C
HC (X) (CH₃)₂, CH₂= CHC (H) (X)
C₂H₅, CH₂= CHC (H) (X) CH (CH₃)
₂, CH₂= CHC (H) (X) C₆H₅, CH₂= C
HC (H) (X) CH₂C₆H₅, CH₂= CHCH₂
C (H) (X) -CO₂R, CH₂= CH (CH₂)₂
C (H) (X) -CO₂R, CH₂= CH (CH₂)₃
C (H) (X) -CO₂R, CH₂= CH (CH₂)₈
C (H) (X) -CO₂R, CH₂= CHCH₂C
(H) (X) -C₆H₅, CH₂= CH (CH₂)₂C
(H) (X) -C₆H₅, CH₂= CH (CH₂)₃C
(H) (X) -C₆H₅, (In each of the above formulas, X is
Represents chlorine, bromine or iodine, and R has 1 to 20 carbon atoms
Represents an alkyl group, an aryl group, or an aralkyl group).
Can be mentioned.

Examples of the sulfonyl halide compound having an alkenyl group include, for example, o-, m-, p-CH ₂ ＝
_{CH- (CH 2) n -C 6} H 4 -SO 2 X, o-, m
_{-, p-CH 2 = CH-} (CH 2) n -O-C 6 H 4 -
SO ₂ X, (in the above formulas, X represents chlorine, bromine, or iodine, and n represents an integer of 0 to 20).

In the case of an initiator having an alkenyl group, it is necessary to pay attention to the polymerization conditions and the reaction conditions with the olefin compound to be added, since the olefin of the initiator may also react with the polymerization terminal. For example, addition of an olefin compound at an early stage of polymerization can be mentioned.

Organic halide having a crosslinkable silyl group
Is not particularly limited, and may be represented, for example, by the following general formula (6).
Having the structure described below. R¹³R¹⁴C (X) -R^Fifteen-R¹⁶-C (H) (R⁸) CH₂− [Si (R ¹ )_2-b(Y)_bO]_m-Si (R²)_3-a(Y)_a (6) (where R⁸, R¹³, R¹⁴, R^Fifteen, R¹⁶,
R¹, R², A, b, m, X, and Y are as described above.
You. )

As the compound represented by the above general formula (6)
Is, for example, XCH₂C (O) O (CH₂)_nSi (O
CH₃)₃, CH₃C (H) (X) C (O) O (C
H₂)_nSi (OCH₃)₃, (CH₃)₂C (X) C
(O) O (CH₂)_nSi (OCH₃)₃, XCH₂C
(O) O (CH₂)_nSi (CH₃) (OCH₃)₂,
CH₃C (H) (X) C (O) O (CH₂)_nSi (C
H₃) (OCH₃)₂, (CH₃)₂C (X) C (O)
O (CH₂)_nSi (CH₃) (OCH₃)₂,(the above
In each formula, X represents chlorine, bromine or iodine, and n is
XCH represents an integer of 0 to 20) XCH₂C (O) O (CH₂)_nO (CH₂)_mSi
(OCH₃)₃, H₃CC (H) (X) C (O) O (C
H₂)_nO (CH₂)_mSi (OCH₃) ₃, (H
₃C)₂C (X) C (O) O (CH₂)_nO (CH₂)
_mSi (OCH₃) ₃, CH₃CH₂C (H) (X) C
(O) O (CH₂)_nO (CH₂)_mSi (OCH₃)
₃, XCH₂C (O) O (CH₂)_nO (CH₂)_mS
i (CH₃) (OCH₃)₂, H₃CC (H) (X) C
(O) O (CH₂)_nO (CH₂)_mSi (CH₃)
(OCH₃)₂, (H₃C)₂C (X) C (O) O (C
H₂)_nO (CH₂)_mSi (CH₃) (OC
H₃)₂, CH₃CH₂C (H) (X) C (O) O (C
H₂)_nO (CH₂)_mSi (CH ₃) (OC
H₃)₂, (In each of the above formulas, X represents chlorine, bromine,
N represents an integer of 1 to 20; m represents 0 to 20;
O, m, p-XCH₂-C₆H₄− (CH₂)₂Si
(OCH₃)₃, O, m, p-CH₃C (H) (X)-
C₆H₄− (CH₂)₂Si (OCH₃) ₃, O, m,
p-CH₃CH₂C (H) (X) -C₆H₄− (C
H₂)₂Si (OCH₃)₃, O, m, p-XCH₂−
C₆H₄− (CH₂)₃Si (OCH₃)₃, O, m,
p-CH₃C (H) (X) -C₆H₄− (CH₂)₃S
i (OCH₃) ₃, O, m, p-CH₃CH₂C (H)
(X) -C₆H₄− (CH₂)₃Si (OCH₃)₃,
o, m, p-XCH₂-C₆H₄− (CH₂)₂-O-
(CH₂)₃Si (OCH₃)₃, O, m, p-CH₃
C (H) (X) -C₆H₄− (CH₂)₂-O- (CH
₂) ₃Si (OCH₃)₃, O, m, p-CH₃CH₂
C (H) (X) -C₆H₄− (CH₂)₂-O- (CH
₂)₃Si (OCH₃)₃, O, m, p-XCH₂-C
₆H₄-O- (CH₂)₃Si (OCH₃)₃, O,
m, p-CH₃C (H) (X) -C₆H₄-O- (CH
₂)₃Si (OCH ₃)₃, O, m, p-CH₃CH₂
C (H) (X) -C₆H₄-O- (CH₂)₃Si (O
CH₃)₃, O, m, p-XCH₂-C₆H₄-O-
(CH₂)₂-O- (CH₂)₃Si (OCH₃)₃,
o, m, p-CH₃C (H) (X) -C₆H₄-O-
(CH₂)₂-O- (CH ₂)₃Si (OCH₃)₃,
o, m, p-CH₃CH₂C (H) (X) -C₆H₄−
O- (CH₂)₂-O- (CH₂)₃Si (OCH₃)
₃, (In each of the above formulas, X is chlorine, bromine, or
And the like).

Further examples of the organic halide having a crosslinkable silyl group include those having a structure represented by the following general formula (7). _{^{(R 2) 3-a (}} Y) a Si- [OSi (R 1) 2-b (Y) b] m -CH 2 - C (H) (R 8) -R 16 -C (R 13) ( ^{X) -R 17 -R 14 (7} ) ( ^{wherein, R 8, R 13, R} 14, R 16, R 17,
R ¹ , R ² , a, b, m, X, and Y are as described above. )

Such compounds include, for example, (C
_{H 3 O) 3 SiCH 2 CH} 2 C (H) (X) C 6 H 5,
(CH ₃ O) ₂ (CH ₃ ) SiCH ₂ CH ₂ C (H)
(X) C ₆ H ₅ , (CH ₃ O) ₃ Si (CH ₂ ) ₂ C
_{(H) (X) -CO 2} R, (CH 3 O) 2 (CH 3) S
_{i (CH 2) 2 C (} H) (X) -CO 2 R, (CH
_{3 O) 3 Si (CH 2} ) 3 C (H) (X) -CO 2 R,
(CH ₃ O) ₂ (CH ₃ ) Si (CH ₂ ) ₃ C (H)
_{(X) -CO 2 R, (} CH 3 O) 3 Si (CH 2) 4 C
_{(H) (X) -CO 2} R, (CH 3 O) 2 (CH 3) S
_{i (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) S
_{i (CH 2) 3 C (} H) (X) -C 6 H 5, (CH
_{3 O) 3 Si (CH 2} ) 4 C (H) (X) -C 6 H 5,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 4 C (H)
_{(X) -C 6 H 5,} ( in each formula above, X is chlorine,
Represents bromine or iodine, and R represents an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group).

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

An organic halide having an amino group, or
The sulfonyl halide compound is not particularly limited,
For example, the following can be mentioned. _{H 2 N- (CH 2) n} -OC (O) C (H) (R)
(X) (In each of the above formulas, X represents chlorine, bromine, or iodine; R represents a hydrogen atom or an alkyl group, an aryl group, or an aralkyl group having 1 to 20 carbon atoms; Indicates an integer.)

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

[0066]

Embedded image

(In the above formulas, X represents chlorine, bromine,
Or, it represents iodine, and R is a hydrogen atom or a carbon number of 1 to 20.
Represents an alkyl group, an aryl group, or an aralkyl group, and n represents an integer of 1 to 20. )

In the present invention, in order to obtain a polymer having two or more olefin terminal structures in one molecule, an organic halide having two or more starting points or a sulfonyl halide compound is used as an initiator. . To give a concrete example,

[0069]

Embedded image

[0070]

Embedded image

And the like.

<Regarding Monomers Constituting Main Chain of Vinyl Polymer> As the monomers composing the main chain of the vinyl polymer used in this polymerization, all of the above-mentioned vinyl monomers are suitably used. Further, since the polymerization system shown below is living polymerization, it is possible to produce a block copolymer by successive addition of a polymerizable monomer.

<Regarding polymerization conditions> The polymerization can be carried out without solvent or in various solvents. These are not particularly limited, and include, for example, hydrocarbon solvents such as benzene and toluene;
Ether solvents such as diethyl ether and tetrahydrofuran; halogenated hydrocarbon solvents such as methylene chloride and chloroform; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert Alcohol solvents such as -butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; ester solvents such as ethyl acetate and butyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate. . These may be used alone or in combination of two or more. Further, the polymerization can be carried out in the range of room temperature to 200 ° C, preferably 50 to 150 ° C.

During and during such polymerizations,
When the compound (I) having an internal olefin is added, the compound is added almost one by one to the terminal. As a result, the functional group of the compound (I) having the internal olefin is introduced to the terminal of the polymer. The end point of the polymerization is defined as the time when preferably 80% or more of the monomer has reacted, more preferably 90% or more, particularly preferably 95% or more, and further preferably 99% or more.
This is the time when the reaction has been completed.

When a compound having an amino group, a hydroxyl group or a carboxylic acid group is allowed to react with the polymerization terminal, the reaction may be carried out as it is. However, since such a group may affect the polymerization terminal or the catalyst, In that case, a compound having a protecting group may be used. Examples of the protecting group include an acetyl group, a silyl group, and an alkoxy group.

The amount of the compound used for introducing these functional groups is not particularly limited. Since the reactivity of the alkenyl group of these compounds is not very high, it is preferable to increase the amount added in order to increase the reaction rate,
On the other hand, in order to reduce the cost, it is preferable that the addition amount is close to the equivalent amount with respect to the growth terminal, and it may be optimized depending on the situation.

The amount of the compound having two or more olefins including an internal olefin to introduce an alkenyl group at the terminal is preferably an excess amount relative to the polymerization growth terminal. If equal or less than the end, both of the two olefins may react and couple the polymerization end. For compounds where the reactivity of the two olefins is equal, the probability of coupling occurring is
It is determined statistically according to the amount added in excess. Therefore, it is preferably at least 1.5 times, more preferably at least 3 times, particularly preferably at least 5 times.

<Functional Group Introduction Method> The vinyl polymer having at least one crosslinkable silyl group can be produced by various methods. Among them, the production methods [A] to [D] of the vinyl polymer whose main chain is obtained by the living polymerization method will be described below, but the invention is not limited thereto. For example, in the production method [C] described below, when a vinyl polymer is synthesized by a living radical polymerization method, a compound having both a polymerizable alkenyl group and a crosslinkable silyl group is reacted with a predetermined vinyl monomer. And a method of polymerizing this by a free radical polymerization method.

[A] A method of adding a hydrosilane compound having a crosslinkable silyl group to a vinyl polymer having at least one alkenyl group. The hydrosilane compound having a crosslinkable silyl group used in the production method [A] is not particularly limited, and may be, for example, the following general formula (8)
And the like. ^{_{H- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (8) ( ^{wherein, R 1, R 2, a} , b, m and Y is as described above.)

Among them, a compound represented by the following general formula (9) is preferable from the viewpoint of easy availability. _{^{H-Si (R 2) 3}} -a (Y) a (9) ( ^{wherein, R} 2, Y and a are as defined above.)

In the above production method [A], a transition metal catalyst is usually used as a hydrosilylation catalyst. The transition metal catalyst is not particularly limited and includes, for example, a dispersion of platinum solids on a carrier such as platinum alone, alumina, silica, and carbon black; chloroplatinic acid; Complex; platinum-olefin complex, platinum (0) -divinyltetramethyldisiloxane complex; RhCl (PPh ₃ ) ₃ , RhCl ₃ , R
uCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , Pd
Compounds other than platinum compounds, such as Cl ₂ .H ₂ O, NiCl ₂ , and TiCl ₄ , may be mentioned. These may be used alone or in combination of two or more.

The method for producing the vinyl polymer having at least one alkenyl group used in the above-mentioned production method [A] is not particularly limited as long as it is a living radical polymerization method, and examples thereof include the following [A-a] to [A-]. Aj].

[B] A method of reacting a vinyl polymer having at least one hydroxyl group with a compound having a functional group capable of reacting with a hydroxyl group such as a crosslinkable silyl group and an isocyanate group. The compound having a functional group capable of reacting with a hydroxyl group such as a crosslinkable silyl group and an isocyanate group used in the above production method [B] is not particularly limited, and examples thereof include γ-isocyanatopropyltrimethoxysilane,
γ-isocyanatopropylmethyldimethoxysilane,
γ-isocyanatopropyltriethoxysilane and the like can be mentioned. These may be used alone or in combination of two or more.

In the reaction in the above-mentioned production method [B], a known catalyst for a urethanization reaction may be used if necessary.

The method for producing the vinyl polymer having at least one hydroxyl group used in the above-mentioned production method [B] is not particularly limited as long as it is a living radical polymerization method. Bf].

[C] A method of reacting a compound having both a polymerizable alkenyl group and a crosslinkable silyl group together with a predetermined vinyl monomer when synthesizing a vinyl polymer by living radical polymerization. The compound having both a polymerizable alkenyl group and a crosslinkable silyl group used in the above production method [C] is not particularly limited, and examples thereof include trimethoxysilylpropyl (meth) acrylate and methyldimethoxysilylpropyl (meth) acrylate. Examples include compounds represented by the following general formula (10).

[0087] _{^{H 2 C = C (R 18}} ) -R 6 -R 7 - [Si (R 1) 2-b (Y) b O] m -S i (R 2) 3-a (Y) a ( 10) (wherein, R ¹ , R ² , Y, a, b, and m are as described above. R ¹⁸ represents hydrogen or a methyl group. R ⁶ represents —C.
(O) O- or an o-, m- or p-phenylene group. R ⁷ represents a direct bond or a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds. These may be used alone or in combination of two or more. )

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

[D] A method of reacting a stabilized carbanion having a crosslinkable silyl group with a vinyl polymer having at least one highly reactive carbon-halogen bond. The stabilized carbanion having a crosslinkable silyl group used in the above production method [D] is not particularly limited, and examples thereof include a compound represented by the following general formula (11).

M⁺C⁻(R⁸) (R⁹) -R¹⁰-C (H) (R¹¹) -CH₂− [Si (R ¹ )_2-b(Y)_bO]_m-Si (R²)_3-a(Y)_a (11) (where R¹, R², Y, a, b and m are as described above.
It is. R⁸And R⁹Are both Carbanion C⁻The stable
Electron-withdrawing groups, or one is an electron-withdrawing group and the other is
Hydrogen or an alkyl group having 1 to 10 carbon atoms or phenyl
Represents a group. R¹⁰Is a direct bond or one or more
A divalent group having 1 to 20 carbon atoms which may contain a ter bond
Indicates the machine base. R¹¹Is hydrogen, alkyl having 1 to 10 carbons
Groups, aryl groups having 6 to 10 carbon atoms or 7 to 10 carbon atoms
Represents an aralkyl group. M⁺Is an alkali metal ion, or
Represents a quaternary ammonium ion. R⁸And R⁹No electricity
-CO 2₂R, -C (O) R and CN
Is preferred. Here, R is hydrogen, alkyl having 1 to 10 carbon atoms.
Group, an aryl group having 6 to 10 carbon atoms or 7 to 10 carbon atoms
Represents an aralkyl group. )

The method for producing the vinyl polymer having at least one highly reactive carbon-halogen bond used in the above-mentioned production method [D] is not particularly limited, and for example, the method of [Da] described later. And the like.

The methods [A-a] to [A-j] for producing the vinyl polymer having at least one alkenyl group used in the above-mentioned production method [A] will be described below, but are not limited thereto. Not something. The following production methods [Aa] to [Ab] are examples of a method for directly synthesizing a vinyl polymer having at least one alkenyl group.

[A-a]
When synthesizing a vinyl polymer, the specified vinyl monomer
Together with a polymerizable alkenyl group and a low polymerizable
A method in which a compound having a kenyl group is also reacted. Made above
Polymerizable alkenyl used in production method [A-a]
And a compound having a low polymerizable alkenyl group
Is not particularly limited, for example, represented by the following general formula (12)
Compounds. H₂C = C (R³) -R⁴-R¹²-C (R¹³) = CH₂ (12) (where R³And R⁴Is as described above. R¹²Is
Having a direct bond or one or more ether bonds
A divalent organic group having 1 to 20 carbon atoms. R ¹³Is
Hydrogen, an alkyl group having 1 to 10 carbon atoms, 6 to 10 carbon atoms
Represents an aryl group or an aralkyl group having 7 to 10 carbon atoms
You. )

The timing at which the compound having both the polymerizable alkenyl group and the compound having a low polymerizable alkenyl group is reacted is not particularly limited. However, when the obtained crosslinked product is expected to have rubber-like properties, the polymerization reaction is carried out. It is preferable to react as the second monomer at the end of the reaction or after the reaction of the predetermined vinyl monomer.

[Ab] When a vinyl polymer is synthesized by living radical polymerization, a compound having at least two alkenyl groups having low polymerizability is added at the end of the polymerization reaction or after the reaction of a predetermined vinyl monomer. How to react. The compound having at least two alkenyl groups having low polymerizability is not particularly limited, and examples thereof include 1,5-hexadiene, 1,7-octadiene, and 1,9-decadiene.

The following production methods [Ac] to [Af] are as follows:
This is an example of a method for obtaining a vinyl polymer having at least one alkenyl group from a vinyl polymer having at least one highly reactive carbon-halogen bond. The polymer having at least one highly reactive carbon-halogen bond can be obtained by the below-described production method [Da] or the like.

[Ac] A vinyl polymer having at least one highly reactive carbon-halogen bond is treated with an alkenyl group-containing organometallic compound represented by organotin such as allyltributyltin and allyltrioctyltin. Reacting to substitute the halogen with an alkenyl group-containing substituent.

[Ad] A vinyl-based polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having an alkenyl group represented by the following general formula (13) or the like. A method in which halogen is substituted with an alkenyl group. ^{M + C - (R 8)} (R 9) -R 14 -C (R 13) = CH 2 (13) ( ^{wherein, R 8, R 9, R} 13 and ^{M +} are as defined above .R ¹⁴ represents a direct bond or a divalent organic group having 1 to 10 carbon atoms which may contain one or more ether bonds.) As the electron-withdrawing groups for R ⁸ and R ⁹ , -CO ₂
R, -C (O) R and CN are preferred. Here, R is as described above.

[A-e] An enolate anion 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 is added to halogen or acetyl. A method of reacting an alkenyl group-containing electrophilic compound such as an alkenyl group-containing compound having a leaving group such as a group, an alkenyl group-containing carbonyl compound, an alkenyl group-containing isocyanate compound, and an alkenyl group-containing acid halide.

[Af] An alkenyl group-containing oxyanion represented by the following general formula (14) or the following general formula (15) is added to a vinyl polymer having at least one highly reactive carbon-halogen bond. Or the like, and reacting the alkenyl group-containing carboxylate anion represented by the above formula to replace the halogen with an alkenyl group-containing substituent. _{^{H 2 C = C (R 13}} ) -R 15 -O - M + (14) ( ^{wherein, R 13} and ^{M +} are as defined above ^{.R 15}
Represents a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds. _{^{) H 2 C = C (R}} 13) -R 16 -C (O) O - M + (15) ( ^{wherein, R 13} and ^{M +} are as defined above ^{.R 16}
Represents a direct bond or a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds. )

The following production methods [Ag] to [Aj] are as follows:
This is an example of a method for obtaining a vinyl polymer having at least one alkenyl group from a vinyl polymer having at least one hydroxyl group. The method for producing the vinyl polymer having at least one hydroxyl group is not particularly limited, and examples thereof include the following production methods [Ba] to [Bf].

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

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

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

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

In the method for producing a vinyl polymer having at least one alkenyl group, a halogen atom is directly involved in introducing an alkenyl group, as in the above-mentioned production methods [A-a] and [A-b]. As a production method that does not use the method, the method [Ab] is more preferable because the control is easier. Among living radical polymerization methods, an atom transfer radical polymerization method is more preferable.

On the other hand, the production methods [Ac] to [A-
f] and the like, an alkenyl group is introduced by converting a halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, such as an organic halide or a sulfonyl halide compound. It is preferable to use a vinyl polymer having at least one highly reactive carbon-halogen bond at a terminal obtained by radical polymerization (atom transfer radical polymerization) using a transition metal complex as a catalyst. The method of [A-f] is more preferable because the control is easier.

The above production methods [B] and [Ag] to [A-
The method for producing the vinyl polymer having at least one hydroxyl group used in j] is not particularly limited, and examples thereof include the following methods [Ba] to [Bf].

[Ba] A compound having both a polymerizable alkenyl group and a hydroxyl group represented by the following general formula (16) together with a predetermined vinyl monomer when a vinyl polymer is synthesized by living radical polymerization. How to react. _{^{H 2 C = C (R 3}} ) -R 4 -R 12 -OH (16) ( ^wherein, R 3, ^{R 4} and ^{R 12} are as defined above.)

The timing at which the compound having both the polymerizable alkenyl group and the hydroxyl group is reacted is not particularly limited. After completion of the reaction of the vinyl-based monomer, it is preferable to cause the reaction as the second monomer.

[Bb] When a vinyl polymer is synthesized by living radical polymerization, at the end of the polymerization reaction or after 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] Hydrolysis of a halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond by a method disclosed in JP-A-4-132706 or a compound containing a hydroxyl group A hydroxyl group is introduced into the terminal by reacting

[Bd] A vinyl-based polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having a hydroxyl group represented by the following general formula (17), etc. A method wherein the halogen is substituted with a hydroxyl group-containing substituent. ^{M + C - (R 8)} (R 9) -R 14 -OH (17) (. ^Wherein, R ^8, R ^{9, R 14} and ^{M +} are as defined above) electron of ^{R 8} and ^{R 9} As a suction group, -CO ₂
R, -C (O) R and CN are preferred. Here, R is as described above.

[Be] An enolate anion 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 aldehyde, Alternatively, a method of reacting ketones.

[Bf] A vinyl-based polymer having at least one highly reactive carbon-halogen bond is added to a hydroxyl group-containing oxyanion represented by the following general formula (18) or the like or the following general formula (19): Reacting a hydroxyl group-containing carboxylate anion represented by formula (1) to replace the halogen with a hydroxyl group-containing substituent. ^{HO-R 15 -O - M +} (18) ( ^{wherein, R 15} and ^{M +} are as defined ^{above.) HO-R 16 -C (} O) O - M + (19) ( wherein, R ¹⁶ and M ⁺ are as described above.)

In the method for producing a vinyl polymer having at least one hydroxyl group, the above-mentioned production method [B-
In the case of a production method in which a halogen atom is not directly involved in introducing a hydroxyl group such as a) to [Bb], the method of [Bb] is more preferable from the viewpoint of easier control. Among living radical polymerization methods, an atom transfer radical polymerization method is more preferable.

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

The above production methods [D], [Ac] to [A-
f] and [Bc] to [Bf].
The method for producing the vinyl polymer having at least one highly reactive carbon-halogen bond is not particularly limited, and examples thereof include the following [Da] method.

[Da] Atom transfer radical polymerization using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst.

In the case where the cured product of the curable composition of the present invention is particularly required to have rubber-like properties, the molecular weight between cross-linking points which greatly affects rubber elasticity can be made large, so that at least one of the cross-linkable silyl groups is required. The individual is preferably at the end of the molecular chain. Those having a crosslinkable silyl group at two molecular chain terminals are more preferable. Those having all the crosslinkable silyl groups at the molecular chain terminals are more preferable.

Accordingly, the vinyl polymer having at least one hydroxyl group, halogen or alkenyl group, which is used for producing the vinyl polymer having at least one crosslinkable silyl group, has these functional groups in the molecular chain. Those having a terminal are preferred.

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

When the above-mentioned atom transfer radical polymerization method is carried out using the above-mentioned organic halide having a crosslinkable silyl group as an initiator, a carbon-silyl group having a crosslinkable silyl group at one end and a highly reactive carbon atom at the other end is obtained. A vinyl polymer having a halogen bond is obtained. If the terminal halogen atom of this vinyl polymer is converted into a crosslinkable silyl group-containing substituent using the method described above, a vinyl polymer having a crosslinkable silyl group at both molecular chain terminals can be obtained.

The above-mentioned crosslinking can also be carried out by coupling the halogen atoms of the vinyl polymer with each other using a compound having a total of two or more identical or different functional groups capable of replacing the above-mentioned terminal halogen atoms. A vinyl polymer having a reactive silyl group at both molecular chain terminals can be obtained.

The compounds having a total of two or more identical or different functional groups capable of replacing the above-mentioned terminal halogen atoms are not particularly restricted but include, for example, polyols, polyamines, polycarboxylic acids, polythiols, and salts thereof; Sulfides and the like can be mentioned.

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

The vinyl polymer having at least one crosslinkable silyl group can be obtained by optionally combining the above-mentioned production methods and the like. Typical synthesis steps include the following synthesis steps A and B. it can.

Synthesis Step A (1) A step of synthesizing a vinyl polymer having a halogen atom at its terminal by polymerizing a vinyl monomer by an atom transfer radical polymerization method, and (2) Obtaining the above step (1). Synthesizing a vinyl polymer having an alkenyl group at the terminal by reacting a vinyl polymer having a halogen atom at the terminal with an oxyanion having an alkenyl group to thereby synthesize a vinyl polymer having an alkenyl group at the terminal; The addition of a crosslinkable silyl group-containing hydrosilane compound represented by the above general formula (1) to the terminal alkenyl group of the vinyl polymer having a terminal alkenyl group obtained in the step (a) is carried out. Converting to a group.

Synthesis Step B (1) A step of synthesizing a vinyl polymer by polymerizing a vinyl monomer by a living radical polymerization method, and (2) a step of polymerizing the vinyl polymer with the vinyl polymer obtained in the step (1). Reacting with a compound having at least two alkenyl groups having low alkenyl groups to synthesize a vinyl polymer having an alkenyl group at the terminal, (3) a vinyl polymer having an alkenyl group at the terminal obtained in the step (2). A step of adding a hydrosilane compound having a crosslinkable silyl group represented by the above general formula (1) to a terminal alkenyl group of the polymer to convert the polymer into a crosslinkable silyl group-containing substituent.

[Compound having a siloxane bond of component (B)] The compound of component (B) used in the present invention is as follows.
It is a compound having a siloxane bond, and is preferably an organopolysiloxane comprising a repeating unit represented by the following general formula (2), and-[Si (R ³ ) (R ⁴ ) ₂ O]-(2) ( In the formula, R ³ and R ⁴ represent hydrogen or a monovalent hydrocarbon group, which may be the same or different.)

[0131]

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Homogeneous or copolymers having a structural unit of, for example, may be mentioned, but are not limited thereto.

The compound having a siloxane bond of the component (B) used in the present invention has at least one hydrolyzable functional group bonded to the terminal and / or silicon atom in the main chain of the above-mentioned organopolysiloxane. However, the present invention is not limited thereto. When a compound having a siloxane bond to which a hydrolyzable functional group is bonded is used, the adhesiveness is not reduced, and in some cases, the adhesiveness is improved.

[0134]

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Still more preferred is an organopolysiloxane represented by the following general formula (3): Z _3-c -Si (R ⁵ ) _c O- [Si (R ⁵ ) ₂ O] _n -Si ( R ⁵ ) _c (Z) _{3 -c} (3) (wherein, R ⁵ represents a same or different monovalent hydrocarbon group, n represents a positive integer of 19 or less, and two R ^{5 s} ) When present, they may be the same or different, c represents 0, 1, 2, or 3, Z represents a hydroxyl group or a hydrolyzable group, and two or more Zs are present. Sometimes, they may be the same or different.)

[0136]

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[0137]

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Although the present invention is not limited thereto. Further is R ⁵ is a methyl group or a phenyl group of the general formula (3), a c = 2, and Z is particularly preferably a hydroxyl group.

In order to increase the compatibility with the vinyl polymer of the component (A), a copolymer of the component (B) having a siloxane bond with a (meth) acrylic acid monomer may be used. For example, as a compound having a siloxane bond having a (meth) acryl group in a side chain, a compound obtained by reacting a methyl hydrogen silicone oil (commonly referred to as H-oil) with a (meth) acryl-based compound having an alkenyl terminal group may be used. Yes, but not limited to this.

-Compounding agent-The curable composition of the present invention may contain a condensation catalyst, if necessary, for the purpose of adjusting various physical properties of the curable composition or the cured product.
Filler, plasticizer, anti-sag, colorant, adhesion promoter,
An anti-aging agent, a flame retardant, a curability adjuster, a weather resistance improver, a mechanical property adjuster, and the like may be added.

The condensation catalyst is not particularly restricted but includes, for example, titanates such as tetrabutyl titanate and tetrapropyl titanate; dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dimethoxide, Organotin compounds such as tin octylate and tin naphthenate; lead octylate, butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine,
Triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine,
Cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,
4,6-tris (dimethylaminomethyl) phenol,
Amine compounds such as morpholine, N-methylmorpholine, 1,3-diazabicyclo (5,4,6) undecene-7 or carboxylates thereof; amine compounds such as a reaction product or a mixture of laurylamine and tin octylate Reaction products and mixtures of compounds with organotin compounds; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction products of excess polyamines and epoxy compounds; silane coupling agents having amino groups, for example γ Known silanol catalysts such as -aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane and the like can be mentioned. These may be used alone or in combination of two or more. When the hydrolyzable group Y is an alkoxy group, it is preferable to use a curing catalyst since the curing rate is relatively slow only with the vinyl polymer of the component (A).

[0142] The filler is not particularly limited.
Reinforcing fillers such as fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, Fillers such as ferric oxide, zinc oxide, activated zinc white and shirasu balloon; fibrous fillers such as asbestos, glass fibers and filaments. In order to obtain a cured product having high strength with these fillers, mainly fumed silica, precipitated silica, silicic anhydride, hydrated silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay and activated zinc A filler selected from flowers and the like can be added. When it is desired to obtain a cured product having low strength and large elongation, a filler selected mainly from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like can be added. These may be used alone or in combination of two or more.

The plasticizer is not particularly limited.
Dibutyl phthalate, diheptyl phthalate, di (2-
Phthalates such as ethylhexyl) phthalate and butylbenzyl phthalate; non-aromatic dibasic esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate and isodecyl succinate; butyl oleate and methyl acetyl risilinolate Aliphatic esters; Polyalkylene glycol esters such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters;
Chlorinated paraffins; hydrocarbon-based oils such as alkyl diphenyl and partially hydrogenated terphenyl; process oils; polyethers such as polyethylene glycol and polypropylene glycol; epoxy plasticizers such as epoxidized soybean oil and benzyl epoxy stearate Plasticizers such as polyester plasticizers. These may be used alone or in combination of two or more. In addition, these plasticizers can be blended at the time of polymer production.

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.

The physical property modifier is not particularly restricted but includes, for example, alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltrimethoxysilane. Isopropenoxysilane, alkylisopropenoxysilane such as γ-glycidoxypropylmethyldiisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, Vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane, N- (β
-Aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Examples thereof include 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 adhesion promoter is not particularly restricted but includes, for example, epoxy resins, phenol resins, sulfur, various silane coupling agents, alkyl titanates, aromatic polyisocyanates and the like. Performance can be improved.

The curable composition of the present invention can be prepared as a one-component type in which all the components are premixed, sealed and stored, and 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 blending agent and the polymer composition may be mixed before use to prepare a two-component type.

The curable composition of the present invention comprises a sealing material,
For paints, powder coatings, coating materials, sealing materials, adhesives, adhesives, potting materials, casting materials, molding materials, elastic adhesives, foams, films, gaskets, resists, various molding materials, artificial marble, etc. Can be used.

[0149]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. "Parts" and "%" in the following Examples and Comparative Examples
Represents “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)”
It was calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column filled with a crosslinked polystyrene gel (shodex GPC K-804; manufactured by Showa Denko KK) was used, and chloroform was used as a GPC solvent.

(Production Example 1) A 10 with a reflux tube and a stirrer
In a separable flask of L, CuBr (42.0 g,
0.293 mol), and the inside of the reaction vessel was purged with nitrogen. Acetonitrile (559 mL) was added, and the mixture was stirred at 70 ° C. for 45 minutes in an oil bath. To this, butyl acrylate (1.00 kg), diethyl 2,5-dibromoadipate (176 g, 0.488 mol), pentamethyldiethylenetriamine (hereinafter triamine) (4.0)
0 mL, 3.32 g, 19.2 mmol) was added to start the reaction. With heating and stirring at 70 ° C., butyl acrylate (4.00 kg) was continuously added dropwise over 190 minutes. During the dropping of butyl acrylate, triamine (4.0
0 mL, 3.32 g, 0.0192 mol). 310 minutes after the start of the reaction, 1,7-octadiene (1.44 L, 1.07 kg, 9.75 mol), triamine (20.5 mL, 17.0 g, 98.1 mol)
l) was added, followed by heating and stirring at 70 ° C. for 210 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-terminated polymer (polymer [1]). The number average molecular weight of the polymer [1] was 14,000, and the molecular weight distribution was 1.3.

In a 10 L separable flask equipped with a reflux tube, polymer [1] (2.7 kg) and potassium benzoate (142) were added.
g) and N, N-dimethylacetamide (2.7 L) were charged and heated and stirred at 70 ° C. for 25 hours under a nitrogen stream. After removing N, N-dimethylacetic acid amide under reduced pressure by heating, the mixture was diluted with toluene. The solids insoluble in toluene (KBr and excess potassium benzoate) were filtered through an activated alumina column. The volatile component of the filtrate was distilled off under reduced pressure to obtain a polymer [2].

In a 2 L round bottom flask equipped with a reflux tube, polymer [2] (2.7 kg), aluminum silicate (540 g, Kyowa Chemical Co., Ltd., Kyoward 700PEL), and toluene (2.7) were added.
L), and the mixture was heated and stirred at 100 ° C. for 5 hours under a nitrogen stream. After the aluminum silicate was removed by filtration, the toluene in the filtrate was distilled off under reduced pressure to obtain a polymer [3].

The polymer [3] (760) was placed in a 1 L pressure-resistant reaction vessel.
g), dimethoxymethylhydrosilane (46.3 mL,
0.38 mol), methyl orthoformate (13.7 mL,
0.13 mmol), and 1,1,3,3-
A tetramethyl-1,3-divinyldisiloxane complex was charged. However, the amount of the platinum catalyst used was 10 ⁻³ equivalent in molar ratio to the alkenyl group of the polymer. The reaction mixture was heated at 100 C for 1 hour. The volatile component of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated polymer (polymer [4]). The number average molecular weight of the obtained polymer is GP
C measurement (in terms of polystyrene) revealed a molecular weight distribution of 15,000 and a molecular weight distribution of 1.4. The average number of silyl groups introduced per molecule of polymer was determined by ¹ H NMR analysis to be 2.0.

(Production Example 2) Dimethylpolysiloxane having vinyl groups at both ends (manufactured by Chisso, DMS-25: number average molecular weight 17200) in a 300 mL pressure-resistant reaction vessel (97.
3g), dimethoxymethylhydrosilane (2.64 m
L, 0.02 mol), and 1,1,3,
A 3-tetramethyl-1,3-divinyldisiloxane complex was charged. However, the amount of the platinum catalyst used was 2 × 10 ⁻³ equivalent in molar ratio to the vinyl group of the polymer. The reaction mixture was heated at 60-70 ° C. By distilling off the volatile components of the mixture under reduced pressure, dimethylpolysiloxane having a silicon group at both terminals (polymer [5]) was obtained. Polymer 1
According to ¹ H NMR analysis, 2.0 silicon groups were introduced per molecule.

Example 1 The polymer [4] obtained in Production Example 1 and the polymer [5] obtained in Production Example 2 were mixed, and a tetravalent Sn catalyst (dibutyltin diacetylacetonate) was mixed. And cured in a room.

Comparative Example 1 Only the polymer [4] obtained in Production Example 1 was cured in a room using a tetravalent Sn catalyst (dibutyltin diacetylacetonate).

The surface tackiness (tack) of the cured product after curing was measured by touch with a finger. The results are shown in Table 1.

[0160]

[Table 1]

[0161]

As described above, the curable composition of the present invention has good flame retardancy, heat resistance and weather resistance with little surface tackiness.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoshiki Nakagawa 1-2-80 Yoshida-cho, Hyogo-ku, Kobe-shi, Hyogo Kanebuchi Chemical Industry Co., Ltd.Kobe Research Laboratory (72) Inventor Kenichi Kitano Kobe, Hyogo Prefecture 1-280 Yoshida-cho, Hyogo-ku, Ichigo-cho Kanebuchi Chemical Industry Co., Ltd.Kobe Research Laboratory (72) Inventor Tadashi Fujita 1-2-80 Yoshida-cho, Hyogo-ku, Kobe-shi, Hyogo Kanebuchi Chemical Industry Co., Ltd. Laboratory Kobe Laboratory F-term (reference) 4J002 BB03W BB12W BC02W BD03W BD12W BF01W BG01W BG02W BG10W BG13W BH02W BL00W CP01W CP03X GH00 GJ01 GJ02 GP00

Claims (17)

[Claims] 1. A curable composition comprising: (A) a vinyl polymer having at least one crosslinkable silyl group; and (B) a compound having a siloxane bond. 2. The curable composition according to claim 1, wherein the vinyl polymer as the component (A) is a vinyl polymer having a crosslinkable silyl group at a molecular terminal. 3. The curing method according to claim 1, wherein the vinyl polymer as the component (A) is a vinyl polymer having a crosslinkable silyl group represented by the general formula (1). Composition. ^{_{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1) ( wherein, ^{R 1} and ^{R 2} are both 1 carbon atoms An alkyl group having 20; an aryl group having 6 to 20 carbon atoms; an aralkyl group having 7 to 20 carbon atoms; or (R ′) ₃ Si—
(R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms,
Three R's may be the same or different), and when two or more R ¹ or R ² are present, they may be the same , May be 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 an integer of 0-19. However, a + mb ≧ 1
Is satisfied. ) 4. The main chain of the vinyl polymer as the component (A) is as follows:
Claims when produced mainly by polymerizing monomers selected from the group consisting of (meth) acrylic acid monomers, nitrile group-containing vinyl monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers and silicon-containing vinyl monomers. Item 4. The curable composition according to any one of Items 1 to 3. 5. The curable composition according to claim 4, wherein the vinyl polymer as the component (A) is a (meth) acrylic polymer. 6. The curable composition according to claim 5, wherein the vinyl polymer as the component (A) is an acrylic polymer. 7. The curable composition according to claim 6, wherein the vinyl polymer as the component (A) is an acrylate polymer. 8. The curable composition according to claim 7, wherein the vinyl polymer (A) is a butyl acrylate polymer. 9. The ratio (Mw / M) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the vinyl polymer of the component (A) measured by gel permeation chromatography.
The curable composition according to any one of claims 1 to 8, wherein the value of n) is less than 1.8. 10. The curable composition according to claim 1, wherein the main chain of the component (A) is produced by a living radical polymerization method. 11. The curable composition according to claim 10, wherein the main chain of the component (A) is produced by an atom transfer radical polymerization method. 12. The catalyst of the atom transfer radical polymerization method, wherein the catalyst is copper,
The curable composition according to claim 11, which is a complex of a metal selected from the group consisting of nickel, ruthenium, and iron. 13. The curable composition according to claim 12, wherein the catalyst for the atom transfer radical polymerization method is a copper complex. 14. The compound having a siloxane bond of the component (B) is an organopolysiloxane comprising a repeating unit represented by the general formula (2).
14. The curable composition according to any one of items 13 to 13. -[Si (R ³ ) (R ⁴ ) ₂ O]-(2) (wherein R ³ and R ⁴ are hydrogen or a monovalent hydrocarbon group, and they may be the same or different. May be.) 15. The curable composition according to claim 1, wherein the component (B) having a siloxane bond is an organopolysiloxane represented by the general formula (3). Composition. ^{_{Z 3-c -Si (R 5}} ) c O- [Si (R 5) 2 O] n -Si (R 5) c (Z) 3-c (3) ( wherein, ^{R 5} is same or different A monovalent hydrocarbon group; n
Is a positive integer of 19 or less, and when two or more R ⁵ are present,
They may be the same or different. ;
c represents 0, 1, 2, or 3; Z represents a hydroxyl group or a hydrolyzable group. When two or more Zs are present, they may be the same or different. ) 16. The organopolysiloxane of the component (B) represented by the general formula (3), wherein R ⁵ is a methyl group or a phenyl group, c = 2, and Z is a hydroxyl group. A curable composition according to claim 15. 17. The curing method according to claim 1, wherein the compound having a siloxane bond as the component (B) is a copolymer with a (meth) acrylic acid-based monomer. Composition.