JP2001271055A - Sealing material composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealing material composition for a siding board whose adhesive property to a hardened material and durability including fine sight are improved. SOLUTION: A sealing material composition for a siding board consisting of a vinyl polymer having at least one of crosslinking functional group. Examples of the vinyl polymer include a polymer obtained by introducing dimethoxymethylsilyl group as the crosslinking functional group into a polymer consisting mainly of butyl acrylate, and having a number average molecular weight of 23,000, a molecular weight distribution of 1.4 and an average number of silyl groups per one molecule of the polymer of 1.7.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a sealant composition. More specifically, the present invention relates to a sealing material composition for a siding board comprising a vinyl polymer having at least one crosslinkable functional group.

[0002]

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

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

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

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

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

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

For example, a vinyl polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having a silicon-containing group capable of being crosslinked by forming a siloxane bond (hereinafter also referred to as “crosslinkable silyl group”). The combined product or the cured product obtained from the composition is excellent in heat resistance or weather resistance, and is used for electric and electronic materials such as sealing materials such as elastic sealing materials for building materials and sealing materials for double glazing, and sealing materials for backside of solar cells. Parts materials, electrical insulation materials such as insulation coatings for wires and cables, adhesives, adhesives, elastic adhesives,
Paints, powder paints, coating materials, foams, potting agents for electric and electronic devices, films, gaskets, casting materials, various molding materials, and rust-proof and waterproof seals for netted glass and laminated glass edges (cut sections) It is used for various applications such as stop materials.

Among them, a sealing material used for sealing an architectural elastic sealant, especially a siding board, particularly a joint of a ceramic siding board, has various requirements such as a waterproof function and maintenance of aesthetics as described below. .

A siding board is a board made of various materials used for an outer wall of a low-rise building or the like. When the siding board itself is attached to a building, a gap (joint) always occurs between the siding board and another member of the building or between the siding board and another siding board. When the building to which this siding board is attached is exposed to the wind and rain, rainwater enters through the gap, so that the building is filled with the sealing material. The sealing material used for sealing the joint is required to maintain the joint's watertightness (waterproofness) and airtightness (cutoff from outside air) for a long period of time.

Generally, the width of a joint changes due to a change in temperature, movement of a building, and the like. Therefore, the sealing material needs to be excellent in rubber properties, that is, excellent in resilience so as to follow the change in the joint width. . In other words, once the joints have been expanded or narrowed, if they return to their original width, it is necessary to restore the sealing material to its original state, and the sealing material has been expanded or shrunk without being restored. In such a state, the appearance is impaired, and the sealing material peels off from the adhesive surface.

In particular, peeling from the adhesive surface is fatal to the sealing material. JIS A for restorability of sealing material
It is listed as durable with reference to the Annex of 5758, and those positioned in section 9030 have excellent resilience. However, even if the sealing material positioned in this section 9030 is used for the joint of the siding board, the sealing material may be separated from the interface relatively quickly but with time as compared with the case where it is used for other joints. .

In order to avoid this peeling accident, a method of increasing the adhesive strength by adding an adhesion-imparting agent to the sealing material or applying a primer to the surface of the siding board (the surface to be adhered) is usually used. A method of reducing the tensile stress of the cured product to reduce the stress on the bonding interface or the like can be considered. However, these methods have problems in that they are complicated, increase the cost, and change the physical properties of the cured product.

On the other hand, as a demand from the market, not only a sealing material for a siding board but also an elastic sealant for construction (particularly, a one-component elastic sealant) has weather resistance which maintains its appearance for a long time after construction. In other words, it is required that color fading, whitening, and cracking do not occur.

As described above, further demands have been made on the sealing material for siding boards with respect to their waterproof function and maintenance of their aesthetic appearance.

[0016]

SUMMARY OF THE INVENTION An object of the present invention is to provide a sealing material composition for a siding board which is excellent in durability including adhesion and appearance.

[0017]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above-mentioned situation, and as a result, many peelings have occurred in places where there is movement in the direction in which the joints spread. Is not a specific movement, that is, expansion and contraction around a fixed joint width (this is equivalent to the durability test listed in the annex of JIS A 5758), but the siding board seen in the early stage of construction. A solution was found by focusing on movement in a certain direction (a direction in which joints spread) caused by shrinkage due to drying, and movement in a certain direction out of the plane of the board due to warping or twisting.

That is, since movements such as displacement and warping of the siding board are concentrated in the early stage of the execution, the joints of the siding board move in a direction to spread in the initial stage. Therefore, stress is applied to the sealing material applied to the joint. However, sealing materials designed for ordinary joints that repeat expansion and contraction have high resilience so as to follow them, and conversely, if the applied sealing material has high resilience to displacement, it will have Later, after the movement of the siding board in the early stage of the operation is stopped, the applied stress becomes large and the siding board is easily peeled.

In such a portion, a sealing material having poor resilience rather than a sealing material having good resilience and having a fixed deformation to relieve stress and reduce a load at an interface is used. It is preferable to use it.

It has been found that even when a sealing material having poor resilience is used, the expansion and contraction is not so large at places where joint expansion and contraction are repeated, and even if the resilience is poor, it can be used satisfactorily.

It has also been found that discoloration, whitening and cracking can be improved by using a vinyl polymer having high weather resistance of the polymer itself.

Therefore, by using the sealing material composition for a siding board comprising the vinyl polymer (I) having at least one crosslinkable functional group, the cured product obtained by curing the composition is used as the joint of the siding board. The present inventors have found that durable adhesiveness and weather resistance can be improved, and solved the above-mentioned problems, and reached the present invention.

That is, the present invention is a sealing material composition for a siding board containing the vinyl polymer (I) having at least one crosslinkable functional group.

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

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

Further, the vinyl polymer (I) is not particularly limited, but has a weight average molecular weight (Mw) and a number average molecular weight (Mw) measured by gel permeation chromatography.
The value of the ratio (Mw / Mn) of n) 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, polymerizable carbon-carbon double bond,
Epoxy groups and the like are preferred.

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

The number of the crosslinkable functional groups of the vinyl polymer (I) is not particularly limited. The number is more preferably 1.5 or more.

[0030]

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

The molecular weight distribution of the polymer (I) of the present invention, that is, the ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography is not particularly limited, but is preferably less than 1.8, 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, more preferably 1000 to 100,000. <Synthesis Method of Main Chain> The synthesis method of the vinyl polymer (I) of the present invention is not limited, but controlled radical polymerization is preferable, living radical polymerization is more preferable, and atom transfer radical polymerization is particularly preferable. These will be described below. Controlled radical polymerization The radical polymerization method is based on a `` general radical polymerization method '' in which a monomer having a specific functional group and a vinyl monomer are simply copolymerized using an azo compound, a peroxide, or the like as a polymerization initiator. It can be classified as a "controlled radical polymerization method" in which a specific functional group can be introduced at a controlled position such as a terminal.

The "general radical polymerization method" is a simple method. However, in this method, a monomer having a specific functional group is introduced into the polymer only stochastically. If it is intended to obtain such a monomer, it is necessary to use this monomer in a considerably large amount. Conversely, if the monomer is used in a small amount, there is a problem that the proportion of the polymer into which this specific functional group is not introduced becomes large. In addition, since it is free radical polymerization, there is a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.

The "controlled radical polymerization method" further includes a "chain transfer agent method" in which 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 substantially as designed can be obtained by growing a polymer growth terminal without causing a termination reaction or the like.

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

Unlike these polymerization methods, the “living radical polymerization method” is a radical polymerization which is difficult to control because the polymerization rate is high and a termination reaction is likely to occur due to coupling between radicals. The reaction hardly occurs and the molecular weight distribution is narrow (Mw / Mn is 1.
(Approximately 1 to 1.5) A polymer can be obtained, and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

Accordingly, the "living radical polymerization method" can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and can introduce a monomer having a specific functional group into almost any position of the polymer. Therefore, the method for producing a vinyl polymer having the specific functional group is more preferable.

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

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

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

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

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

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

Hereinafter, living radical polymerization will be described.

First, a method using a radical scavenger such as a nitroxide compound will be described. In this polymerization, a stable nitroxy free radical (= N
-O.) Is used as a radical capping agent. Such compounds include, but are not limited to, 2, 2,
6,6-substituted-1-piperidinyloxy radicals and 2,
Preferred are nitroxy free radicals from cyclic hydroxyamines, such as 2,5,5-substituted-1-pyrrolidinyloxy radicals. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group and an ethyl group is suitable. Specific nitroxy free radical compounds include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl-1- Piperidinyloxy radical, 2,
2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-
1-pyrrolidinyloxy radical, 1,1,3,3-tetramethyl-2-isoindolinyloxy radical,
N, N-di-t-butylamineoxy radical and the like can be mentioned. Instead of the nitroxy free radical, a stable free radical such as galvinoxyl free radical may be used.

The above radical capping agent is used in combination with a radical generator. It is considered that the reaction product of the radical capping agent and the radical generator serves as a polymerization initiator, and the polymerization of the addition-polymerizable monomer proceeds. The combination ratio of the two is not particularly limited, but 0.1 to 10 mol of the radical initiator is appropriate for 1 mol of the radical capping agent.

As the radical generator, various compounds can be used, but a peroxide capable of generating a radical under polymerization temperature conditions is preferable. Examples of the peroxide include, but are not limited to, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide; dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide; diisopropyl peroxydicarbonate; Peroxycarbonates such as (4-t-butylcyclohexyl) peroxydicarbonate, t-butyl peroxyoctoate, t-
There are alkyl peresters such as butyl peroxybenzoate. Particularly, benzoyl peroxide is preferred. Further, a radical generator such as a radical-generating azo compound such as azobisisobutyronitrile may be used instead of the peroxide.

Macromolecules 199
5, 28, 2993, instead of using a radical capping agent and a radical generator together,
An alkoxyamine compound as shown below may be used as an initiator.

[0049]

Embedded image When an alkoxyamine compound is used as the initiator, if it has a functional group such as a hydroxyl group as shown in the above figure, a polymer having a functional group at the terminal can be obtained. When this is used in the method of the present invention, a polymer having a functional group at a terminal can be obtained.

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

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

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

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

Specific examples of the organic halide having an alkenyl group represented by the general formula 1 include XCH ₂ C
(O) O (CH ₂ ) _n CH = CH ₂ , H ₃ CC (H) (X)
C (O) O (CH ₂ ) _n CH = CH ₂ , (H ₃ C) ₂ C
(X) C (O) O (CH ₂ ) _n CH = CH ₂ , CH ₃ CH ₂
C (H) (X) C (O) O (CH ₂ ) _n CH = CH ₂ ,

[0055]

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

[0056]

Embedded image(In each of the above formulas, X represents chlorine, bromine, or iodine.
Prime, n is an integer of 1 to 20, m is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four− (CH_Two)_n-CH = C
H_Two, O, m, p-CH_ThreeC (H) (X) -C₆H_Four− (C
H_Two)_n-CH = CH_Two, O, m, p-CH_ThreeCH_TwoC
(H) (X) -C₆H_Four− (CH_Two)_n-CH = CH_Two,
(In each of the above formulas, X represents chlorine, bromine, or iodine.
Prime, n is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four− (CH_Two)_n-O- (C
H_Two)_m-CH = CH_Two, O, m, p-CH_ThreeC (H)
(X) -C₆H_Four− (CH_Two)_n-O- (CH_Two)_m-CH =
CH_Two, O, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H
_Four− (CH_Two)_n-O- (CH_Two)_mCH = CH_Two,(above
In each formula, X is chlorine, bromine, or iodine, and n is 1
O, m, p-XCH_Two-C₆H_Four-O- (CH_Two)_n-CH
= CH_Two, O, m, p-CH_ThreeC (H) (X) -C₆H_Four−
O- (CH_Two)_n-CH = CH_Two, O, m, p-CH _ThreeCH
_TwoC (H) (X) -C₆H_Four-O- (CH_Two)_n-CH = C
H_Two, (In each of the above formulas, X is chlorine, bromine, or
Iodine, n is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four-O- (CH_Two)_n-O-
(CH_Two)_m-CH = CH_Two, O, m, p-CH_ThreeC (H)
(X) -C₆H_Four-O- (CH_Two)_n-O- (CH_Two) _m-C
H = CH_Two, O, m, p-CH_ThreeCH_TwoC (H) (X)-
C₆H_Four-O- (CH _Two)_n-O- (CH_Two)_m-CH = CH
_Two, (In each of the above formulas, X is chlorine, bromine, or
Urine, n is an integer of 1 to 20, m is an integer of 0 to 20) As an organic halide having an alkenyl group,
The compound represented by the general formula 2 is exemplified. H_TwoC = C (R^Three) -R⁷-C (R^Four) (X) -R⁸-R^Five (2) (where R^Three, R^Four, R^Five, R⁷, X is the same as above, R
⁸Is a direct bond, -C (O) O- (ester group), -C
(O)-(keto group) or o-, m-, p-phenyl
Represents a len group) R⁶Is a direct bond or a divalent organic group having 1 to 20 carbon atoms
(Which may contain one or more ether bonds)
Is a direct bond, the carbon to which the halogen is bonded
With a vinyl group bonded to the halogenated allylic compound
is there. In this case, carbon-halogenation is achieved by adjacent vinyl groups.
Is activated, so that R⁸As C (O) O
It is not necessary to have a group or phenylene group, etc.
It may be a combination. R⁷Is not a direct bond,
In order to activate the halogen-halogen bond, R⁸As C
(O) O, C (O) and phenylene groups are preferred.

If the compound of the general formula 2 is specifically exemplified, CH ₂ ＣＨCHCH ₂ X, CH ₂ ＣC (CH ₃ ) CH
₂ X, CH ₂ ＣＨCHC (H) (X) CH ₃ , CH ₂ ＣC (C
H ₃ ) C (H) (X) CH ₃ , CH ₂ ＣＨCHC (X) (C
H ₃ ) ₂ , CH ₂ （CHC (H) (X) C ₂ H ₅ , CH ₂ ＣC
HC (H) (X) CH (CH 3) 2, CH 2 = CHC
(H) (X) C ₆ H ₅ , CH ₂ ＣＨCHC (H) (X) CH _{2
C 6 H 5, CH 2 =} CHCH 2 C (H) (X) -CO 2 R,
_{CH 2 = CH (CH 2)} 2 C (H) (X) -CO 2 R, CH
_{2 = CH (CH 2) 3} C (H) (X) -CO 2 R, CH 2 =
_{CH (CH 2) 8 C (} H) (X) -CO 2 R, CH 2 = CH
_{CH 2 C (H) (X} ) -C 6 H 5, CH 2 = CH (CH 2) 2
C (H) (X) -C 6 H 5, CH 2 = CH (CH 2) 3 C
_{(H) (X) -C 6} H 5, ( in each formula above, X is chlorine, bromine or iodine, R represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group,) and the like, etc. it can.

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

Organic halogen having crosslinkable silyl group
The compound is not particularly limited.
One having a structure is exemplified. R^FourR^FiveC (X) -R⁶-R⁷-C (H) (R^Three) CH_Two− [Si (R⁹)_2-b(Y)_b O]_m-Si (R^Ten)_3-a(Y)_a (3) (where R^Three, R^Four, R^Five, R⁶, R⁷, X is the same as above,
R⁹, R^TenIs an alkyl group having 1 to 20 carbon atoms,
Aryl group, aralkyl group, or (R ′)_ThreeSiO-
(R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms,
The three R's may be the same or different
I) represents a triorganosiloxy group represented by⁹Ma
Or R^TenWhen two or more exist, they are the same.
Or may be different. Y is a hydroxyl group or water
A decomposable group, and when two or more Y
They may be one or different. a is 0, 1,
2, or 3, and b represents 0, 1, or 2.
m is an integer of 0-19. Where a + mb ≧ 1
To specifically exemplify the compound of the general formula 3, XCH_Two
C (O) O (CH_Two)_nSi (OCH_Three)_Three, CH_ThreeC
(H) (X) C (O) O (CH_Two)_nSi (OCH_Three)_Three,
(CH_Three)_TwoC (X) C (O) O (CH_Two)_nSi (OCH
_Three)_Three, XCH_TwoC (O) O (CH_Two)_nSi (CH_Three) (O
CH_Three)_Two, CH _ThreeC (H) (X) C (O) O (CH_Two)_n
Si (CH_Three) (OCH_Three)_Two, (CH_Three)_TwoC (X) C
(O) O (CH_Two)_nSi (CH_Three) (OCH_Three)_Two,(Up
In each of the above formulas, X is chlorine, bromine, iodine, and n is 0 to
An integer of 20) XCH_TwoC (O) O (CH_Two)_nO (C
H_Two)_mSi (OCH_Three)_Three, H_ThreeCC (H) (X) C
(O) O (CH_Two)_nO (CH_Two)_mSi (OCH_Three)_Three,
(H_ThreeC)_TwoC (X) C (O) O (CH_Two)_nO (CH_Two)_m
Si (OCH_Three)_Three, CH_ThreeCH_TwoC (H) (X) C (O)
O (CH_Two)_nO (CH_Two)_mSi (OCH_Three)_Three, XCH_Two
C (O) O (CH_Two)_nO (CH_Two)_mSi (CH_Three) (O
CH_Three)_Two, H_ThreeCC (H) (X) C (O) O (CH_Two)_n
O (CH_Two)_m-Si (CH_Three) (OCH_Three)_Two, (H_ThreeC)
_TwoC (X) C (O) O (CH_Two)_nO (CH_Two)_m-Si
(CH_Three) (OCH_Three)_Two, CH_ThreeCH _TwoC (H) (X) C
(O) O (CH_Two)_nO (CH_Two)_m-Si (CH_Three) (O
CH_Three)_Two, (In each of the above formulas, X represents chlorine, bromine,
U, n is an integer of 1 to 20, m is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four− (CH_Two)_TwoSi (OC
H_Three)_Three, O, m, p-CH_ThreeC (H) (X) -C₆H_Four−
(CH_Two)_TwoSi (OCH_Three)_Three, O, m, p-CH_ThreeCH_Two
C (H) (X) -C₆H_Four− (CH_Two)_TwoSi (OC
H_Three)_Three, O, m, p-XCH_Two-C₆H_Four− (CH_Two)_ThreeS
i (OCH_Three)_Three, O, m, p-CH_ThreeC (H) (X)-
C₆H_Four− (CH_Two)_ThreeSi (OCH_Three)_Three, O, m, p-C
H_ThreeCH_TwoC (H) (X) -C₆H_Four− (CH_Two)_ThreeSi (O
CH_Three)_Three, O, m, p-XCH_Two-C₆H_Four− (CH_Two)_Two
-O- (CH_Two)_ThreeSi (OCH_Three)_Three, O, m, p-CH
_ThreeC (H) (X) -C₆H_Four− (CH_Two)_Two-O- (CH_Two)
_ThreeSi (OCH_Three)_Three, O, m, p-CH_ThreeCH_TwoC (H)
(X) -C₆H_Four− (CH_Two)_Two-O- (CH_Two)_ThreeSi (O
CH_Three)_Three, O, m, p-XCH_Two-C₆H_Four-O- (C
H_Two)_ThreeSi (OCH_Three)_Three, O, m, p-CH_ThreeC (H)
(X) -C₆H_Four-O- (CH_Two)_ThreeSi (OCH_Three)_Three,
o, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H_Four-O-
(CH_Two)_Three-Si (OCH_Three)_Three, O, m, p-XCH_Two
-C₆H_Four-O- (CH_Two)_Two-O- (CH_Two)_Three-Si (O
CH_Three)_Three, O, m, p-CH_ThreeC (H) (X) -C₆H_Four
-O- (CH_Two)_Two-O- (CH_Two)_ThreeSi (OCH_Three)_Three,
o, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H_Four-O-
(CH_Two)_Two-O- (CH_Two)_ThreeSi (OCH_Three)_Three,(the above
In each formula, X is chlorine, bromine, or iodine), etc.
No.

As the organic halide having a crosslinkable silyl group, those having a structure represented by the following general formula 4 are further exemplified. ^{_{(R 10) 3-a (}} Y) a Si- [OSi (R 9) 2-b (Y) b] m -CH 2 -C (H) (R 3) -R 7 -C (R 4) ( ^{X) 8 -R 5 (4)} ( wherein ^{-R, R 3, R 4,} R 5, R 7, R 8, R 9, R 10, a,
b, m, X, and Y are the same as described above. If such a compound is specifically exemplified, (CH ₃
O) ₃ SiCH ₂ CH ₂ C (H) (X) C ₆ H ₅ , (CH
_{3 O) 2 (CH 3)} SiCH 2 CH 2 C (H) (X) C
_{6 H 5, (CH 3 O} ) 3 Si (CH 2) 2 C (H) (X) -C
O ₂ R, (CH ₃ O) ₂ (CH ₃ ) Si (CH ₂ ) ₂ C (H)
(X) —CO ₂ R, (CH ₃ O) ₃ Si (CH ₂ ) ₃ C
_{(H) (X) -CO 2} R, (CH 3 O) 2 (CH 3) Si
_{(CH 2) 3 C (H} ) (X) -CO 2 R, (CH 3 O) 3 S
_{i (CH 2) 4 C (} H) (X) -CO 2 R, (CH 3 O) 2
_{(CH 3) Si (CH 2} ) 4 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 9 C (H) (X) -CO
_{2 R, (CH 3 O)} 2 (CH 3) Si (CH 2) 9 C (H)
(X) —CO ₂ R, (CH ₃ O) ₃ Si (CH ₂ ) ₃ C
_{(H) (X) -C 6} H 5, (CH 3 O) 2 (CH 3) Si
_{(CH 2) 3 C (H} ) (X) -C 6 H 5, (CH 3 O) 3 Si
_{(CH 2) 4 C (H} ) (X) -C 6 H 5, (CH 3 O) 2 (C
_{H 3) Si (CH 2)} 4 C (H) (X) -C 6 H 5, ( in each formula above, X is chlorine, bromine or iodine, R represents an alkyl group having 1 to 20 carbon atoms, aryl Group, aralkyl group) and the like.

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

[0062]

Embedded image (In each of the above formulas, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
An aryl group, an aralkyl group, and n is an integer of 1 to 20) In order to obtain a polymer having two or more terminal structures in one molecule of the present invention, an organic halide having two or more starting points or halogen Preferably, a sulfonyl halide compound is used as the initiator. To give a concrete example,

[0063]

Embedded image

[0064]

Embedded image And the like.

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

The transition metal complex used as the polymerization catalyst is not particularly limited, but is preferably 7 in the periodic table.
It is a metal complex complex having a Group 7, 8, 9, 10 or 11 element as a central metal. More preferably,
Examples thereof include complexes of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, and divalent nickel. Among them, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, and the like. is there. When a copper compound is used, 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine and the like for enhancing the catalytic activity A ligand such as a polyamine is added. Tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ )
Are also suitable as catalysts. When a ruthenium compound is used as a catalyst, aluminum alkoxides are added as an activator. Furthermore, bis (triphenylphosphine) complex of divalent iron (FeCl ₂ (PPh ₃ ) ₂ ) and bistriphenylphosphine complex of divalent nickel (NiCl
₂ (PPh ₃ ) ₂ ) and bistributylphosphine complex of divalent nickel (NiBr ₂ (PBu ₃ ) ₂ ) are also suitable as the catalyst.

The polymerization can be carried out without solvent or in various solvents. Examples of the solvent include hydrocarbon solvents such as benzene and toluene, ether solvents such as diethyl ether and tetrahydrofuran, halogenated hydrocarbon solvents such as methylene chloride and chloroform, and ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone. Solvent, methanol, ethanol, propanol, isopropanol, n-butyl alcohol, alcohol solvents such as tert-butyl alcohol, acetonitrile, propionitrile, nitrile solvents such as benzonitrile, ethyl acetate, ester solvents such as butyl acetate, Examples thereof include carbonate solvents such as ethylene carbonate and propylene carbonate, which may be used alone or in combination of two or more. Also, although not limited, polymerization is 0
C. to 200.degree. C., preferably 50.degree.
１５０150 ° C. <Functional group> The crosslinkable functional group of the vinyl polymer (I) is not limited, but may be a crosslinkable silyl group, an alkenyl group, a hydroxyl group, an amino group, a polymerizable carbon-carbon double bond,
Epoxy groups and the like are preferred.

All of these crosslinkable functional groups can be properly used depending on the use / purpose. Position of crosslinkable functional group When the cured product of the sealing material composition of the present invention is particularly required to have rubber-like properties, the molecular weight between crosslink points having a large effect on rubber elasticity can be increased, so that the crosslinkable functional group Is preferably at the end of the molecular chain.
More preferably, all the crosslinkable functional groups have at the molecular chain terminal.

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

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

Examples of the hydrolyzable group include groups generally used 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.

The hydrolyzable group and the hydroxyl group can be bonded to one silicon atom in the range of 1 to 3 and (a + Σ
b) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silyl group, they may be the same or different. The number of silicon atoms forming a crosslinkable silyl group is one or more. In the case of silicon atoms linked by a siloxane bond or the like, the number is preferably 20 or less. In particular, a crosslinkable silyl group represented by the general formula 6-Si (R ¹⁰ ) _3-a (Y) _a (6) (wherein R ¹⁰ , Y and a are the same as above) is easily available. Is preferred. Alkenyl group for the alkenyl group present invention include, but are not limited, it is preferable that the general formula 7. H ₂ C ＝ C (R ¹¹ )-(7) (wherein, R ¹¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms) In the general formula 7, R ¹¹ is a hydrogen atom or a carbon atom having 1 to 20 carbon atoms.
There are 20 hydrocarbon groups, specifically, the following groups. _{- (CH 2) n -CH 3} , -CH (CH 3) -
_{(CH 2) n -CH 3,} -CH (CH 2 CH 3) - (CH 2)
_{n -CH 3, -CH (CH 2} CH 3) 2, -C (CH 3) 2 -
_{(CH 2) n -CH 3,} -C (CH 3) (CH 2 CH 3) -
_{(CH 2) n -CH 3,} -C 6 H 5, -C 6 H 5 (CH 3), -
_{C 6 H 5 (CH 3)} 2, - (CH 2) n -C 6 H 5, - (C
_{H 2) n -C 6 H 5} (CH 3), - (CH 2) n -C 6 H 5 (C
H ₃ ) ₂ (n is an integer of 0 or more, and the total carbon number of each group is 20
Hereinafter, among these, a hydrogen atom is preferable.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In the present invention, when a halogen is not directly involved in the 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 halogen having at least one highly reactive carbon-halogen bond may be used. Halide, or a sulfonyl halide compound as an initiator,
Obtained by radical polymerization of a vinyl monomer using a transition metal complex as a catalyst (atom transfer radical polymerization method).
At least one highly reactive carbon-halogen bond at the terminal
It is preferable to use a vinyl polymer having two or more vinyl polymers. The method (Af) is more preferable because the control is easier.

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

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

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

(Ba) When a vinyl polymer is synthesized by radical polymerization, for example, a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule as shown in the following general formula 15 may be used as a second compound. A method of reacting as a monomer. H ₂ C ＝ C (R ¹⁴ ) —R ¹⁵ —R ¹⁶ —OH (15) (wherein R ¹⁴ , R ¹⁵ and R ¹⁶ are the same as above) A polymerizable alkenyl group and a hydroxyl group in one molecule There is no limitation on the timing of reacting the compound having 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 the completion of the reaction of a predetermined monomer. Is preferred.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Among the above compounds having both an amino group and an oxyanion, the salts of aminophenols represented by the general formula 25 or the salts 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 comprise also good to 19 carbon atoms and .R ¹² is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, two R ¹² are different may be the same with each other And M ⁺ may be mutually connected at the other end to form a cyclic structure. M ⁺ is the same as described above.) The compound having an oxyanion represented by any one of the general formulas 24 to 26 has the general formula It can be easily obtained by reacting the compound represented by No. 23 with a basic compound.

Various compounds can be used as the basic compound. For example, sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, sodium-tert-butoxide, potassium-tert-butoxide, sodium carbonate, potassium carbonate, lithium carbonate, hydrogen hydrogen carbonate Sodium, sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, methyllithium, ethyllithium, n-butyllithium, ter
t-butyllithium, lithium diisopropylamide,
Lithium hexamethyldisilazide and the like. The amount of the base used is not particularly limited, but is 0.5 to 5 equivalents, preferably 0.8 to 1.2 equivalents, based on the precursor.

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

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

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

When the amino group of the amino group-containing compound used in the nucleophilic substitution reaction affects the nucleophilic substitution reaction, it is preferable to protect the amino group with a suitable substituent. Such substituents include a benzyloxycarbonyl group,
Examples thereof include a tert-butoxycarbonyl group and a 9-fluorenylmethoxycarbonyl group.

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

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

The compound represented by the general formula 28 is not particularly limited, and specific examples of R ¹³ include, for example,-
_{H, -CH 3, -CH 2 CH} 3, - (CH 2) n CH 3 (n represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -
CN, etc., and is preferably -H, -CH _3. M ⁺ is a counter cation of the oxyanion, and examples of M ⁺ include an alkali metal ion, specifically, a lithium ion, a sodium ion, a potassium ion, and a quaternary ammonium ion. Examples of the quaternary ammonium ion include a tetramethylammonium ion, a tetraethylammonium ion, a tetrabenzylammonium ion, a trimethyldodecylammonium ion, a tetrabutylammonium ion, and a dimethylpiperidinium ion, and a sodium ion and a potassium ion are preferable. The amount of the oxyanion of the general formula 28 to be used is preferably 1 to 5 equivalents, more preferably 1.0 to 1.2 equivalents, to the halogen group of the general formula 27. The solvent for carrying out this reaction is not particularly limited, but a polar solvent is preferred because it is a nucleophilic substitution reaction.For example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphonic Triamide, acetonitrile, and the like are used. The temperature at which the reaction is carried out is not limited.
The reaction is preferably carried out at a temperature of 50 ° C. to room temperature to 100 ° C. in order to retain a polymerizable terminal group.

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

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

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

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

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

(D) Stabilization of a vinyl polymer having at least one carbon-halogen bond represented by the general formula 27 obtained by atom transfer radical polymerization and having a hydroxyl group represented by the general formula 33 A method in which a halogen is substituted by reacting a carbanion. ^{M + C - (R 36)} (R 37) 35 -OH (33) ( wherein -R, R ³⁵ are the same as those described above .R ³⁶ and R ³⁷ together carbanion C ^- electrons stabilize The attraction group, or one of them, represents the above-mentioned electron withdrawing group and the other represents hydrogen or an alkyl group having 1 to 10 carbon atoms or a phenyl group.
^Examples of the electron withdrawing group for R ³⁶ and R ³⁷ include —CO ₂ R (ester group), —C (O) R (keto group), and —CON
(R ₂ ) (amide group), —COSR (thioester group), —CN (nitrile group), —NO ₂ (nitro group) and the like. The substituent R is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 20 carbon atoms.
And preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group. As R ³⁶ and R ³⁷ , —CO ₂ R, —C (O) R and —CN are particularly preferred. (E) General formula 27 obtained by atom transfer radical polymerization
A vinyl polymer having at least one carbon-halogen bond represented by is reacted with a metal simple substance such as zinc or an organometallic compound to prepare an enolate anion, and then an aldehyde or ketone is prepared. How to react.

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

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

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

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

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

In order to make better use of weather resistance, it is preferable to use a diisocyanate compound having no aromatic ring, such as hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate. << Sealant Composition >> Some of the sealant compositions of the present invention require a curing catalyst or a curing agent depending on each crosslinkable functional group. Further, various compounding agents may be added according to the desired physical properties. <Curing Catalyst / Curing Agent> In the case of a crosslinkable silyl group A polymer having a crosslinkable silyl group is crosslinked and cured by forming a siloxane bond in the presence or absence of various conventionally known condensation catalysts. As the properties of the cured product, a wide range from rubbery to resinous can be prepared according to the molecular weight of the polymer and the main chain skeleton.

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

In the sealing material composition of the present invention,
For greater activity of the condensation catalyst of the general formula _{^{37 R 49 a Si (OR 50}} ) 4-a (37) ( wherein, R ⁴⁹ and R ^50, each independently, a carbon number 1
To 20 substituted or unsubstituted hydrocarbon groups. A is 0, 1, 2, or 3. ), A silicon compound having no silanol group may be added.

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

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

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

[0148]

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

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

[0150]

Embedded image (Wherein, R ⁵⁷ represents hydrogen or a methyl group.
i ≦ 10 and j are integers satisfying 0 ≦ j ≦ 8 and 3 ≦ i + j ≦ 10. C ₆ H ₅ represents a phenyl group. ) The hydrosilyl group-containing compound further includes a low molecular weight compound having two or more alkenyl groups in the molecule represented by the following general formula 3
Compounds obtained by subjecting the hydrosilyl group-containing compounds represented by Nos. 8 to 44 to an addition reaction so that some hydrosilyl groups remain even after the reaction can also be used. Various compounds can be used as the compound having two or more alkenyl groups in the molecule. To illustrate, 1,
Hydrocarbon compounds such as 4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene and 1,9-decadiene;
O'-diallylbisphenol A, ether compounds such as 3,3'-diallylbisphenol A, ester compounds such as diallyl phthalate, diallyl isophthalate, triallyl trimellitate and tetraallyl pyromellitate, diethylene glycol diallyl carbonate and the like And carbonate-based compounds.

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

[0152]

Embedded image The polymer and the curing agent can be mixed in any ratio, but from the viewpoint of curability, the molar ratio of the alkenyl group to the hydrosilyl group is preferably in the range of 5 to 0.2, and more preferably 2.5 to 0.2. It is particularly preferred that the value be 0.4. When the molar ratio is 5 or more, only a cured product with insufficient curing and insufficient tackiness is obtained, and when it is less than 0.2, a large amount of active hydrosilyl groups remains in the cured product even after curing. , Cracks and voids are generated, and a uniform and strong cured product cannot be obtained.

The curing reaction between the polymer and the curing agent proceeds by mixing and heating the two components, but a hydrosilylation catalyst can be added to accelerate the reaction more quickly. Such a hydrosilylation catalyst is not particularly limited, and examples thereof include a radical initiator such as an organic peroxide and an azo compound, and a transition metal catalyst.

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

The transition metal catalyst is not particularly limited, either. For example, platinum solid, dispersion of platinum solid in a carrier such as alumina, silica or carbon black, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, Examples include a complex with a ketone, a platinum-olefin complex, and a platinum (0) -divinyltetramethyldisiloxane complex. Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , R
hCl ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl
_{3, PdCl 2 · H 2 O} , NiCl 2, TiCl 4 , and the like. These catalysts may be used alone or in combination of two or more. The amount of the catalyst is not particularly limited, but 1 mol of the alkenyl group of the vinyl polymer (I).
On the other hand, the amount is preferably in the range of 10 ^-1 to 10 ^-8 mol, and more preferably in the range of 10 ^-3 to 10 ^-6 mol. If the amount is less than 10 ^-8 mol, the curing does not proceed sufficiently. In addition, since the hydrosilylation catalyst is expensive, it is 10 ^-1.
It is preferable not to use more than mol.

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

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

Hereinafter, these crosslinking reactions will be described in detail.

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.

[0161]

Embedded image

[0162]

Embedded image

[0163]

Embedded image

[0164]

Embedded image

[0165]

Embedded image Styrene-based monomers include styrene, α-methylstyrene, etc., acrylamide-based monomers include acrylamide, N, N-dimethylacrylamide, etc., and conjugated diene-based monomers include butadiene and isoprene.
Examples of the vinyl ketone-based monomer include methyl vinyl ketone.

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

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

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

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

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

The photopolymerization initiator used in the present invention is not particularly limited, but a photoradical initiator and a photoanion initiator are preferable, and a photoradical initiator is particularly preferable. For example, acetophenone, propiophenone, benzophenone, xanthol, fluorein, benzaldehyde,
Anthraquinone, triphenylamine, carbazole,
3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophen, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone 4,4'-dimethoxybenzophenone,
4-chloro-4′-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-
Chloro-8-nonyl xanthone, benzoyl, benzoin methyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzyl methoxy ketal, 2-chlorothioxanthone and the like. These initiators may be used alone or in combination with other compounds. Specific examples include a combination with an amine such as diethanolmethylamine, dimethylethanolamine, and triethanolamine, further combined with an iodonium salt such as diphenyliodonium chloride, and a combination with a dye and an amine such as methylene blue. Can be

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

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

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

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 3
3), 2,2'-azobis (2-amidinopropane) dihydrochloride (VAZO 50), 2,2'-azobis (2,
4-dimethylvaleronitrile) (VAZO 52),
2,2'-azobis (isobutyronitrile) (VAZO
64), 2,2'-azobis-2-methylbutyronitrile (VAZO 67), 1,1-azobis (1-cyclohexanecarbonitrile) (VAZO 88) (all available from DuPont Chemical), 2,
2'-azobis (2-cyclopropylpropionitrile) and 2,2'-azobis (methylisobutyl
G) (V-601) (available from Wako Pure Chemical Industries).

Suitable peroxide initiators include, but are not limited to, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, 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; And tertiary amines, such as systems based on benzoyl peroxide and dimethylaniline; and systems based on organic hydroperoxides and transition metals, such as systems based on cumene hydroperoxide and cobalt naphthate.

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

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

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

The method for curing the thermosetting composition of the present invention is not particularly limited. The temperature varies depending on the type of the thermal initiator, the polymer (I), the compound to be added, etc. 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 the adhesion imparting agent is added, the danger that the sealing material peels off from the siding board can be further reduced because the joint width or the like fluctuates due to external force. 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) aminopropyl Methyldiethoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-
Amino group-containing silanes such as γ-aminopropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-
Mercapto group-containing silanes such as mercaptopropylmethyldimethoxysilane and γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxy Epoxy group-containing silanes such as silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β
Carboxysilanes such as -carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyl Vinyl-type unsaturated group-containing silanes such as oxypropylmethyldimethoxysilane and γ-acroyloxypropylmethyltriethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; tris (trimethoxysilyl) isocyanurate And the like isocyanurate silanes. Amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, and the like, which are derivatives thereof, can also be used as the silane coupling agent. .

The silane coupling agent used in the present invention is
Usually, 0.1 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 the addition amount is too large, the cured product obtained by curing the sealing material composition loses rubber elasticity, and may not function as a sealing material. In addition, when adding to a two-component type described later,
It is preferred that the total amount added to both components be within the above range. The effect of the silane coupling agent to be added to the sealing material composition of the present invention is various adherends, that is, glass, aluminum, stainless steel, zinc, copper, an inorganic base such as mortar, PVC, acrylic,
When used for an organic substrate such as polyester, polyethylene, polypropylene, and polycarbonate, it exhibits a remarkable effect of improving adhesiveness under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving the adhesion to various adherends is particularly significant.

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

The above-mentioned adhesiveness-imparting agents may be used alone or in combination of two or more. The addition of these adhesion-imparting agents can improve the adhesion to the adherend. <Plasticizer> Various plasticizers are used in the sealing material composition of the present invention as needed. The plasticizer is not particularly limited, but for the purpose of adjusting physical properties, adjusting properties, etc.,
For example, dibutyl phthalate, diheptyl phthalate,
Phthalates such as di (2-ethylhexyl) phthalate and butylbenzyl phthalate; non-aromatic dibasic esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate and isodecyl succinate; butyl oleate and acetyl ricinolinol Esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; phosphates such as tricresyl phosphate and tributyl phosphate; trimellitic esters Polystyrenes such as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene; Fin like; alkyl diphenyl,
Hydrocarbon oils such as partially hydrogenated terphenyl; process oils; polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol; and derivatives obtained by converting hydroxyl groups of these polyether polyols into ester groups, ether groups, and the like. Polyethers such as epoxidized soybean oil and benzyl epoxy stearate; dibasic acids such as sebacic acid, adipic acid, azelaic acid and 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; seed Can be used in the above mixing, it does not necessarily need. In addition, these plasticizers can be blended at the time of polymer production.

The amount of the plasticizer used is not limited, but may be 5 to 100 parts by weight of the vinyl polymer (I).
The amount is from 150 to 150 parts by weight, preferably from 10 to 120 parts by weight, more preferably from 20 to 100 parts by weight. If it is less than 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product will be insufficient. <Filler> Various fillers are used as needed in the sealing material composition 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 hull powder, graphite, diatomaceous earth, clay, fumed silica, and precipitated silica. Reinforcing fillers such as crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid, carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, Fillers such as titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, zinc dust and shirasu balloon; fibrous such as asbestos, glass fiber and filament Fillers and the like. Among these fillers, precipitated silica, fumed silica, crystalline silica, fused silica, dolomite, carbon black, calcium carbonate, titanium oxide, and talc are preferred. In particular, when it is desired to obtain a cured product having high strength with these fillers, mainly fumed silica, precipitated silica,
A filler selected from silicic anhydride, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, crystalline silica, fused silica, calcined clay, clay, activated zinc white and the like can be added. Also, when it is desired to obtain a cured product having low strength and large elongation, mainly titanium oxide, calcium carbonate,
A filler selected from talc, ferric oxide, zinc oxide, shirasu balloon and the like can be added. In general,
If the specific surface area of calcium carbonate is small, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product may not be sufficient. As the value of the specific surface area is larger, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product becomes larger. Further, it is more preferable that calcium carbonate has been subjected to surface treatment using a surface treatment agent. When the surface-treated calcium carbonate is used, the workability of the composition of the present invention is improved as compared with the case where the surface-treated calcium carbonate is not used, and the adhesiveness and weather resistance of the sealing material composition are improved. It is considered that the improvement effect is further improved.
As the surface treatment agent, organic substances such as fatty acids, fatty acid soaps and fatty acid esters and various surfactants, and various coupling agents such as silane coupling agents and titanate coupling agents are used. Specific examples include, but are not limited to, caproic acid, caprylic acid,
Fatty acids such as pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid and the like, salts of these fatty acids such as sodium and potassium, and alkyl esters of these fatty acids Can be 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 treatment amount of this surface treatment agent is
The treatment is preferably performed in the range of 0.1 to 20% by weight, more preferably in the range of 1 to 5% by weight, based on calcium carbonate. 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 composition may be insufficient. May drop. <Addition amount> When the filler is used, the amount of the filler is 5 to 100 parts by weight based on 100 parts by weight of the vinyl polymer (I).
It is preferably used in the range of 0 parts by weight,
More preferably, it is used in the range of 40 parts by weight.
It is particularly preferred to use it in the range of 0 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. Performance may be reduced. 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 composition of the present invention, if necessary.

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

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. Other Additives Various additives may be added to the sealing material composition of the present invention as needed for the purpose of adjusting various properties of the sealing material composition or the cured product. Examples of such additives include, for example, flame retardants, curability modifiers, antioxidants, radical inhibitors, ultraviolet absorbers, metal deactivators,
Ozone deterioration inhibitor, light stabilizer, phosphorus peroxide decomposer,
Examples include a lubricant, a pigment, a foaming agent, a fungicide, a rust preventive, and a photocurable resin. These various additives may be used alone or in combination of two or more.

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

The sealing material composition of the present invention can be prepared as a one-component type in which all the components are premixed, sealed and stored, and cured by the moisture in the air after application. Ingredients such as a filler, a plasticizer, and water may be blended in advance, and the blended material and the polymer composition may be mixed before use to prepare a two-component type. 2
In the case of the component type, a coloring agent can be added when mixing the two components, and when providing a sealing material that matches the color of the siding board, it is possible to perform abundant color alignment with limited stock. For example, it is easier to cope with multicolor demands from the market, and is more preferable for low-rise buildings and the like. As the colorant, for example, a pigment and a plasticizer, and in some cases, a mixture of a filler and a paste are used to facilitate the operation. Further, by adding a retarder when mixing the two components, the curing speed can be finely adjusted at the work site. << Curing Product >> The heat compression recovery ratio in the present invention is J
After one cycle at 90 ° C. according to the durability test listed in the Annex of IS A 5758 for reference,
Using the numbers measured after standing at room temperature for one day,
It is calculated by the formula. (Heating compression recovery rate) = (L ₂ −L ₁ / L ₀ −L ₁ ) × 100 (A) (where L _{0 is} the thickness of the sealing material in the compression direction before heating and compression, and L _{1 is} the thickness during heating and compression. Thickness in the compression direction of the sealing material, L ₂ : Thickness in the compression direction after one cycle of the above JIS durability 9030 test and standing at room temperature for one day. In the above, the cured product obtained by curing the sealing material composition preferably has a heat compression recovery ratio of 10% or less.

The stress relaxation property in the present invention is defined by JIS
It is represented by the value measured using the same test specimen as the H-type tensile adhesiveness of A 5758. That is, using an adherend having a size of 50 × 50 mm square, a test body joined with a sealing material so as to have a width of 12 mm (12 × 12 × 50 mm) is prepared. This specimen was heated at 23 ° C. and 55% R.C. H. After curing for 28 days at 23.degree. H. At 50%. That is, the width of the sealing material between the adherends is set to the first 1
It extends from 2 mm to 18 mm and is fixed with a spacer or the like. After standing for 14 days while being stretched, the spacer is removed and the stretch is released, and immediately the width between the adherends is measured. Assuming that the width of 12 mm between the adherends before extension is 0% and the width of 18 mm between the adherends during extension is 100%, the width of the sealing material between the adherends after release of extension is 1
Expressed as a 00 fraction. The value represented by this 100 percentage is defined as the stress relaxation property in the present invention.

The cured product obtained by curing the sealing material composition of the present invention has a stress relaxation of 80% after deformation by external force.
It is preferable to achieve the above.

The cured product having a thickness of 100 μm or less obtained by curing the sealing material composition of the present invention containing a filler preferably has a weather resistance of 120 hours or more in a sunshine weather meter test, and has a weather resistance of 240 hours or more. It is still more preferable to exhibit the weather resistance of 1000 hours or more.

Further, a cured product having a thickness of 100 μm or less obtained by curing the vinyl polymer (I) of the present invention without adding a filler or the like exhibits weather resistance of not less than 20 hours in a sunshine weather meter test. More preferably, it exhibits 60 hours or more of weather resistance, further preferably 120 hours or more of weather resistance, and more preferably 500 hours or more of weather resistance.

The weather resistance of the cured product having a thickness of 100 μm or less in the present invention is determined by visually observing the surface of the cured product. For example, a weather resistance of 20 hours or more means that the surface is wavy or disappears due to elution of the polymer,
Alternatively, it means that an initial good surface state is maintained for 20 hours or more without being changed by cracking, discoloration (in the case of a colored product), whitening (chalking), or the like.

The weather resistance test in the present invention is as follows.
Refers to the test according to JIS A 1415 WS type.

[0200]

EXAMPLES Hereinafter, specific examples of the present invention will be described together with comparative examples, but the present invention is not limited to the following examples.

In the following Examples and Comparative Examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

In the following examples, "number average molecular weight" and "molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)"
Is a gel permeation chromatography (GP
Calculated by standard polystyrene conversion method using C).
However, a GPC column filled with a polystyrene cross-linked gel (shodex GPC K-804; manufactured by Showa Denko KK) was used, and chloroform was used as a GPC solvent. (Production Example 1) In a 2 L separable flask equipped with a reflux tube and a stirrer, CuBr (8.39 g, 0.0585 m
ol), and the inside of the reaction vessel was purged with nitrogen. Add acetonitrile (112 mL) and add 3 at 70 ° C in an oil bath.
Stirred for 0 minutes. Add butyl acrylate (224m
L) Diethyl 2,5-dibromoadipate (23.4)
g, 0.0650 mol) and pentamethyldiethylenetriamine (0.500 mL, 0.244 mmol) (hereinafter triamine) were added to initiate the reaction. 7
While stirring with heating at 0 ° C., butyl acrylate (895 m
L) was continuously dropped over 150 minutes. During the dropping of butyl acrylate, triamine (2.50 mL, 12.0 mL
mmol) was added. 310 minutes after the start of the reaction, 1,7-octadiene (288 mL, 1.95 mol
l), triamine (4.0 mL, 0.0195 mol)
Was added and the mixture was heated and stirred at 70 ° C. for 240 minutes. After diluting the reaction mixture with hexane and passing through an activated alumina column, volatile components were distilled off under reduced pressure to obtain an alkenyl group-terminated polymer (polymer [1]). The number average molecular weight of the polymer [1] was 20,000, and the molecular weight distribution was 1.3.
Polymer [1] is placed in a 2 L separable flask equipped with a reflux tube.
(1.0 kg), potassium benzoate (34.8 g),
N, N-dimethylacetamide (1 L) was charged and heated and stirred at 70 ° C. for 15 hours under a nitrogen stream. N,
After removing N-dimethylacetic acid amide, the mixture was diluted with toluene. Solids insoluble in toluene (KBr and excess potassium benzoate were filtered through an activated alumina column. The volatiles in the filtrate were distilled off under reduced pressure to obtain a polymer [2]. 2 L round bottom flask equipped with a reflux tube In addition, polymer [2] (1k
g), aluminum silicate (200 g, Kyowa Chemical Co., Ltd., Kyoward 700 PEL), and toluene (1 L) were charged and heated and stirred at 100 ° C. for 5.5 hours under a nitrogen stream. After the aluminum silicate was removed by filtration, the toluene in the filtrate was distilled off under reduced pressure to obtain a polymer [3]. In a 1 L pressure-resistant reaction vessel, polymer [3] (718.80 g), dimethoxymethylhydrosilane (27.55 mL, 0.223 mol), methyl orthoformate (8.14 mL, 0.074 mmol),
And zero-valent platinum 1,1,3,3-tetramethyl-1,
A 3-divinyldisiloxane complex was charged. However, the amount of the platinum catalyst used was 5 × 10 ⁻⁴ equivalent in molar ratio to the alkenyl group of the polymer. The reaction mixture is
Heated for 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 was 23,000 by GPC measurement (in terms of polystyrene), 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) To 100 parts of the polymer [4] obtained in Production Example 1, 150 parts of calcium carbonate (white luster CCR: made of Shiraishi calcium) and 50 parts of a plasticizer (DOP) were mixed.
Using a divalent Sn catalyst (dibutyltin diacetylacetonate), a specimen having the same H-type tensile adhesiveness as JIS A 5758 was prepared and cured in a room for 2 days at 50 ° C. for 3 days to obtain a cured product. . Comparative Example 1 A cured product was obtained in the same manner as in Example 1 except that a mixture of 3 parts of tin octylate and 1 part of laurylamine was used as the divalent Sn catalyst instead of the tetravalent Sn catalyst used in Example 1. Was prepared. (Evaluation 1) The heat compression restoration ratio of each cured product was measured. The results are shown in Table 1. (Evaluation 2) Further, each cured product was subjected to a tensile deformation of 30%, allowed to stand at room temperature for one month, and then observed for adhesion. The results are shown in Table 1.

[0203]

[Table 1] (Example 2) 5 parts of titanium oxide (rutile type: Taipaque R820, manufactured by Ishihara Sangyo) and 0.1 parts of carbon black (# 55G: manufactured by Asahi Carbon) were added to 100 parts of the polymer [4] obtained in Production Example 1. , And a cured product having a thickness of about 100 μm was applied on an aluminum plate using a tetravalent Sn catalyst (dibutyltin diacetylacetonate).
After curing and curing at 3 ° C. for 3 days, a thin layer cured product was obtained. (Evaluation 3) The cured product obtained in Example 2 was measured using a xenon weather meter (Suga Test Machine SX120, 300 to 400).
irradiance of 180 W / m ² in nm, black panel temperature of 63 ° C., irradiation for 2 hours and rainfall of 18 minutes) for 4000 h
Irradiation was performed and the surface condition was observed thereafter. No abnormalities such as whitening and cracks were observed. The degree of acceleration of deterioration by the xenon weather meter used in this example is as follows.
From another experiment, it was compared with the WS type of JISA 1415 (although the irradiation conditions and the like were the same), and it was confirmed in advance that the composition of the vinyl polymer was equal to or higher than that of the composition. I have.

[0204]

According to the present invention, at least one crosslinkable functional group is provided.
It is made of a sealing material composition for a siding board comprising the vinyl polymer (I), and the cured product is excellent in durability including adhesion and appearance.

Claims (27)

[Claims] 1. A siding board sealing material composition comprising a vinyl polymer (I) having at least one crosslinkable functional group. 2. The molecular weight distribution of the vinyl polymer (I) is 1.
The sealant composition according to claim 1, which is less than 8. 3. The main chain of the vinyl polymer (I) is (meth)
2. The method according to claim 1, wherein the monomer is produced by mainly polymerizing a monomer selected from the group consisting of an acrylic monomer, an acrylonitrile monomer, an aromatic vinyl monomer, a fluorine-containing vinyl monomer and a silicon-containing vinyl monomer.
Or the sealing material composition of 2. 4. The sealing material composition according to claim 1, wherein the vinyl polymer (I) is a (meth) acrylic polymer. 5. The sealing material composition according to claim 1, wherein the vinyl polymer (I) is an acrylic polymer. 6. The sealing material composition according to claim 5, wherein the vinyl polymer (I) is an acrylate polymer. 7. The sealing material composition according to claim 6, wherein the vinyl polymer (I) is a butyl acrylate polymer. 8. The crosslinkable functional group of the vinyl polymer (I) is
The sealing material composition according to any one of claims 1 to 7, which is a crosslinkable silyl group. 9. The crosslinkable functional group of the vinyl polymer (I) is
The sealing material composition according to any one of claims 1 to 7, which is an alkenyl group. 10. The sealing material composition according to claim 1, wherein the crosslinkable functional group of the vinyl polymer (I) is a hydroxyl group. 11. The sealing material composition according to claim 1, wherein the crosslinkable functional group of the vinyl polymer (I) is an amino group. 12. The method according to claim 1, wherein the crosslinkable functional group of the vinyl polymer (I) is a group having a polymerizable carbon-carbon double bond. Sealant composition. 13. The sealing material composition according to claim 1, wherein the crosslinkable functional group of the vinyl polymer (I) is an epoxy group. 14. The sealing material composition according to claim 1, wherein the main chain of the vinyl polymer (I) is produced by a living radical polymerization method. . 15. The sealing material composition according to claim 14, wherein the living radical polymerization is atom transfer radical polymerization. 16. The method according to claim 7, wherein the atom transfer radical polymerization comprises
The sealing material composition according to claim 15, wherein the catalyst is a complex selected from transition metal complexes having a group metal of Group 8, Group 8, Group 9, Group 10, or Group 11 as a central metal. 17. The sealing material composition according to claim 16, wherein the metal complex used as a catalyst is a complex selected from the group consisting of copper, nickel, ruthenium, and iron complexes. 18. The sealant composition according to claim 17, wherein the metal complex used as a catalyst is a copper complex. 19. The sealing according to claim 1, wherein the cured product obtained by curing the composition comprising the vinyl polymer (I) has a heat compression recovery ratio of 10% or less. Material composition. 20. A cured product obtained by curing a composition comprising a vinyl polymer (I) has a stress relaxation property of 8 after deformation by an external force.
The sealing material composition according to any one of claims 1 to 19, which achieves 0% or more. 21. A cured product having a thickness of 100 μm or less, obtained by curing a composition comprising a vinyl polymer (I) containing a filler, exhibits a weather resistance of 120 hours or more in a sunshine weather meter test. Item 21. The sealing material composition according to any one of Items 1 to 20. 22. A cured product having a thickness of 100 μm or less, obtained by curing a composition comprising a vinyl polymer (I) containing a filler, exhibits a weather resistance of 240 hours or more in a sunshine weather meter test. Item 23. The sealing material composition according to Item 21. 23. A cured product having a thickness of 100 μm or less obtained by curing a composition comprising a vinyl polymer (I) containing a filler, exhibits a weather resistance of 1000 hours or more in a sunshine weather meter test. Item 23. The sealing material composition according to Item 21. 24. A vinyl polymer containing no filler (I)
24. The sealing material composition according to any one of claims 1 to 23, wherein a cured product having a thickness of 100 µm or less obtained by curing the composition comprising: exhibits a weather resistance of 20 hours or more in a sunshine weather meter test. 25. A vinyl polymer containing no filler (I)
25. The sealing material composition according to claim 24, wherein a cured product having a thickness of 100 μm or less obtained by curing a composition comprising: exhibits a weather resistance of 60 hours or more in a sunshine weather meter test. 26. A vinyl polymer (I) containing no filler
25. The sealing material composition according to claim 24, wherein a cured product having a thickness of 100 μm or less obtained by curing the composition comprising: exhibits a weather resistance of 120 hours or more in a sunshine weather meter test. 27. A vinyl polymer containing no filler (I)
25. The sealing material composition according to claim 24, wherein a cured product having a thickness of 100 μm or less obtained by curing the composition comprising: exhibits a weather resistance of 500 hours or more in a sunshine weather meter test.