JP2001303023A - Sealing material for ssg system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new sealing material for SSG(structural sealant glazing) system which has various characteristics (especially weather-resistant glass adhesivity) equal to those of conventional silicone sealing materials and does not stain glass, while the conventional sealing materials easily form stripe-like stains caused by the silicones on glass or store to mar the fine sight of a building and further require the consideration of gondola rails for cleaning the stains, when the building is designed. SOLUTION: This sealing material for SSG-making method, characterized by containing (I) a vinylic polymer having at least one cross-linkable functional group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a sealing material for SSG construction.

[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 using a polysulfide having a hydroxyl group, and a silyl group is added to the terminal by utilizing the reactivity of the hydroxyl group. A method for synthesizing a (meth) acrylic polymer 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, the molecular weight and molecular weight distribution (ratio of the number average molecular weight to the number average molecular weight) of the obtained polymer are obtained.
Is difficult to control.

[0005] In contrast to such conventional techniques, the 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 a “crosslinkable silyl group”), or Cured products obtained from the composition are excellent in heat resistance or weather resistance, sealing materials such as elastic sealing materials for building materials and sealing materials for double glazing, electric and electronic parts materials such as solar cell back surface sealing materials, Electrical insulation materials such as insulation coating materials for electric wires and cables, adhesives, adhesives, elastic adhesives, paints, powder coatings, coating materials, foams, potting agents for electric and electronic devices, films, gaskets, casting materials, various types It is used for various purposes such as molding materials, netted glass and sealing materials for rust prevention and waterproofing of the end face (cut portion) of laminated glass.

Among them, the sealing material used for the SSG construction method is required to have various requirements such as adhesion durability including a waterproof function and maintenance of aesthetic appearance as described below. Figure 1 shows the SSG
1 shows a conceptual diagram of a construction method. With the SSG construction method, the flat glass that constitutes the windows and outer walls of the building is inserted into the grooves of the sash and supported.
Instead of fixing, as shown in Fig. 1, a structural sealant such as silicone rubber is filled in the gap between the glass sheet and the support member to form a structural adhesive system, and can be safely protected against various external forces applied to the glass sheet. This is a construction method aimed at supporting and fixing. The role of the structural sealant in the SSG construction method is to structurally fix the glass to the bonding profile and to transfer all the wind load received by the glass to the bonding profile.
Another is to maintain its performance for a long time. Therefore, the characteristics required as a structural sealant include the following items.

(Adhesiveness) ・ High adhesive strength ・ Good adhesiveness to glass / adhesive material ・ Good durability (Physical properties) ・ High modulus ・ Moderate flexibility ( Workability)-Fast curing and good workability As described above, the structural sealant supports the structure, but the waterproofing sealant does not directly support the structure and simply maintains watertightness and airtightness. (See FIG. 1). As a sealing material that meets these required properties,
At present, silicone sealants are generally used.

[0008]

When a silicone-based sealing material is used for the SSG construction method, streak-like dirt caused by silicone is liable to adhere to glass and stone materials, which not only impairs the appearance of buildings as glass contamination, There is also a design challenge in that gondola rails must be considered during design to clean the dirt. An object of the present invention is to provide a sealing material for an SSG construction method that has various characteristics (particularly, glass weather resistance) of a conventional silicone-based SSG construction method sealing material and has no glass contamination. .

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above-mentioned current situation, and as a result, have found a technique which simultaneously satisfies the above-mentioned various characteristics. As a result, a sealing material for SSG construction which can achieve the above object can be obtained, and the present invention has been completed. That is, the present invention relates to a sealing material for an SSG construction method comprising, as an essential component, a vinyl polymer having at least one crosslinkable functional group. In particular, the present invention relates to a waterproofing sealing material for SSG construction, which comprises a vinyl polymer having at least one crosslinkable functional group as an essential component. The main chain of the vinyl polymer (I) is not particularly limited, but is selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and silicon-containing vinyl monomers. It is preferred to be produced by mainly polymerizing at least one type of monomer,
More preferably, it is produced by polymerization using a (meth) acrylic monomer, more preferably an acrylic monomer, more preferably an acrylate ester monomer, and most preferably a butyl acrylate monomer.

The main chain of the vinyl polymer (I) is not particularly limited, but is preferably produced by living radical polymerization, more preferably atom transfer radical polymerization. Further, in the atom transfer radical polymerization, there is no limitation, but the group 7 and group 8 of the periodic table,
It is preferable to use, as a catalyst, at least one selected from transition metal complexes having a Group 9 element, 10 group, or 11 element as a central metal, and a complex selected from the group consisting of copper, nickel, ruthenium, and iron complexes. More preferred are copper complexes. Further, the vinyl polymer (I) is not particularly limited, but has a molecular weight distribution, that is,
The ratio (M) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography
(w / Mn) is preferably less than 1.8.

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, group having a polymerizable carbon-carbon double bond, epoxy group, 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 polymer end. In addition, a similar functional group may be provided inside the main chain. However, when rubber elasticity is required for a crosslinked cured product, it is preferable that the functional group be provided only at the polymer terminal. 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, on average one or more, preferably 1.2 or more, Preferably, the number is 1.5 or more. The present invention is also a one-component sealing material for an SSG construction method, comprising a vinyl polymer (I) having at least one crosslinkable functional group and a curing catalyst. Further, the present invention provides a two-component sealing for SSG construction method comprising a first component containing a vinyl polymer (I) having at least one crosslinkable functional group and a second component containing a curing agent and a curing catalyst as essential components. It is also a material. Further, the present invention provides an SSG using a sealing material containing a vinyl polymer (I) having at least one crosslinkable functional group.
It is also a construction method. Hereinafter, the present invention will be described in detail.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is a sealing material for SSG construction, comprising a vinyl polymer (I) having at least one crosslinkable functional group. S of the present invention
The sealing material for the SG construction method is a conventional silicone SSG
It has the same properties (especially glass weather resistance) as the construction method sealing material and has no glass contamination.

<< Regarding 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 may be used. be able to. 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. It is preferably at most 1.7, more preferably at most 1.6,
It is more preferably at most 1.5, particularly preferably at most 1.4, most preferably at most 1.3.
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, and more preferably 1000 to 100,000.

<Effect of Main Chain on Weather Resistance> The sealing material comprising the vinyl polymer (I) of the present invention is compared with a sealing material comprising a conventional rubber polymer such as an oxyalkylene polymer. As a result, the weather resistance and the weather resistance of the glass are significantly improved. <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.

[0016]Controlled radical polymerization  In the radical polymerization method, an azo compound is used as a polymerization initiator.
Using an oxide or the like, a monomer having a specific functional group
"General Radiation" which simply copolymerizes with vinyl monomers
Cal polymerization method, and specific government
"Controlled radical polymerization method" capable of introducing functional groups
Can be classified. "General radical polymerization method" is a simple method
However, in this method, a monomer having a specific functional group is used.
Is introduced into the polymer only stochastically, so the functionalization rate
When trying to obtain a polymer with high
It is necessary to use a considerably large amount.
When the percentage of polymers in which certain functional groups are not introduced increases
There is a problem. It is also a free radical polymerization
Only high-viscosity polymers with a wide molecular weight distribution
There is also a problem.

The "controlled radical polymerization method" further includes a "chain transfer agent method" in which a vinyl polymer having a functional group at a terminal is obtained by performing polymerization using a chain transfer agent having a specific functional group. It can be classified as a "living radical polymerization method" in which a polymer having a molecular weight almost as designed can be obtained by growing a polymerized growth terminal without causing a termination reaction or the like. The “chain transfer agent method” can obtain a polymer having a high functionalization rate, but requires a considerably large amount of a chain transfer agent having a specific functional group with respect to the initiator, and includes a process. There is an economic problem. 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 '' has a narrow molecular weight distribution and can obtain a polymer having a low viscosity, and can introduce a monomer having a specific functional group into almost any position of the polymer, It is more preferable as a method for producing the vinyl polymer having the specific functional group. In the narrow sense, living polymerization refers to polymerization in which a terminal always has activity and a molecular chain grows, but in general, one in which a terminal is inactivated and one in which a terminal is activated are generally used. Pseudo-living polymerization that grows in an equilibrium state is also included. The definition in the present invention is also the latter.

Various groups have been actively studying the "living radical polymerization method" 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 by 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, '' a vinyl-based polymer having a specific functional group 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,
There is no particular limitation on which of these living radical polymerization methods to use, but an atom transfer radical polymerization method is preferred.

In the following, living radical polymerization will be described in detail. Before that, one of the controlled radical polymerizations which can be used for the production of the polymer (I) described later, a chain transfer agent is used. 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,
1-2271306, Japanese Patent No. 2594402,
In this method, a hydroxyl-terminated polymer is obtained by using a hydroxyl group-containing mercaptan or a hydroxyl group-containing polysulfide as a chain transfer agent as disclosed in JP-A-54-47782.

Hereinafter, the living radical polymerization will be described. First, a method using a radical scavenger such as a nitroxide compound will be described. In this polymerization, generally stable nitroxy free radicals (= 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 2,2,
Preference is given to nitroxy free radicals from cyclic hydroxyamines, such as 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-iso Indolinyloxy 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 preferred. Examples of the peroxide include, but are not limited to, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide; dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide; diisopropyl peroxydicarbonate; 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. Macromolecule
s, 1995, 28, 2993, an alkoxyamine compound as shown below may be used as an initiator instead of using a radical capping agent and a radical generator together.

[0025]

Embedded image

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

[0027]Atom transfer radical polymerization  Next, more preferable as the living radical polymerization of the present invention.
The atom transfer radical polymerization method will be described. This atom
In transfer radical polymerization, organic halides, especially reactive
Having high carbon-halogen bond content
(For example, a carbonyl compound having a halogen at the α-position
Or a compound having a halogen at the benzyl position), or
Sulfonyl halide compounds are used as initiators
You.

As a specific example, C₆H₅-CH
₂X, C₆H₅-C (H) (X) CH₃, C₆H₅-C
(X) (CH₃)₂  (Where C₆H₅Is a phenyl group, X is chlorine, bromine, and
Is iodine) R¹-C (H) (X) -CO₂R², R¹-C (C
H₃) (X) -CO₂R², R¹-C (H) (X) -C
(O) R², R¹-C (CH₃) (X) -C (O)
R ², Where R¹, R²Is a hydrogen atom or a group having 1 to 20 carbon atoms
An alkyl group, an aryl group, or an aralkyl group, and X is a salt
Element, bromine or iodine) R¹-C₆H₄-SO₂X (where R¹Is a hydrogen atom or an alkyl having 1 to 20 carbon atoms
X, chlorine, odor,
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 represented by the following 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;
X 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, pentyl group, hexyl group and the like. R ⁴ and R ⁵ may be linked at the other end to form a cyclic skeleton. Specific examples of the organic halide having an alkenyl group represented by the general formula 1 include XCH ₂ C (O) O (CH ₂ ) _n CH ＝ CH ₂ , H ₃ C
C (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 (CH ₂ ) _n C
H = CH ₂ ,

[0031]

Embedded image

(In each of the above formulas, X represents chlorine, bromine,
Or iodine, n is an integer of 0 to 20) XCH ₂ C (O) O (CH ₂ ) _n O (CH ₂ ) _m CH =
_{CH 2, H 3 CC (H} ) (X) C (O) O (CH 2) n
O (CH ₂ ) _m CH = CH ₂ , (H ₃ C) ₂ C (X) C
(O) O (CH ₂ ) _n O (CH ₂ ) _m CH = CH ₂ , C
_{H 3 CH 2 C (H)} (X) C (O) O (CH 2) n O
(CH ₂ ) _m CH = CH ₂ ,

[0033]

Embedded image

(In each of the above formulas, X represents chlorine, bromine,
Or iodine, n represents an integer of 1 to 20, m is an integer of _{0~20) o, m, p-} XCH 2 -C 6 H 4 - (CH 2) n -CH
_{= CH 2, o, m,} p-CH 3 C (H) (X) -C 6 H
_{4 - (CH 2) n -CH} = CH 2, o, m, p-CH 3
_{CH 2 C (H) (X} ) -C 6 H 4 - (CH 2) n -CH
ＣＨCH ₂ , wherein X is chlorine, bromine or iodine, and n is an integer of 0 to 20. o, m, p-XCH ₂ —C ₆ H ₄ — (CH ₂ ) _n —O—
_{(CH 2) m -CH = CH} 2, o, m, p-CH 3 C
_{(H) (X) -C 6} H 4 - (CH 2) n -O- (C
_{H 2) m -CH = CH 2} , o, m, p-CH 3 CH 2 C
_{(H) (X) -C 6} H 4 - (CH 2) n -O- (C
H ₂ ) _m CH = CH ₂ , wherein X is chlorine, bromine or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20. o, m, p-XCH ₂ − _{C 6 H 4 -O- (CH 2} ) n -
_{CH = CH 2, o, m} , p-CH 3 C (H) (X) -C
_{6 H 4 -O- (CH 2)} n -CH = CH 2, o, m, p
_{-CH 3 CH 2 C (H)} (X) -C 6 H 4 -O- (CH
_{2) n -CH = CH 2,} ( in each formula above, X is chlorine, bromine or iodine, n represents 0 to 20 _{integer) o, m, p-XCH} 2 -C 6 H 4 -O-, ( CH ₂ ) _n −
_{O- (CH 2) m -CH =} CH 2, o, m, p-CH 3
_{C (H) (X) -C} 6 H 4 -O- (CH 2) n -O-
_{(CH 2) m -CH = CH} 2, o, m, p-CH 3 CH
_{2 C (H) (X)} -C 6 H 4 -O- (CH 2) n -O-
(CH ₂ ) _m —CH ＝ CH ₂ , wherein X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20.

The organic halide having an alkenyl group further includes a compound represented by the general formula 2. _{^{H 2 C = C (R 3}} ) -R 7 -C (R 4) (X) -R 8 -R 5 (2) ( ^{wherein, R 3, R 4, R} 5, R 7, X in the above Same, R
⁸ is a direct bond, -C (O) O- (ester group), -C
(O)-(keto group) or o-, m-, p-phenylene group) R ⁶ is a direct bond or a divalent organic group having 1 to 20 carbon atoms (one or more ether bonds May be included), but in the case of a direct bond, a vinyl group is bonded to the carbon to which the halogen is bonded, and the compound is a halogenated allylic compound. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, C (O) O is used as R ^8.
It is not always necessary to have a group or a phenylene group, and a direct bond may be used. When R ⁷ is not a direct bond, R ⁸ may be C to activate a carbon-halogen bond.
(O) O group, C (O) group and phenylene group are preferred.

If the compound of the general formula 2 is specifically exemplified,
If CH₂= CHCH₂X, CH₂= C (CH₃) CH
₂X, CH₂= CHC (H) (X) CH₃, CH₂= C
(CH₃) C (H) (X) CH₃, CH₂= CHC
(X) (CH₃)₂, CH₂= CHC (H) (X) C₂
H₅, CH₂= CHC (H) (X) CH (CH₃)₂,
CH₂= CHC (H) (X) C₆H₅, CH₂= CHC
(H) (X) CH₂C₆H₅, CH₂= CHCH₂C
(H) (X) -CO₂R, CH₂= CH (CH₂)₂C
(H) (X) -CO₂R, CH₂= CH (CH ₂)₃C
(H) (X) -CO₂R, CH₂= CH (CH₂)₈C
(H) (X) -CO₂R, CH₂= CHCH₂C (H)
(X) -C₆H₅, CH₂= CH (CH ₂)₂C (H)
(X) -C₆H₅, CH₂= CH (CH₂)₃C (H)
(X) -C₆H₅(In the above formulas, X represents chlorine, bromine, or iodine.
And R represents an alkyl group having 1 to 20 carbon atoms, an aryl group,
Aralkyl group) and the like. Alkenyl group
Do not give specific examples of the sulfonyl halide compounds having
O-, m-, p-CH₂= CH- (CH₂)_n-C₆H
₄-SO₂X, o-, m-, p-CH₂= CH- (CH
₂)_n-OC₆H₄-SO₂X, (In each of the above formulas, X is chlorine, bromine, or iodine.
And n is an integer of 0 to 20).

The organic halide having a crosslinkable silyl group is not particularly limited, and examples thereof include those having a structure represented by the following general formula 3. ^{R 4 R 5 C (X)} -R 6 -R 7 -C (H) (R 3) CH 2 - [Si (R 9) 2- b (Y) b O] m -Si (R 10) 3- _a (Y) _a (3) (wherein, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and X are the same as above, and R ⁹ and R ¹⁰ are all alkyl groups having 1 to 20 carbon atoms. , An aryl group, an aralkyl group, or (R ′) ₃ S
a triorganosiloxy group represented by iO- (R 'is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different); , R
When two or more ⁹ or R ¹⁰ are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Ys are present, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2.
Is shown. m is an integer of 0-19. However, a + mb
Satisfies ≧ 1)

If the compound of the general formula 3 is specifically exemplified,
XCH₂C (O) O (CH₂)_nSi (OCH₃)₃,
CH₃C (H) (X) C (O) O (CH₂)_nSi (O
CH₃)₃, (CH₃)₂C (X) C (O) O (C
H₂)_nSi (OCH₃)₃, XCH₂C (O) O (C
H₂)_nSi (CH₃) (OCH₃)₂, CH₃C
(H) (X) C (O) O (CH₂)_nSi (CH₃)
(OCH₃)₂, (CH₃)₂C (X) C (O) O (C
H₂)_nSi (CH₃) (OCH₃)₂(In each of the above formulas, X is chlorine, bromine, iodine, and n is
An integer from 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)_m-Si (CH₃)
(OCH₃)₂, (H₃C)₂C (X) C (O) O (C
H₂)_nO (CH₂)_m-Si (CH₃) (OCH₃)
₂, CH₃CH₂C (H) (X) C (O) O (CH₂)
_nO (CH₂)_m-Si (CH₃) (OCH₃)₂(In each of the above formulas, X is chlorine, bromine, iodine, and n is
An integer of 1 to 20, m is an integer of 0 to 20)

O, m, p-XCH₂-C₆H₄− (CH
₂)₂Si (OCH₃)₃, O, m, p-CH₃C
(H) (X) -C₆H₄− (CH₂)₂Si (OC
H₃)₃, O, m, p-CH₃CH₂C (H) (X)-
C₆H₄− (CH₂)₂Si (OCH₃)₃, O, m,
p-XCH₂-C₆H₄− (CH₂)₃Si (OC
H₃)₃, O, m, p-CH₃C (H) (X) -C₆H
₄− (CH₂)₃Si (OCH₃)₃, O, m, p-C
H₃CH₂C (H) (X) -C₆H₄− (CH₂)₃S
i (OCH₃)₃, O, m, p-XCH₂-C₆H₄−
(CH₂)₂-O- (CH₂) ₃Si (OCH₃)₃,
o, m, p-CH₃C (H) (X) -C₆H₄− (CH
₂)₂-O- (CH₂)₃Si (OCH₃)₃, O,
m, p-CH₃CH₂C (H) (X) -C₆H₄− (C
H₂)₂-O- (CH₂)₃Si (OCH₃)₃, O,
m, p-XCH₂-C₆H₄-O- (CH₂)₃Si
(OCH₃)₃, O, m, p-CH₃C (H) (X)-
C₆H₄-O- (CH₂)₃Si (OCH₃) ₃, O,
m, p-CH₃CH₂C (H) (X) -C₆H₄-O-
(CH₂)₃-Si (OCH₃)₃, O, m, p-XC
H₂-C₆H₄-O- (CH₂)₂-O- (CH₂)₃
-Si (OCH₃)₃, O, m, p-CH₃C (H)
(X) -C ₆H₄-O- (CH₂)₂-O- (CH₂)
₃Si (OCH₃)₃, O, m, p-CH₃CH₂C
(H) (X) -C₆H₄-O- (CH₂)₂-O- (C
H₂) ₃Si (OCH₃)₃(In the above formulas, X represents chlorine, bromine, or iodine.
Element) and the like.

Organic halogen having crosslinkable silyl group
The compound further has a structure represented by the general formula 4.
Are exemplified. (R¹⁰)_3-a(Y)_aSi- [OSi (R⁹)_2-b(Y)_b]_m-CH₂ -C (H) (R³) -R⁷-C (R⁴) (X) -R⁸-R⁵ (4) (where R³, R⁴, R⁵, R⁷, R⁸, R⁹,
R¹⁰, A, b, m, X, and Y are the same as described above.₃O)₃SiCH₂CH₂C (H) (X) C₆H
₅, (CH₃O)₂(CH₃) SiCH₂CH₂C
(H) (X) C₆H₅, (CH₃O)₃Si (CH₂)
₂C (H) (X) -CO₂R, (CH₃O)₂(C
H₃) Si (CH₂)₂C (H) (X) -CO₂R,
(CH₃O)₃Si (CH₂)₃C (H) (X) -CO
₂R, (CH₃O)₂(CH₃) Si (CH₂)₃C
(H) (X) -CO₂R, (CH₃O)₃Si (C
H₂)₄C (H) (X) -CO₂R, (CH₃O)
₂(CH₃) Si (CH₂)₄C (H) (X) -CO₂
R, (CH₃O)₃Si (CH₂)₉C (H) (X)-
CO₂R, (CH₃O)₂(CH₃) Si (CH₂)₉
C (H) (X) -CO₂R, (CH₃O)₃Si (CH
₂)₃C (H) (X) -C₆H₅, (CH₃O)₂(C
H₃) Si (CH₂)₃C (H) (X) -C ₆H₅,
(CH₃O)₃Si (CH₂)₄C (H) (X) -C₆
H₅, (CH₃O)₂(CH₃) Si (CH₂)₄C
(H) (X) -C₆H₅(In the above formulas, X represents chlorine, bromine, or iodine.
And R represents an alkyl group having 1 to 20 carbon atoms, an 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) n} -OC (O) C (H) (R)
(X) (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,
(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.

[0042]

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(In each of the above formulas, X represents chlorine, bromine,
Or iodine and R are 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 growing terminal structures in one molecule. Preferably, an organic halide having two or more starting points or a sulfonyl halide compound is used as the initiator. To give a concrete example,

[0044]

Embedded image

[0045]

Embedded image

And the like. There are no particular restrictions on the vinyl monomer used in this polymerization, 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 a group 7, 8, 9 or 10 of the periodic table.
A metal complex complex having a Group 11 or Group 11 element as a central metal. More preferred are zero-valent copper, monovalent copper,
Examples thereof include complexes of divalent ruthenium, divalent iron, and divalent nickel. Among them, a copper complex is preferable. Specific examples of the monovalent copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide,
Cuprous perchlorate and the like. 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. Also, 2
Tristriphenylphosphine complex of trivalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, aluminum alkoxides are added as an activator.
Further, bistriphenylphosphine complex of divalent iron (F
eCl ₂ (PPh ₃ ) ₂ , a bistriphenylphosphine complex of divalent nickel (NiCl ₂ (PP
h 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 50.degree.
１５０150 ° C.

<Functional group> Crosslinkability of vinyl polymer (I)
Examples of the functional group include, but are not limited to, a crosslinkable silyl group,
Alkenyl group, hydroxyl group, amino group, polymerizable carbon-carbon
A group having a double bond, an epoxy group and the like are preferable. these
All crosslinkable functional groups can be used properly according to their use / purpose
be able to.Location of crosslinkable functional group  The cured product of the sealing material for SSG construction of the present invention
Significant effect on rubber elasticity when properties are particularly required
The molecular weight between cross-linking points that gives
Preferably, at least one of the functional groups is at the end of the molecular chain.
New More preferably, all crosslinkable functional groups are at the end of the molecular chain.
At the 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.

[0050]Crosslinkable silyl group  The crosslinkable silyl group of the present invention has the general formula 5:-[Si (R⁹)_2-b(Y)_bO]_m-Si (R¹⁰)_3-a(Y)_a (5) 中 where R⁹, R¹⁰Are all those having 1 to 20 carbon atoms.
Alkyl group, aryl group having 6 to 20 carbon atoms, 7 to 2 carbon atoms
An aralkyl group of 0, or (R ′)₃SiO- (R 'is
A monovalent hydrocarbon group having 1 to 20 carbon atoms,
R 'may be the same or different.
A triorganosiloxy group represented by⁹Or R
¹⁰When two or more are present, even if they are the same
Well, they can be different. Y is hydroxyl group or hydrolysis
And when Y is two or more, they are the same
May be present or different. a is 0, 1, 2,
Or 3 and b represents 0, 1, or 2. m is
It is an integer of 0 to 19. However, a + mb ≧ 1
Is satisfied. Group represented by｝
You.

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 a 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, the general formula _{^{6 -Si (R 10) 3-}} a (Y) a (6) ( ^{wherein, R} 10, Y, a is the same. As above) is crosslinkable silyl group represented by readily available Is preferred.

[0052]Alkenyl group  The alkenyl group in the present invention is not limited,
It is preferably represented by the general formula 7. H₂C = C (R¹¹)-(7) (wherein, R¹¹Is a hydrogen atom or a carbon having 1 to 20 carbon atoms
In general formula 7, R¹¹Is a hydrogen atom or carbon number 1
To 20 hydrocarbon groups, specifically the following groups
Is exemplified. − (CH₂)_n-CH₃, -CH (CH₃)-(C
H₂)_n-CH₃, -CH (CH₂CH₃)-(C
H₂)_n-CH₃, -CH (CH₂CH₃)₂, -C
(CH₃)₂− (CH₂)_n-CH₃, -C (CH₃)
(CH₂CH₃)-(CH₂)_n-CH₃, -C
₆H₅, -C₆H₅(CH₃), -C₆H₅(CH₃)
₂,-(CH₂)_n-C₆H₅,-(CH₂)_n-C₆
H₅(CH₃),-(CH₂)_n-C₆H₅(CH₃)
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 bonding form of the alkenyl group and the main chain of the polymer is not particularly limited, but may be a carbon-carbon bond, an ester bond, an ester bond, a carbonate bond,
It is preferable that they are bonded via an amide bond, a urethane bond, or the like.

[0054]Amino group  Although the amino group in the present invention is not limited,¹² ₂  (R¹²Is hydrogen or a monovalent organic group having 1 to 20 carbon atoms
There are two R¹²Are the same or different
And interconnected at the other end to form a ring structure
It may be formed. ), But-(NR¹² ₃)⁺X⁻  (R¹²Is the same as above. X⁻Is a counter anion. )
There is no problem with ammonium salts. The above formula
Medium, R¹²Is hydrogen or a monovalent organic group having 1 to 20 carbon atoms
For example, hydrogen, an alkyl group having 1 to 20 carbon atoms,
C6-20 aryl group, C7-20 aral
And a kill group. Two R¹²Are the same as each other
Well, they can be different. Also, at the other end,
They may be connected to form a ring structure.

[0055]Group having a polymerizable carbon-carbon double bond  A group having a polymerizable carbon-carbon double bond is preferably
Is represented by the general formula 8: —OC (O) C (R¹³) = CH₂ (8) (where R¹³Is hydrogen or monovalent having 1 to 20 carbon atoms
Represents an organic group. ), More preferably
Is R¹³Is a group that is hydrogen or a methyl group
You. In the general formula 8, R¹³Specific examples of
Not specified, for example, -H, -CH₃, -CH₂CH₃,
− (CH₂)_nCH₃(N represents an integer of 2 to 19),
-C₆H₅, -CH₂OH, -CN and the like,
Preferably -H, -CH₃It is.

<Method for Introducing Functional Group> The method for introducing a functional group into the vinyl polymer (I) of the present invention will be described below.
It is not limited to this. First, a method for introducing a crosslinkable silyl group, alkenyl group, and hydroxyl group by terminal functional group conversion will be described. Since these functional groups can be precursors to each other, they are described in the order starting from the crosslinkable silyl group.

As a method for synthesizing a vinyl polymer having at least one crosslinkable silyl group, (A) a hydrosilane compound having a crosslinkable silyl group in a vinyl polymer having at least one alkenyl group may be used as a hydrosilylation catalyst. (B) adding at least one hydroxyl group in the presence of
A method in which a compound having a crosslinkable silyl group and a group capable of reacting with a hydroxyl group such as an isocyanate group in one molecule is reacted with a vinyl polymer having one compound, and (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, and (D) using a chain transfer agent having a crosslinkable silyl group when synthesizing a vinyl polymer by radical polymerization. And (E) a method in which a vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a compound having a crosslinkable silyl group and a stable carbanion in one molecule.

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 a vinyl polymer is synthesized by radical polymerization, for example, a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule as shown in the following general formula 9 may be used. A method of reacting as monomer 2. _{^{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 o-, m-, p-phenylene group, and R ¹⁶ is a direct bond,
Represents a valent organic group, and may contain one or more ether bonds. R ¹⁷ is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or 7 to
In addition, there is no limitation on the time when a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule is reacted, but a rubbery property is expected particularly 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 completion of the reaction of a predetermined monomer.

(Ab) When a vinyl 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 metal compounds having an alkenyl group such as an organic tin such as allyltributyltin and allyltrioctyltin are added to a vinyl polymer having at least one highly reactive carbon-halogen bond. A method of substituting halogen by reacting.

(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 carbon atom 1
Represents an alkyl group of 10 to 10 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, those having a -C (O) R and -CN structure 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 having an alkenyl group or a carboxy group 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, same ^{.R 21} to R 17, ^{M +} is above 1 -C
H ₂ C = C (R ¹⁷ ) -R ²² -C (O) O ^- M ⁺ (12) wherein the divalent organic group may have one or more ether bonds. R ¹⁷ and M ⁺ are the same as described above, and R ²² is a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds.

The 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. Further, the vinyl polymer having at least one alkenyl group can be obtained from a vinyl polymer having at least one hydroxyl group, and the methods exemplified below can be used, but the invention is not limited thereto. (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 a living radical polymerization method. Is preferred. The method (Ab) is more preferable because the control is easier. When an alkenyl group is introduced by converting a halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halide having at least one highly reactive carbon-halogen bond, or A vinyl polymer having at least one highly reactive carbon-halogen bond at a terminal obtained by radical polymerization of a vinyl monomer (atom transfer radical polymerization) using a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst. It is preferred to use coalescence. 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 one 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, R 10} are both carbons 1 Alkyl group having 20 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, 7 to 2 carbon atoms
An aralkyl group of 0, or (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′s may be the same or different. A) a triorganosiloxy group represented by R ⁹ or R ^9
When two or more ¹⁰ are present, 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 an integer of 0-19. However, it is assumed that a + mb ≧ 1 is satisfied. ｝

Among these hydrosilane compounds, particularly, a crosslinkable compound 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 described above) Compounds having a group are preferred in that they are easily available.

When a hydrosilane compound having a crosslinkable silyl group is added 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 , RhCl
₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlC
_{l 3, PdCl 2 · H 2} O, NiCl 2, TiCl 4 , and the like.

The method for producing a vinyl polymer having at least one hydroxyl group used in the methods (B) and (Ag) to (Aj) is 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 is reacted as a second monomer. How to let. 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) A polymerizable alkenyl group and a hydroxyl group 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 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) A method of radically polymerizing a vinyl monomer using a large amount of a hydroxyl group-containing chain transfer agent such as a hydroxyl group-containing polysulfide disclosed in JP-A-5-262808. (Bd) For example, JP-A-6-239912, JP-A-8-
A method of radically polymerizing a vinyl monomer using hydrogen peroxide or a hydroxyl group-containing initiator as shown in 283310. (Be) A method in which a vinyl monomer is radically polymerized using an excess of alcohols as described in, for example, JP-A-6-11612.

(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 method in which a vinyl-based polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having a hydroxyl group as shown in the general formula 16 to substitute 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,-
Those having the structures of C (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, an oxyanion or a carboxylate anion having a hydroxyl group as shown in the general formula 17 or 18 to form a halogen. How to replace. ^{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 synthesizing a vinyl polymer by living radical polymerization, at the end of the polymerization reaction or after the completion of the reaction of a predetermined monomer, an alkenyl having a low polymerizability in one molecule is used as a second monomer. A method of reacting a compound having a group and a hydroxyl group. Such a 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.

In the present invention, when a halogen is not directly involved in the 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 or a sulfonyl halide compound is used as an initiator, and a transition metal complex is used as a catalyst. It is preferable to use a vinyl polymer having at least one highly reactive carbon-halogen bond at a terminal obtained by radical polymerization of a vinyl monomer (atom transfer radical polymerization method). 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 can be mentioned, and if necessary, a generally known catalyst for a urethane-forming 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 Where R ⁹ , R ¹⁰ , R ¹⁴ , R ¹⁵ , Y, a, b,
m is the same as above. R ²³ is a direct bond or a group having 1 carbon atom.
The divalent organic group of -20 may contain one or more ether bonds. The timing of reacting a compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule is not particularly limited. However, particularly in the case of living radical polymerization, where rubber-like properties are expected, the end of the polymerization reaction or After completion of the reaction of the predetermined monomer, it is preferable to react as a second 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. The method for synthesizing the vinyl polymer having at least one highly reactive carbon-halogen bond, which is used in the method (E), uses the above-described organic halide or the like as an initiator and prepares a transition metal complex. Examples include, but are not limited to, atom transfer radical polymerization using 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,
m is the same as above. R ^{2 4} is a direct bond or a carbon number 1
R ²⁵ may be hydrogen, or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a C 7 to C 10 bivalent organic group which may contain one or more ether bonds. And 10 aralkyl groups. ) As the electron-withdrawing groups for R ¹⁸ and R ¹⁹ , -CO ₂ R,-
Those having the structures of C (O) R and -CN are particularly preferred.

[0077]Epoxy group  In the present invention, a vinyl-based polymer having a reactive functional group at its terminal
The coalescence is not limited, but includes the following steps: (1) A vinyl monomer is prepared by a living radical polymerization method.
(2) Then, the reactive functional group and the ethylenically unsaturated group are combined.
And reacting the compound with the compound. In addition, in atom transfer radical polymerization,
Alcohol and then react with hydroxyl and halogen
And a method of epoxy cyclization.

[0078]Amino group  Vinyl-based heavy having at least one amino group at the terminal of the main chain
The following steps may be mentioned as a method for producing the union.
You. (1) Bis having at least one halogen group at the terminal of the main chain
And (2) converting the terminal halogen to an amino
Conversion to a substituent having an amino group using a group-containing compound
You. The substituent having an amino group is not particularly limited.
However, a group represented by the general formula 22 is exemplified. -OR²⁶-NR¹² ₂ (22) (wherein, R²⁶Represents one or more ether linkages or
Divalent organic having 1 to 20 carbon atoms which may contain
Represents a group. R¹²Is hydrogen or a monovalent of 1 to 20 carbon atoms
An organic group, two R¹²May be the same or different
May be connected to each other at the other end to form a ring.
May be formed. )

In the above general formula 22, R ²⁶ is a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds or ester bonds.
20 alkylene group, an arylene group having 6 to 20 carbon atoms, but like an aralkylene group having 7 to 20 carbon ^{_{atoms, -C 6 H 4 -R 27 -}} ( _wherein, C 6 _{H 4} is a phenylene group, R ²⁷ represents a direct bond or a divalent organic group having 1 to 14 carbon atoms which may contain one or more ether bonds or ester bonds.)
Or —C (O) —R ²⁸ — (wherein R ²⁸ has a carbon number of 1 to 1 which may include a direct bond or one or more ether bonds or ester bonds.
9 represents a divalent organic group. Is preferred.

By converting the terminal halogen of the vinyl polymer, an amino group can be introduced into the terminal of the polymer. The substitution method is not particularly limited, but a nucleophilic substitution reaction using an amino group-containing compound as a nucleophile is preferable in that the reaction is easily controlled. Examples of such a nucleophilic agent include a compound having both a hydroxyl group and an amino group represented by the general formula 23. 12 2 (23) (wherein ^{HO-R 26 _-NR,} R ²⁶ is, ^{.R 12} representing one or more ether bond or a divalent organic group having carbon atoms which may contain 1 to 20 ester bond Is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and 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. May be.)

In the above general formula 23, R²⁶Is one or more
It may contain the above ether bond or ester bond
A divalent organic group having 1 to 20 carbon atoms, for example, having 1 carbon atom
-20 alkylene groups, arylenes having 6-20 carbon atoms
And aralkylene groups having 7 to 20 carbon atoms.
You. Among these compounds having both hydroxyl and amino groups
And R ²⁶Is -C₆H₄-R²⁷− (Where C₆H₄Is a phenylene group, R²⁷Is a direct join
Or contains one or more ether or ester bonds
Which may represent a divalent organic group having 1 to 14 carbon atoms)
Aminophenols represented; -C (O) -R²⁸-Where R²⁸Is a direct bond or one or more ethers
1 to 1 carbon atoms which may contain a bond or an ester bond
9 represents a divalent organic group).
Good. As a specific compound, for example, ethanol
O, m, p-aminophenol; o, m, p-NH
₂-C₆H₄-CO₂H; glycine, alanine, amino
Butanoic acid and the like.

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, and 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. 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 of the aminophenols represented by the general formula 26 are preferable 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 having 1 to 19 carbon atoms, which may include: R ¹² is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and two R ¹² may be the same as or different from each other And may be connected to each other at the other end to form a cyclic structure. M ⁺ is the same as described above.)

Compounds having an oxyanion represented by any one of formulas 24 to 26 can be easily obtained by reacting a compound represented by formula 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, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, methyllithium, ethyllithium, n-butyllithium, tert- Butyllithium, lithium diisopropylamide, lithium hexamethyldisilazide and the like. The amount of the base used is
Although not particularly limited, it is 0.5 to 5 equivalents, preferably 0.8 to 1.2 equivalents, based on the precursor. As a solvent used when reacting the above precursor and the above base,
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; Alcohol solvents such as 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, propylene Carbonate solvents such as 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 wherein M ⁺ is a quaternary ammonium ion can be obtained by preparing a compound wherein 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 temperature can be from 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.

For accelerating 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-containing compound with an appropriate substituent. Examples of such a substituent include a benzyloxycarbonyl group, a tert-butoxycarbonyl group, and a 9-fluorenylmethoxycarbonyl group. Further, a method of substituting a halogen terminal of a vinyl polymer with an azide anion and then reducing the same with LAH or the like may be used.

[0088]Polymerizable carbon-carbon double bond  A polymerizable carbon-carbon double bond is added to the polymer (I) of the present invention.
The method of introduction is not limited, but is as follows:
Methods. The halogen group of the vinyl polymer is replaced with a radical polymerizable carbon.
By substitution with a compound having a carbon-carbon double bond
How to make. A specific example is represented by general formula 27.
A vinyl polymer having a structure represented by general formula 28:
Method by reaction with a compound. -CR²⁹R³⁰X (27) (wherein, R²⁹, R³⁰Is the vinyl monomer
Group bonded to an unsaturated group. X is chlorine, bromine, or
Represents iodine. ) M⁺-OC (O) C (R¹³) = CH₂ (28) (wherein, R¹³Is hydrogen or organic having 1 to 20 carbon atoms
Represents a group. M⁺Is an alkali metal or quaternary ammonium
Mion. )

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 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
By reacting with a compound represented by the formula: HO-R ³¹ -OC (O) C (R ¹³ ) = CH ₂ (30) (wherein, R ¹³ represents hydrogen or an organic group having 1 to 20 carbon atoms. R ³¹ has 2 to 20 carbon atoms. Represents a divalent organic group.)

Hereinafter, each of these methods will be described in detail. 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. —CR ²⁹ R ³⁰ X (27) (wherein, R ²⁹ and R ³⁰ are groups bonded to an ethylenically unsaturated group of a vinyl monomer. X is chlorine, bromine, or
Represents iodine. ) M ⁺ -OC (O) C (R ¹³ ) = CH ₂ (28) (wherein, R ¹³ represents hydrogen or an organic group having 1 to 20 carbon atoms. M ⁺ represents an alkali metal or a quaternary. Represents ammonium ion.)

The vinyl polymer having a terminal structure represented by the general formula 27 can be obtained 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 ,
It is produced by a method of polymerizing a vinyl monomer using a halogen compound as a chain transfer agent, but the former is preferred.

[0092] Examples of the compound represented by the general formula 28 is not particularly limited, specific examples of R ¹³ include -
_{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., preferably -H, -CH
₃ . M ⁺ is a counter cation of the oxyanion;
Examples of the type 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 use amount of the oxyanion of the general formula 28 is preferably 1 to 5 equivalents, more preferably 1.0 to 5 equivalents to the halogen group of the general formula 27.
1.2 equivalents. The solvent for carrying out this reaction is not particularly limited, but a polar solvent is preferred because it is a nucleophilic substitution reaction. Triamide, acetonitrile,
Are used. The temperature at which the reaction is carried out is not limited, but is generally from 0 to 150 ° C, preferably from room temperature to 100 ° C in order to maintain the 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) (In the formula, R ¹³ represents hydrogen or an organic group having 1 to 20 carbon atoms. X represents chlorine, bromine, or a hydroxyl group.) is not particularly restricted but includes compounds represented by formula ^29, specific examples of ^{R 13} are, for example, -H, -C
_{H 3, -CH 2 CH 3,} - (CH 2) n CH 3 (n is 2
Represents an integer of _{~19), - C 6 H 5} , -CH 2 OH, -
CN, etc., and is preferably -H, -CH _3.

The vinyl polymer having a hydroxyl group at the terminal, preferably at the terminal, is obtained 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 of polymerizing a vinyl monomer 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) A method in which a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule represented by the following general formula 31 and the like is reacted as a second monomer when a vinyl polymer is synthesized by living radical polymerization. _{^{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.
³⁴ represents a direct bond or a divalent organic group having 1 to 20 carbon atoms which may have one or more ether bonds. R
^A compound in which ³³ is an ester group is a (meth) acrylate compound, and a compound in which R ³³ is a phenylene group is a styrene compound. The timing of reacting a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule is not limited, but particularly when rubbery properties are expected, after the end of the polymerization reaction or after the reaction of a predetermined monomer is completed. , As the second monomer.

(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. Such a 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 polymer with a hydroxyl group-containing compound. (D) General formula 27 obtained by atom transfer radical polymerization
A method in which a vinyl-based polymer having at least one carbon-halogen bond represented by the following formula is reacted with a stabilized carbanion having a hydroxyl group as shown in the general formula 33 to replace halogen. ^{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 withdrawing group or one electron withdrawing group .R ³⁶ and R ³⁷ represents an alkyl group or phenyl group the other is C1-10 hydrogen or carbon in the electron-withdrawing group,, -CO
₂ R (ester group), -C (O) R (keto group), -CO
N (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. R ³⁶ and R
³⁷ includes —CO ₂ R, —C (O) R, and —CN
Is particularly preferred. )

(E) A vinyl-based polymer having at least one carbon-halogen bond represented by the general formula 27 obtained by atom transfer radical polymerization is reacted with a simple metal such as zinc or an organometallic compound. A method in which an enolate anion is prepared and then reacted with an aldehyde or a ketone. (F) A vinyl-based polymer having at least one halogen at the terminal of the polymer, preferably a halogen represented by the general formula 27, is added to a hydroxyl-containing oxyanion represented by the following general formula 34 or the like or a general formula 35 represented by the following general formula 35 A method of reacting the hydroxyl group-containing carboxylate anion represented 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 described above.)

In the present invention, when a halogen is not directly involved in the method for introducing a hydroxyl group as in (a) and (b), the method (b) is more preferable because control is easier. When a hydroxyl group is introduced by converting a halogen of a vinyl polymer having at least one carbon-halogen bond as in (c) to (f), the control of (f) The method 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 represents hydrogen or an organic group having 1 to 20 carbon atoms. R ³¹ has 2 to 20 carbon atoms. It represents a divalent organic group.) the compound represented by the general formula 36 is not particularly limited, specific examples of R ¹³ are, for example, -H, -C
_{H 3, -CH 2 CH 3,} - (CH 2) n CH 3 (n is 2
Represents an integer of _{~19), - C 6 H 5} , -CH 2 OH, -
CN, etc., and is preferably -H, -CH _3. Specific compounds include 2-hydroxypropyl methacrylate. The vinyl polymer having a hydroxyl group at the terminal is as described above.

The diisocyanate compound is not particularly limited, and any conventionally known diisocyanate compound can be used. For example, 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. To take advantage of better weather resistance, for example,
It is preferable to use a diisocyanate compound having no aromatic ring, such as hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate.

<< SSG Construction Method Sealing Material >> Some of the SSG construction method sealing materials 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>For crosslinkable silyl groups  Polymers having a crosslinkable silyl group can be prepared by various known condensation methods.
Form siloxane bonds in the presence or absence of a catalyst
It crosslinks and cures when formed. As properties of cured product
Is rubbery depending on the molecular weight of the polymer and the main chain skeleton
From resin to resin.

Examples of such a condensation catalyst include dibutyltin dilaurate, dibutyltin phthalate, dibutyltin diacetate, dibutyltin bisacetylacetonate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethylmalate and dibutyltin. Tin diethyl malate, dibutyl tin dibutyl malate, dibutyl tin diisooctyl malate, dibutyl tin ditridecyl malate, dibutyl tin dibenzyl malate, dibutyl tin maleate, dioctyl tin diacetate, dioctyl tin distearate, dioctyl tin dilaurate, Tetravalent tin compounds such as dioctyltin diethyl malate, dioctyltin diisooctylmalate, dibutyltin dimethoxide, dibutyltin bisnonylphenoxide, dibutenyltin oxide; Divalent tin compounds such as tin lute, tin naphthenate and tin stearate; titanates such as tetrabutyl titanate and tetrapropyl titanate; aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum Organic aluminum compounds such as ethyl acetoacetate; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; lead octylate; butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanol Amine,
Diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine,
Diethylaminopropylamine, xylylenediamine,
Triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) Amine compounds such as undecene-7 (DBU), or salts of these amine compounds with carboxylic acids and the like; reaction of amine compounds such as a reaction product or a mixture of laurylamine and tin octylate with an organotin compound Products and mixtures; low molecular weight polyamide resin obtained from excess polyamine and polybasic acid; reaction product of excess polyamine and epoxy compound; γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropyl Silane coupling having an amino group such as methyldimethoxysilane And other known silanol condensation catalysts such as acidic catalysts and basic catalysts.

Among these catalysts, although not particularly limited, tetravalent tin compounds are preferable in order to enhance the stress relaxation of the cured product obtained by curing the sealing material for SSG construction. When a divalent tin compound such as a reaction product or a mixture of laurylamine and tin octylate is used alone, the restoration rate increases, and as a result, a large stress tends to remain after the application. These catalysts may be used alone or in combination of two or more. The amount of the condensation catalyst is preferably about 0.1 to 20 parts, and more preferably 1 to 10 parts based on 100 parts (parts by weight, hereinafter the same) of the vinyl polymer (I) having at least one crosslinkable silyl group. Is more preferred. 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, if 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,
The pot life becomes too short, which is not preferable from the viewpoint of workability.

In the sealing material for SSG construction of the present invention, in order to further enhance 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 Is each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.
A is 0, 1, 2, or 3. ), A silicon compound having no silanol group may be added.

The silicon compound is not limited, but may be any one of the following general formulas (1) such as phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and triphenylmethoxysilane. R ⁴⁹ is an aryl group having 6 to 20 carbon atoms,
This is preferable because 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 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.

[0108]For alkenyl groups  When crosslinking with an alkenyl group, there is no limitation.
However, a hydrosilyl group-containing compound is used as a curing agent,
Cross-linking by hydrosilylation reaction using silylation catalyst
Preferably. Hydrosilyl group-containing compound
Can be cured by crosslinking with a polymer having an alkenyl group.
There is no particular limitation as long as it is a hydrosilyl group-containing compound,
Various types can be used. For example, the general formula 38
Or a linear polysiloxane represented by 39; R⁵¹ ₃SiO- [Si (R⁵¹)₂O]_a− [Si (H) (R⁵²) O]_b-[Si (R⁵²) (R⁵³) O]_c-SiR⁵¹ ₃ (38) HR⁵¹ ₂SiO- [Si (R⁵¹)₂O]_a− [Si (H) (R⁵²) O]_b − [Si (R⁵²) (R⁵³) O]_c-SiR⁵¹ ₂H (39) (wherein, R⁵¹And R⁵²Is alkyl having 1 to 6 carbon atoms
Group or phenyl group, R⁵³Is a group having 1 to 10 carbon atoms.
Represents an alkyl group or an aralkyl group. a is 0 ≦ a ≦ 10
0, b satisfies 2 ≦ b ≦ 100, c satisfies 0 ≦ c ≦ 100
Indicates an integer. A) a cyclic siloxane represented by the general formula 40;

[0109]

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(Wherein R⁵⁴And R⁵⁵Has 1 to 1 carbon atoms
6, an alkyl group or a phenyl group, R⁵⁶Is the carbon number
1 to 10 alkyl groups or aralkyl groups. d is
0 ≦ d ≦ 8, e is 2 ≦ e ≦ 10, f is an integer of 0 ≦ f ≦ 8
And satisfies 3 ≦ d + e + f ≦ 10. ) Etc.
Compounds can be used. Even if these are used alone,
A mixture of more than one species may be used. These shiroki
View of compatibility with (meth) acrylic polymer even among sun
From the viewpoint, the following general formulas 41 and 42 having a phenyl group
Represented by the following general formulas 43 and 44:
Cyclic siloxanes are preferred. (CH₃)₃SiO- [Si (H) (CH₃) O]_g− [Si (C₆H₅)₂O]_h-Si (CH₃)₃ (41) (CH₃)₃SiO- [Si (H) (CH₃) O]_g− [Si (CH₃) ｛CH ₂ C (H) (R⁵⁷) C₆H₅｝ O]_h-Si (CH₃)₃ (42) (wherein, R⁵⁷Represents hydrogen or a methyl group. g is 2 ≦
g ≦ 100 and h indicate an integer of 0 ≦ h ≦ 100. C₆H
₅Represents a phenyl group. )

[0111]

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(Wherein, R ⁵⁷ represents hydrogen or a methyl group. I is 2 ≦ i ≦ 10, j is 0 ≦ j ≦ 8, and 3 ≦ i
An integer satisfying + j ≦ 10 is shown. 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 obtained by slowly dropping the above-mentioned alkenyl group-containing compound in the presence of a hydrosilylation catalyst, to an excess amount of the hydrosilyl group-containing compound represented by the above general formulas 38 to 44. . 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.

[0114]

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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. It is particularly preferred that it is 2.5 to 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 ,
RhCl ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , A
lCl 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 is preferably used in the range of 10 ^-1 to 10 ^-8 mol, preferably 10 ^-3 to 10 ^-6 mol, per 1 mol of the alkenyl group of the vinyl polymer (I).
It is good to use in the range of l. If the amount is less than 10 ⁻⁸ mol, the curing does not proceed sufficiently. Since the hydrosilylation catalyst is expensive, it is preferable not to use 10 ^-1 mol or more. The curing temperature is not particularly limited, but is generally 0 ° C.
The curing is preferably performed at a temperature of from 200C to 200C, preferably from 30C to 150C, and more preferably from 80C to 150C.

[0118]For hydroxyl group  The polymer having a hydroxyl group of the present invention can react with the hydroxyl group
Use of a compound having two or more functional groups as a curing agent
With this, it is cured uniformly. As specific examples of the curing agent,
For example, having two or more isocyanate groups in one molecule
Polyisocyanate compounds, methylolated melamine and
And their alkyl ethers or low condensation products
Minoplast resin, polyfunctional carboxylic acid and its halogen
And the like. Cure using these curing agents
When preparing the product, use an appropriate curing catalyst.
Can be

[0119]In the case of amino group  The polymer having an amino group of the present invention reacts with the amino group.
Using a compound having two or more functional groups as a curing agent
As a result, it is cured uniformly. As a specific example of a curing agent
Represents, for example, two or more isocyanate groups in one molecule.
Polyvalent isocyanate compound, methylolated melamine
And its alkyl ethers or low condensates
Aminoplast resins, polyfunctional carboxylic acids and their
And the like. Using these curing agents
When preparing a cured product, use an appropriate curing catalyst.
Can be used.

[0120]For epoxy group  As the curing agent for the polymer having an epoxy group of the present invention,
Although not limited to, for example, aliphatic amines, alicyclic
Mines, aromatic amines; acid anhydrides; polyamides;
Dazoles; amine imides; urea; melamine and its derivatives
Conductor; Polyamine salt; Phenolic resin; Polymercap
Tan, polysulfide; aromatic diazonium salt, diali
Luiodonium salt, triallylsulfonium salt, thoria
Light / ultraviolet curing agents such as rilselenium salts are used.
You.

[0121]In the case of a polymerizable carbon-carbon double bond  The polymer having a polymerizable carbon-carbon double bond is
Crosslinked by polymerization reaction of compatible carbon-carbon double bond
be able to. As a method of crosslinking, active energy rays
Curing with heat or curing with heat
It is. In active energy ray-curable compositions, light weight
The initiator is a photo-radical initiator or a photo-anion
Preferably it is an initiator. In thermosetting compositions
Means that the thermal polymerization initiator is an azo initiator, a peroxide,
And a redox initiator.
Is preferred. The details of these crosslinking reactions are described below.
explain about.

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.

[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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As the styrene monomer, styrene, α
-Methylstyrene and the like; acrylamide-based monomers include acrylamide and N, N-dimethylacrylamide; conjugated diene-based monomers include butadiene and isoprene; and vinylketone-based monomers include methylvinylketone and the like.

Examples of the polyfunctional monomers 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.

Examples of the oligomer include 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, polyol (polytetramethylene glycol, ethylene Polyester diol of 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, hexamethyl Diisocyanates, xylylene diisocyanates, etc.) to obtain hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and pentaerythritol triacrylate. Examples thereof include a urethane acrylate resin obtained by the reaction, a resin in which a (meth) acryl group is introduced into the above polyol via an ester bond, and a polyester acrylate resin.
These monomers and oligomers are selected according to the initiator and curing conditions used. Further, 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 the compatibility is good.

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. When 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

As the 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 addition amount of the photopolymerization initiator is not particularly limited because it is only necessary to slightly photofunctionalize the system.
It is preferably from 0.01 to 10 parts by weight.

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 for crosslinking a polymer having a polymerizable carbon-carbon double bond, heat is preferably used. In the case of 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 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 33), 2,2'-azobis (2-
Amidinopropane) dihydrochloride (VAZO 50), 2,
2'-azobis (2,4-dimethylvaleronitrile)
(VAZO 52), 2,2'-azobis (isobutyronitrile) (VAZO 64), 2,2'-azobis-
2-methylbutyronitrile (VAZO 67), 1,1
-Azobis (1-cyclohexanecarbonitrile) (V
AZO 88) (All DuPont Chemical
, 2,2'-azobis (2-cyclopropylpropionitrile), and 2,2'-azobis (methylisobutyrate) (V-601) (available from Wako Pure Chemical Industries, Ltd.). .

Suitable peroxide initiators include, but are not limited to, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di (4-t- Butylcyclohexyl) peroxydicarbonate (Perkadox)
16S) (available from Akzo Nobel), di (2-ethylhexyl) peroxydicarbonate, t
-Butyl peroxypivalate (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; Examples include systems based on tertiary amines, such as systems based on benzoyl peroxide and dimethylaniline; and systems based on organic hydroperoxides and transition metals, such as systems based on cumene hydroperoxide and cobalt naphthate. Other initiators include, but are not limited to, tetraphenyl 1,1,2,2-
Pinacol such as ethanediol is exemplified.

Preferred thermal radical initiators are selected from the group consisting of azo initiators and peroxide initiators. 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 an amount is not limited, but typically includes a polyacrylic group having at least one terminal acrylic functional group in the present invention. It is about 0.01 to 5 parts by weight, more preferably about 0.025 to 2 parts by weight, when the total amount of the combined monomer and oligomer mixture is 100 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, and the temperature varies depending on the type of the thermal initiator, the polymer (I), the compound to be added and the like. 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. When adding an adhesion-imparting agent, the joint width and the like fluctuate due to external force,
It is possible to further reduce the risk of the sealing material peeling off from the siding board. In some cases, the necessity of using a primer used for improving the adhesiveness is eliminated, and simplification of the work is expected. Specific examples of the silane coupling agent include isocyanate group-containing silanes such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatopropylmethyldimethoxysilane; γ
-Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2 -Aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane,
Amino group-containing silanes such as γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane Silanes containing a mercapto group such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxy Silane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Epoxy group-containing silanes such as riethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxy Carboxysilanes such as silanes; vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acroyloxypropylmethyltriethoxysilane; γ-chloro Halogen-containing silanes such as propyltrimethoxysilane; and isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate. Further, derivatives of these modified amino-modified silyl polymer, silylated amino polymer, unsaturated aminosilane complex, phenylamino long-chain alkylsilane, aminosilylated silicone,
Silylated polyesters and the like can also be used as the silane coupling agent.

The silane coupling agent used in the present invention is
Usually, 0.1 to 100 parts of the vinyl polymer (I) is used.
Used in the range of 20 parts. In particular, it is preferable to use it in the range of 0.5 to 10 parts. If too much is added, SSG
In some cases, the cured product obtained by curing the structural sealing material loses its rubber elasticity, and may not function as a sealing material. In addition, when adding to the two-component type mentioned later, it is preferable that the total amount added to both of the two components falls within the above range. The effect of the silane coupling agent added to the sealing material for SSG construction method of the present invention is as follows: various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, and mortar; When used for organic substrates such as polyethylene, polypropylene, polycarbonate, etc., a remarkable adhesive improvement effect is exhibited 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 limited, and include, for example, epoxy resins, phenol resins, sulfur, alkyl titanates, aromatic polyisocyanates and the like. The adhesiveness imparting agent is 1
They may be used alone or as a mixture of two or more. The addition of these adhesion-imparting agents can improve the adhesion to the adherend.

<Plasticizer> Various plasticizers are used in the sealing material for SSG construction according to the present invention, if necessary. The plasticizer is not particularly limited. For example, phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, and butyl benzyl phthalate; and dioctyl adipate for the purpose of adjusting physical properties and adjusting properties. 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, triethylene glycol dibenzoate, and pentane Esters of polyalkylene glycol such as erythritol ester; phosphates such as tricresyl phosphate and tributyl phosphate;
Trimellitic esters; polystyrene and poly-α-
Polystyrenes such as methylstyrene; polybutadiene;
Polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene; chlorinated paraffins; hydrocarbon-based oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils;
Polyether polyols such as polypropylene glycol and polytetramethylene glycol and polyethers such as derivatives obtained by converting hydroxyl groups of these polyether polyols into ester groups and ether groups; epoxidized soybean oil;
Epoxy plasticizers such as benzyl epoxy stearate;
Dibasic acids such as sebacic acid, adipic acid, azelaic acid, phthalic acid and ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol,
Polyester plasticizers obtained from dihydric alcohols such as dipropylene glycol; vinyl polymers obtained by polymerizing vinyl monomers such as acrylic plasticizers by various methods, alone or in combination. These can be mixed and used, but are not always required. In addition, these plasticizers can be blended at the time of polymer production. The amount of the plasticizer used is not limited, but is 5 to 150 parts by weight, preferably 10 to 120 parts by weight, more preferably 20 to 100 parts by weight, based on 100 parts by weight of the vinyl polymer (I). is there. If it is less than 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product will be insufficient.

<Filler> Various fillers are used as necessary for the sealing material for the SSG construction method of the present invention. Examples of the filler include, but are not particularly limited to, wood flour, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica,
Walnut shell powder, rice husk powder, graphite, diatomaceous earth, terra alba, fumed silica, precipitated silica, crystalline silica,
Reinforcing fillers such as fused silica, dolomite, silicic anhydride, hydrous silicic acid, carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, Fillers such as organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, zinc powder and shirasu balloon; fibrous fillers such as asbestos, glass fibers and filaments; Can be Among these fillers, precipitated silica, fumed silica, crystalline silica, fused silica, dolomite, carbon black, calcium carbonate, titanium oxide,
Talc is preferred. In particular, when it is desired to obtain a high-strength cured product with these fillers, mainly fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, crystalline silica, fused silica A filler selected from silica, calcined clay, clay and activated zinc white can be added. When it is desired to obtain a cured product having low strength and large elongation, a filler mainly selected from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like can be added. In general, when the specific surface area of calcium carbonate is small, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of a 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. Further, it is more preferable that calcium carbonate has been subjected to surface treatment using a surface treatment agent. When using surface-treated calcium carbonate,
It is considered that the workability of the composition of the present invention is improved as compared with the case where calcium carbonate without surface treatment is used, and the effects of improving the adhesiveness and weather resistance of the sealing material for SSG construction are 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 0.1% with respect to calcium carbonate.
The treatment is preferably performed in the range of 1 to 20% by weight,
It is more preferable to treat in the range of weight%. If the treatment amount is less than 0.1% by weight, the effect of improving workability, adhesion and weather resistance may not be sufficient, and if it exceeds 20% by weight, the storage stability of the sealing material for SSG construction may be insufficient. May decrease.

<Addition Amount> When the filler is used, the amount of the filler is preferably in the range of 5 to 1,000 parts by weight, preferably 20 to 20 parts by weight, based on 100 parts by weight of the vinyl polymer (I). It is more preferably used in the range of 500 parts by weight, particularly preferably in the range of 40 to 300 parts by weight. If the amount is less than 5 parts by weight, the effect of improving the breaking strength, elongation at break, adhesion and weather resistance of the cured product may not be sufficient.
The workability of the sealing material for the G construction method may decrease.
The filler may be used alone or in combination of two or more.

<Physical Property Adjusting Agent> A physical property adjusting agent for adjusting the tensile properties of the resulting cured product may be added to the sealing material for SSG construction of the present invention, if necessary. The physical property adjuster is not particularly limited, and for example, alkyl alkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy Silane, alkylisopropenoxysilane such as γ-glycidoxypropylmethyldiisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane,
Alkoxysilanes having functional groups such as vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane Varnishes; silicone varnishes; polysiloxanes and the like. 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)> In the sealing material for SSG construction of the present invention, a thixotropic agent (anti-sagging agent) for preventing sagging and improving workability, if necessary. May be added. The anti-sagging agent is not particularly limited, and examples thereof include polyamide waxes;
Hydrogenated castor oil and derivatives thereof; and 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.

<Light Stabilizer> Further, when the sealing material for the SSG construction method of the present invention is used in a portion directly or indirectly exposed to sunlight, particularly a weather-resistant adhesive is required. An agent may be added. The addition amount of the light stabilizer is preferably in the range of about 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the vinyl polymer (I). If the amount of the light stabilizer falls below this range, the weather resistance to glass may not be able to be exhibited. On the other hand, if it exceeds this range, the physical properties and workability of the compound may decrease, and it is not preferable from the viewpoint of cost.

[0149]Other additives  The SSG construction sealing material of the present invention includes
For the purpose of adjusting various physical properties of the sealing material or cured product,
Various additives may be added as needed. like this
Examples of additives include, for example, flame retardants,
Agents, anti-aging agents, radical inhibitors, UV absorbers, metals
Deactivator, ozone deterioration inhibitor, phosphorus-based peroxide decomposition
Agents, lubricants, pigments, foaming agents, fungicides, rust inhibitors, photocurable
Resins. These various additives are used alone
Or two or more of them may be used in combination.

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 sealing material for SSG construction method 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. It is also possible to prepare a two-component type in which components such as a material, a plasticizer, and water are blended in advance, and the blended material and the polymer composition are mixed before use.

[0151]

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)" were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, GP
A column filled with a polystyrene crosslinked gel as a C column (shodex GPC K-804; Showa Denko KK)
And GPC solvent was chloroform.

(Production Example 1) 2 equipped with a reflux tube and a stirrer
In a separable flask of L, CuBr (8.39 g,
0.0585 mol), and the inside of the reaction vessel was purged with nitrogen. Acetonitrile (112 mL) was added, and the mixture was stirred in an oil bath at 70 ° C. for 30 minutes. To this, butyl acrylate (224 mL), diethyl 2,5-dibromoadipate (23.4 g, 0.0650 mol), pentamethyldiethylenetriamine (0.500 mL, 0.244 m
mol) (hereinafter triamine) was added to initiate the reaction. With heating and stirring at 70 ° C., butyl acrylate (895 mL) was continuously added dropwise over 150 minutes.
During the dropping of butyl acrylate, triamine (2.50 m
L, 12.0 mmol). 31 from the start of the reaction
After 0 minutes, 1,7-octadiene (288 mL, 1.
95 mol), triamine (4.0 mL, 0.0195)
mol), 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 [1]). The number average molecular weight of the polymer [1] is 20,000, and the molecular weight distribution is 1.
It was 3. In a 2 L separable flask equipped with a reflux tube, polymer [1] (1.0 kg) and potassium benzoate (34.8) were added.
g), N, N-dimethylacetic acid amide (1 L) was charged,
The mixture was heated and stirred at 70 ° C. for 15 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 polymer [2].

A polymer [2] (1 kg), aluminum silicate (200 g, Kyoward 700PEL, manufactured by Kyowa Chemical Co., Ltd.) and toluene (1 L) were charged into a 2 L round-bottom flask equipped with a reflux tube. The mixture was heated and stirred for 5 hours. After the aluminum silicate was removed by filtration, the toluene in the filtrate was distilled off under reduced pressure to obtain a polymer [3]. 1L
In a pressure-resistant reaction vessel, polymer [3] (718.80 g), dimethoxymethylhydrosilane (27.55 mL, 0.22
3 mol), methyl orthoformate (8.14 mL, 0.0
74 mmol), and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zero-valent platinum. 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 5 hours. 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
As a result of C measurement (polystyrene conversion), the molecular weight distribution was 23,000, 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 1.7.

(Example 1) 100 parts of the polymer [4] obtained in Production Example 1 was added to colloidal calcium carbonate (Hakushinka CC
R: 150 parts made of calcium Shiroishi, 20 parts of heavy calcium carbonate (Nanox 25A: made of Maruo Calcium), 10 parts of titanium oxide (rutile type: Taipaque R-820: made by Ishihara Sangyo), 50 parts of plasticizer (DIDP), Anti-aging agent (Tinuvin 213: manufactured by Ciba Specialty Chemicals)
1 part, light stabilizer (Sanol LS-765: manufactured by Sankyo) 1
Part, photocurable resin (Aronix M309: manufactured by Toagosei Co., Ltd.), 3 parts, thixotropic agent (Disparon # 6500:
2 parts by Kusumoto Chemicals, adhesion promoter (A-1120, A-1)
87: manufactured by Nippon Unicar)
Divalent tin catalyst (dibutyltin diacetylacetonate, U-
220: manufactured by Nitto Kasei) and H of JISA 5758
A test body (substrate: glass) having the same mold tensile adhesion was prepared and cured in a room for 7 days at 50 ° C. for 7 days to obtain a cured product.

Comparative Example 1 A cured product was obtained in the same manner as in Example 1 by using a commercially available silicone sealant for SSG, Sealant 90 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone rubber cured at room temperature, curing type: dealcohol type). Was prepared. (Evaluation) The tensile properties of each cured product were measured. The results are shown in Table 1.

[0156]

[Table 1]

(Example 2 and Comparative Example 2) Using the compound obtained in Example 1 and the commercially available silicone sealant for SSG and sealant 90 used in Comparative Example 1 for 5 m each,
A sheet-shaped cured product having a thickness of m is prepared, and is subjected to JIS A 5758.
After curing for 7 days in a room and 7 days at 50 ° C. according to -1992, it was exposed outdoors (45 ° south slope) in the Hyogo Ward, Kobe City, Hyogo Prefecture, and the contamination status of the surface of the cured product was evaluated over time. Observed. The results are shown in Table 2.

[0158]

[Table 2]

(Example 3 and Comparative Example 3) Using the compound obtained in Example 1 and the commercially available silicone sealant for SSG and sealant 90 used in Comparative Example 1, each having a width of 1
Fill 2mm x 8mm deep joints according to JIS A57
According to 58-1992, the composition was cured and cured at 50 ° C for 7 days in a room to prepare a cured product. As the adherend, artificial marble (Neoparrier: 15 mm × 100 mm × 150 mm) was used. Then, it exposed outdoors (45 degree south side inclination) in the Hyogo-ku area of Kobe-shi, Hyogo, and observed the contamination state around the hardened | cured material with time. The results are shown in Table 3.

[0160]

[Table 3]

(Example 4 and Comparative Example 4) Using the compound obtained in Example 1 and the commercially available silicone sealant for SSG and sealant 90 used in Comparative Example 1, the same kind of glass coating as in Example 1 was used. A cured product was prepared on the body.
Each cured product was treated with a xenon weather meter (Suga Tester SX120, radiation intensity at 300 to 400 nm, 180 W / m ² , black panel temperature 63 ° C., irradiation 2).
Irradiation was performed for 1000 hours from the glass surface side during rainfall for 18 minutes during the time, and then a destruction state was observed by a hand peel test. All of the samples showed a tendency to cohesive failure and were confirmed to have good weather resistance.

Example 5 and Comparative Example 5 The cured products obtained in Example 3 and Comparative Example 3 were subjected to a xenon weather meter (Suga tester SX120, radiation intensity at 300 to 400 nm, 180 W / m ² , black panel temperature). 63
2 hours, 18 hours during rainfall for 2 hours)
Thereafter, the surface condition was observed. No abnormalities such as whitening (chalking) and cracks were observed, and it was confirmed that they had good weather resistance.

[0163]

According to the present invention, when the curable composition of the present invention is used for SSG applications, it can be applied to adherends such as float glass, surface-treated various heat ray reflective glasses, etc., for a long time. Express stable adhesive properties over a long period of time. The rubber-like material obtained by curing the composition of the present invention has no contamination to glass, weather resistance, weather resistance,
Heat resistance and water resistance are as good as conventional silicone sealants.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram of an SSG construction method.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08F 14/18 C08F 14/18 20/00 20/00 20/18 20/18 20/44 20/44 30/08 30 / 08 E04B 1/682 E04B 1/68 LF term (reference) 2E001 DA01 HD11 MA02 MA06 4H017 AA04 AA31 AB01 AD05 AE03 4J015 CA04 4J100 AA02P AA03P AB02P AB03P AB04P AB07P AB08P AC01P AC03P AC04 AG02P ACP AG04P AL04P AL05P AL08P AL09P AL10P AL11P AL39P AL41P AM02P AM15P AM43P AM47P AM48P AP16P AS02P AS03P BA03P BA05P BA06P BA08P BA29P BA56P BA77P BB10P BB18P BC04P BC43P CA01 CA31 DA01 DA49 FA03 HA53 JA01

Claims (22)

[Claims] 1. An SSG comprising a vinyl polymer (I) having at least one crosslinkable functional group.
Sealing material for construction method. 2. The sealing material for SSG construction according to claim 1, which is a sealing material for waterproofing in SSG construction. 3. The sealing material for SSG construction according to claim 1, wherein the molecular weight distribution of the vinyl polymer (I) is less than 1.8. 4. 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 sealing material for an SSG construction method according to any one of claims 1 to 3, which is produced by mainly polymerizing at least one kind of the monomer. 5. The sealant for SSG construction according to claim 1, wherein the vinyl polymer (I) is a (meth) acrylic polymer. 6. The SSG according to claim 1, wherein the vinyl polymer (I) is an acrylic polymer.
Sealing material for construction method. 7. The sealing material for SSG construction according to claim 6, wherein the vinyl polymer (I) is an acrylate polymer. 8. The sealing material for SSG construction according to claim 7, wherein the vinyl polymer (I) is a butyl acrylate polymer. 9. The sealing material for an SSG construction method according to claim 1, wherein the crosslinkable functional group of the vinyl polymer (I) is a crosslinkable silyl group. 10. The sealant for SSG construction according to claim 1, wherein the crosslinkable functional group of the vinyl polymer (I) is an alkenyl group. 11. The sealant according to claim 1, wherein the crosslinkable functional group of the vinyl polymer (I) is a hydroxyl group. 12. The sealant for SSG construction according to claim 1, wherein the crosslinkable functional group of the vinyl polymer (I) is an amino group. 13. The sealing for an SSG construction 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. Wood. 14. The sealing material for an SSG method according to claim 1, wherein the crosslinkable functional group of the vinyl polymer (I) is an epoxy group. 15. The main chain of the vinyl polymer (I) is produced by a living radical polymerization method.
15. The sealing material for an SSG construction method according to any one of items 14 to 14. 16. The sealing material for SSG construction according to claim 15, wherein the living radical polymerization is atom transfer radical polymerization. 17. The atom transfer radical polymerization, wherein at least one selected from transition metal complexes having a central metal of Group 7, 8, 9, 10 or 11 of the periodic table as a catalyst. 17. The sealing material for an SSG construction method according to 16. 18. The sealing material according to claim 17, wherein the metal complex used as the catalyst is at least one selected from the group consisting of a complex of copper, nickel, ruthenium and iron. 19. The sealing material according to claim 18, wherein the metal complex used as the catalyst is a copper complex. 20. A one-component sealing material for SSG construction, comprising: a vinyl polymer (I) having at least one crosslinkable functional group; and a curing catalyst. 21. An SSG method comprising, as essential components, a first component containing a vinyl polymer (I) having at least one crosslinkable functional group and a second component containing a curing agent and a curing catalyst. Two-part sealing material. 22. An SSG method using a sealing material containing a vinyl polymer (I) having at least one crosslinkable functional group.