JP2008050448A - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition providing a cured product excellent in recoverability and creep resistance, having little surface tackiness within a short period after curing, having little stain of the surface over a long period, not causing crack and discoloration on the surface even under long-term use outdoors and excellent in weather resistance. <P>SOLUTION: The curable composition comprises (A) a vinylic polymer having at least one crosslinkable silyl group represented by general formula (1): -[Si(R<SP>1</SP>)<SB>2-b</SB>(Y)<SB>b</SB>O]<SB>m</SB>-Si(R<SP>2</SP>)<SB>3-a</SB>(Y)<SB>a</SB>, (B) a carboxylic acid metal salt and/or (C) a carboxylic acid and/or carboxylic acid derivative and (D) amine compounds, and the amine compounds (D) are composed of at least two kinds of compounds and at least one thereof is a primary and/or secondary amine compound having ≥20°C melting point. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a curable composition comprising a vinyl polymer having at least one crosslinkable silyl group as a main component.

An organic polymer containing at least one crosslinkable silyl group in the molecule is crosslinked at room temperature by the formation of a siloxane bond accompanied by a hydrolysis reaction of a reactive silicon group due to moisture or the like. It is known to have an interesting property of being obtained.
Among these polymers having a crosslinkable silyl group, (A) a vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1), and (F) represented by the general formula (1) Polyether polymers having at least one crosslinkable silyl group have been disclosed (Patent Documents 1 to 7), which are already industrially produced and widely used in applications such as sealing materials, adhesives and paints. .

Adhesive resins used in interior panel adhesives, exterior panel adhesives, tile adhesives, stone adhesives, wall finish adhesives, vehicle panel adhesives, etc. If the creep resistance is poor, the adhesive layer may be deformed over time due to the weight of the adherend or external stress, and the panel, tile, stone, etc. may be displaced. Also, in the case of ceiling finishing adhesives and floor finishing adhesives, if the resilience and creep resistance are inferior, the adhesive layer may be deformed over time, resulting in unevenness of the ceiling surface or floor surface. Furthermore, if the adhesive for electrical / electronic / precision equipment assembly has poor resilience and creep resistance, the adhesive layer may be deformed over time, leading to equipment performance degradation. Therefore, these adhesive compositions are required to be excellent in resilience and creep resistance.

Sealing materials are generally used for the purpose of filling watertightness and airtightness by filling joints and gaps between various members. Therefore, since followability to the use site over a long period of time is extremely important, the cured product is required to have high elongation and high strength. In particular, sealing materials for working joints (caps, glass, window frames, sashes, curtain walls, various exterior panels) of buildings with large joint width fluctuations, direct glazing, and double-glazing The composition used for the sealant for the SSG method is required to have excellent resilience and durability.
These curable compositions containing an organic polymer having a reactive silicon group are cured using a silanol condensation catalyst and usually have a carbon-tin bond such as dibutyltin bis (acetylacetonate). Organotin catalysts are widely used. However, in recent years, the toxicity of organotin compounds has been pointed out, and when an organotin catalyst is used, there is a problem that the restorability and creep resistance of the curable composition are poor.

On the other hand, a divalent carboxylic acid tin salt can also be used as a silanol condensation catalyst (Patent Documents 8 to 11). When this divalent carboxylic acid tin salt is used, a cured product having improved restoration rate and creep resistance can be obtained. The divalent carboxylic acid tin salt can be improved in curability when used in combination with a carboxylic acid. However, even when a catalyst in which a divalent carboxylic acid tin salt and a carboxylic acid described in the above patent are used in combination, there is still a case where there is no practical curability.
On the other hand, a curable composition containing a polymer having a crosslinkable silyl group is filled with a sealing material for construction to prevent the invasion of wind and rain by filling between the interior and exterior members of the building and the joint joint, and various bases. It is used as an adhesive for bonding materials. A so-called modified silicone sealant having a polyoxyalkylene polymer with a main chain structure and a crosslinkable silyl group is widely used because of its good workability and flexibility in a wide temperature range. There is a problem that the weather resistance is insufficient to meet the long-term durability needs, and the surface of the sealing material after the construction remains sticky (hereinafter referred to as surface tack) for a long time, resulting in the surface of the sealing material becoming dirty. .

In order to reduce the surface tack, an air curable compound typified by dry oil is added (Patent Document 12), but the short-term surface tack reducing effect is insufficient.
In addition, a method of adding a photocurable compound has been proposed (Patent Document 13), but this also has an insufficient short-term surface tack reduction effect, and the surface hardness is high when polymerization proceeds in the long term. And the surface is easily broken.
It has been proposed to add a silicone surfactant, an air curable compound and a polyoxyalkylene polymer to the modified silicone sealant (Patent Document 14), but the long-term surface tack improvement effect is small, and the weather resistance The nature is also insufficient.
Also, a method of combining a modified silicone sealant with a silicone surfactant, an air curable compound, and a photocurable compound has been proposed (Patent Document 15), but this also has insufficient weather resistance.
JP-A-52-73998 Japanese Patent Laid-Open No. 5-125272 JP-A-3-72527 Japanese Patent Laid-Open No. 63-6003 JP 09-272714 A Japanese Patent Laid-Open No. 11-043512 JP 2000-154205 A JP 55-9669 A Japanese Patent No. 3062626 JP-A-6-322251 JP 2000-345054 A Japanese Patent Publication No. 5-82860 Japanese Examined Patent Publication No. 62-26349 JP 2000-204346 A JP 2000-204347 A

An object of the present invention is to provide a curable composition comprising as a main component a vinyl polymer having at least one crosslinkable silyl group, and is excellent in resilience and creep resistance, with improved surface tack and a long-term surface. It is an object of the present invention to provide a curable composition that can give a cured product having a good weather resistance so that cracks and discoloration do not occur on the surface even under long-term outdoor use.

As a result of intensive studies to solve such problems, the present inventors have (B) carboxylic acid metal salt and / or (C) carboxylic acid and / or as a curing catalyst for vinyl polymer. Or, by using a carboxylic acid derivative and further using (D) an amine compound, it exhibits a sufficiently practical curability while being a non-organotin catalyst, has good restorability and creep resistance, and further has a melting point. By using a primary and / or secondary amine compound having a temperature of 20 ° C. or higher, the surface tack after curing is improved, the surface is less soiled over a long period of time, and there are cracks on the surface even under long-term use outdoors. It has been found that a curable composition having good weather resistance that does not cause discoloration can be obtained, and the present invention has been achieved.

That is, the present invention
(A) Vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1)-[Si (R ¹ ) _2-b (Y) _b O] _m -Si (R ² ) _3-a (Y) _a (1)
{Wherein R ¹ and R ² are the same or different and are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) _3. A triorganosiloxy group represented by SiO- (R 'represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different); When two or more R ¹ or R ² are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2 or 3, and b represents 0, 1 or 2. m shows the integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. },
(B) a carboxylic acid metal salt, and
(D) An amine compound is contained, and the (D) amine compound is composed of at least two kinds, at least one of which is a primary and / or secondary amine compound having a melting point of 20 ° C. or higher. It relates to a curable composition characterized.
Moreover, this invention relates to the said curable composition characterized by containing (C) carboxylic acid and / or a carboxylic acid derivative further.

Furthermore, the present invention provides:
(A) a vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1) (C) a carboxylic acid and / or a carboxylic acid derivative, and
(D) An amine compound is contained, and the (D) amine compound is composed of at least two kinds, at least one of which is a primary and / or secondary amine compound having a melting point of 20 ° C. or higher. It relates to a curable composition characterized.
Further, the present invention further refers to (F) a polyether polymer having at least one crosslinkable silyl group represented by the general formula (1) (hereinafter, simply referred to as “(F) polyether polymer”). The curable composition is characterized by comprising:

As a preferred embodiment, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography of the vinyl polymer of the component (A) is less than 1.8. Some of the above curable compositions;
(A) The said curable composition whose main chain of the vinyl polymer of a component is a (meth) acrylic polymer;
(A) The said curable composition whose principal chain of the vinyl polymer of a component is manufactured by the living radical polymerization method;
The curable composition wherein the main chain of the vinyl polymer (A) is produced by an atom transfer radical polymerization method;
The vinyl polymer of the component (A) is the curable composition having at least one crosslinkable silyl group represented by the general formula (1) at the molecular chain terminal.

As a preferred embodiment, the vinyl polymer as the component (A) has the following steps:
(1) A vinyl polymer having a halogen at its terminal is produced by radical polymerization of a vinyl monomer using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst,
(2) A vinyl polymer having an alkenyl group at the terminal is produced by reacting an oxyanion having an alkenyl group to replace halogen.
(3) reacting a hydrosilane compound having a crosslinkable silyl group represented by the general formula (1);
It is the said curable composition which is a polymer obtained by.

As a preferred embodiment, the carboxylic acid metal salt of the component (B) is tin carboxylate, lead carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, titanium carboxylate, zirconium carboxylate, hafnium carboxylate, carboxyl The curable composition which is at least one selected from vanadium acid, manganese carboxylate, iron carboxylate, cobalt carboxylate, nickel carboxylate and cerium carboxylate;
(B) The said curable composition whose component is a carboxylic acid tin salt;
(B) The said curable composition whose component is divalent carboxylic acid tin salt;
(B) The said curable composition whose carbon atom adjacent to the carbonyl group which comprises the carboxylic acid of a component is quaternary carbon;
(A) 100 parts by weight of component, or (F) when component is contained 0.01 to 20 parts by weight of component (B) with respect to a total of 100 parts by weight of component (A) and component (F) It is said curable composition characterized by doing.

In a preferred embodiment, the curable composition (C) is a fatty acid or a derivative thereof;
(C) The said curable composition whose carbon atom adjacent to the carbonyl group which comprises the carboxylic acid of a component is quaternary carbon;
(A) 100 parts by weight of the component, or (F) when the component is contained, 0.01 to 20 parts by weight of the (C) component with respect to 100 parts by weight of the total of the (A) component and the (F) component It is said curable composition characterized by doing.

In a preferred embodiment, the amine compound as component (D) includes an amine compound containing a hydrocarbon group having at least one hetero atom as a substituent;
The curable composition as described above, wherein the amine compound as the component (D) includes an amine compound containing a hydrocarbon group having a hetero atom on the 2nd to 4th carbon atoms;
100 parts by weight of component (A) or (F) When component (F) is included, 100 parts by weight of component (A) and component (F), and 0.1 to 20 parts by weight of component (D) It is said curable composition characterized by doing.

In a preferred embodiment, the primary and / or secondary amine compound having a melting point of 20 ° C. or higher is a compound that reacts with water to form a primary and / or secondary amine. The above curable composition.
In a preferred embodiment, the curable composition is characterized in that the polyether polymer of component (F) is essentially polypropylene oxide.

The present invention also relates to a sealing material using the curable composition and an adhesive using the curable composition.

Below, the curable composition of this invention is explained in full detail.
The curable composition of the present invention comprises:
(A) Vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1)-[Si (R ¹ ) _2-b (Y) _b O] _m -Si (R ² ) _3-a (Y) _a (1)
{Wherein R ¹ and R ² are the same or different and are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) _3. A triorganosiloxy group represented by SiO- (R 'represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different); When two or more R ¹ or R ² are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2 or 3, and b represents 0, 1 or 2. m shows the integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. },
(B) a carboxylic acid metal salt, and
(D) An amine compound is contained, and the (D) amine compound is composed of at least two kinds, at least one of which is a primary and / or secondary amine compound having a melting point of 20 ° C. or higher. It is a feature.
The curable composition may further contain (C) a carboxylic acid and / or a carboxylic acid derivative.
Moreover, the curable composition of the present invention comprises:
(A) a vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1) (C) a carboxylic acid and / or a carboxylic acid derivative, and
(D) An amine compound is contained, and the (D) amine compound is composed of at least two kinds, at least one of which is a primary and / or secondary amine compound having a melting point of 20 ° C. or higher. It is also a feature.

<< (A) Vinyl Polymer >>
The vinyl polymer having at least one crosslinkable silyl group represented by the following general formula (1) as the component (A) is crosslinked by forming a siloxane bond.
^{_{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
{Wherein R ¹ and R ² are the same or different and are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) _3. A triorganosiloxy group represented by SiO- (R 'represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different); When two or more R ¹ or R ² are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2 or 3, and b represents 0, 1 or 2. m shows the integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. }

The alkyl group having 1 to 20 carbon atoms of R ¹ and R ² is not particularly limited, and for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl, tetradecyl , Octadecyl and the like.
It does not specifically limit as a C6-C20 aryl group of R < ¹ >, R < ² >, For example, a phenyl group, a naphthyl group, a toluyl group etc. are mentioned.
The aralkyl group having 7 to 20 carbon atoms of R ¹ and R ² is not particularly limited, and examples thereof include a benzyl group and a phenylethyl group.
The monovalent hydrocarbon group having 1 to 20 carbon atoms of R ′ is not particularly limited, and for example, an alkyl group having 1 to 20 carbon atoms and the like are preferable, and specific examples thereof are the same as those described above.

The hydrolyzable group for Y is not particularly limited, and examples thereof include a hydrogen atom, a halogen 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 do. Of these, alkoxy groups are preferred because they are mildly hydrolyzable and easy to handle.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
As an alkoxy group, a C1-C20 thing is preferable, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned.
As the acyloxy group, those having 1 to 20 carbon atoms are preferable, and examples thereof include formyloxy group, acetyloxy group, propionyloxy group and the like.
Preferred examples of the ketoximate group include those having 1 to 20 carbon atoms.
As the alkenyloxy group, those having 2 to 20 carbon atoms are preferable, and examples thereof include a vinyloxy group, an allyloxy group, and a butenyloxy group.

Y can be bonded to one silicon atom in the range of 1 to 3. Further, in order to satisfy a + mb ≧ 1, at least one Y is included in the general formula (1). Further, the total sum of Y is preferably in the range of 1 to 5.
One silicon atom constituting the crosslinkable silyl group may be present, or two or more silicon atoms may be present. In the case of silicon atoms connected by a siloxane bond, up to about 20 may be used, and m is 0 to 19.

In particular, the general formula _{^{-Si (R 2) 3-a}} (Y) a
A crosslinkable silyl group represented by the formula (wherein R ² and Y are the same as described above, and a is an integer of 1 to 3) is preferable because it is easily available.

In the vinyl polymer of component (A), the number of crosslinkable silyl groups represented by the general formula (1) is at least 1 per molecule (that is, 1 or more on average per molecule). The number is not particularly limited as long as it is from the viewpoint of the curability of the composition and the physical properties of the cured product, but preferably 1.1 or more and 4.0 or less, more preferably 1.2 or more and 3.5 or less. is there.

The monomer constituting the main chain of the vinyl polymer (A) having at least one crosslinkable silyl group is not particularly limited as long as it is a vinyl monomer, and examples thereof include (meth) acrylic acid and (meth) acrylic. Methyl acid, (meth) acrylic acid ethyl, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid- tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid-n-heptyl, (meth) acrylic acid-n-octyl , (Meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecy , (Meth) acrylic acid phenyl, (meth) acrylic acid toluyl, (meth) acrylic acid benzyl, (meth) acrylic acid-2-methoxyethyl, (meth) acrylic acid-3-methoxypropyl, (meth) acrylic acid- 2-hydroxyethyl, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane , Ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, (meth) acrylic acid-2-perfluoroethylethyl, (meth) Acrylic acid-2-perfluoroethyl-2-perfluorobutylethyl , (Meth) acrylic acid-2-perfluoroethyl, (meth) acrylic acid perfluoromethyl, (meth) acrylic acid diperfluoromethyl methyl, (meth) acrylic acid-2-perfluoromethyl-2-perfluoroethyl (Meth) acrylic acid monomers such as methyl, (meth) acrylic acid-2-perfluorohexylethyl, (meth) acrylic acid-2-perfluorodecylethyl, (meth) acrylic acid-2-perfluorohexadecylethyl Styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene and vinylidene fluoride; vinyltrimethoxysilane, vinyl Silicon-containing resins such as triethoxysilane Maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide , Maleyl monomers such as octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl acetate , Vinyl esters such as vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; Examples include kennes; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, and the like.

These may be used alone or in combination of two or more.
In the above expression format, for example, (meth) acrylic acid indicates acrylic acid and / or methacrylic acid. The same applies to the following.
As the vinyl polymer having at least one crosslinkable silyl group, from the viewpoint of physical properties, (meth) acrylic obtained by synthesizing 40 wt% or more of (meth) acrylic acid monomer among the above monomers. A polymer is preferred.
Furthermore, an acrylic polymer obtained by synthesizing 30% by weight or more of an acrylic acid monomer among the above monomers is more preferable.

The molecular weight of the vinyl polymer (A) having at least one crosslinkable silyl group is not particularly limited, but is preferably in the range of 500 to 100,000. When the molecular weight is less than 500, the original characteristics of the vinyl polymer tend not to be expressed, and when it exceeds 100,000, handling tends to be difficult.

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

The method for synthesizing the vinyl polymer (A) having at least one crosslinkable silyl group is not particularly limited, and various methods can be used. However, from the viewpoint of the versatility of the monomer and ease of control, a method of directly introducing a crosslinkable silyl group into the main chain by radical polymerization, and a specification that can be converted to a crosslinkable silyl group by one or several steps of reaction A method of converting this specific functional group into a crosslinkable silyl group after obtaining a vinyl polymer having a functional group of 1 by radical polymerization is preferred.

The radical polymerization method used in the method of synthesizing a vinyl polymer having a specific functional group containing a crosslinkable silyl group has a specific functional group using an azo compound, a peroxide, or the like as a polymerization initiator. Classifying into “general radical polymerization method” in which monomers and vinyl monomers are simply copolymerized and “controlled radical polymerization method” in which specific functional groups can be introduced at controlled positions such as terminals. Can do.

The “general radical polymerization method” is a simple method and can be used in the present invention, but a monomer having a specific functional group is introduced into the polymer only stochastically. For this reason, when trying to obtain a polymer having a high functionalization rate, it is necessary to use a large amount of this monomer, and there is a problem that the control range of physical properties is narrowed. Conversely, if the amount of the monomer having the specific functional group is small, there is a problem that the proportion of the polymer into which the specific functional group is not introduced increases. Moreover, since it is free radical polymerization, there is also a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.

The “controlled radical polymerization method” further includes a “chain transfer agent method” in which a vinyl polymer having a functional group at a terminal is obtained by polymerization using a chain transfer agent having a specific functional group, It can be classified as a “living radical polymerization method” in which a polymer having a molecular weight almost as designed is obtained by growing the terminal without causing a termination reaction or the like.

The “chain transfer agent method” can obtain a polymer having a higher functionalization rate than the “general radical polymerization method” and can be used in the present invention. A chain transfer agent having a large amount of a specific functional group is necessary, and there is a problem in terms of economy including treatment. Further, like the above-mentioned “general radical polymerization method”, there is a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained because of free radical polymerization.

Unlike these polymerization methods, the “living radical polymerization method” is a radical polymerization that is difficult to control because the polymerization rate is high and a termination reaction due to coupling between radicals is likely to occur. It is difficult to obtain a polymer having a narrow molecular weight distribution (Mw / Mn is about 1.1 to 1.5), and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.
Accordingly, the “living radical polymerization method” can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and a monomer having a specific functional group can be introduced at almost any position of the polymer. The method for producing the vinyl polymer having the specific functional group is more preferable.

In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity and the molecular chain grows, but in general, the terminal is inactivated and the terminal is activated. It also includes pseudo-living polymerization that grows in an equilibrium state. The definition in the present invention is also the latter.
The “living radical polymerization method” is not particularly limited as long as it is a radical polymerization method that satisfies the above definition. This “living radical polymerization method” has been actively studied in various groups in recent years, and examples thereof include, for example, Journal of American Chemical Society (J. Am. Chem. Soc.), 1994. 116, using a cobalt porphyrin complex as shown in page 7943, using a radical scavenger such as a nitroxide compound as shown in Macromolecules, 1994, 27, 7228, Examples thereof include “Atom Transfer Radical Polymerization” (ATRP) using an organic halide as an initiator and a transition metal complex as a catalyst.

Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” for polymerizing vinyl monomers using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above “living radical polymerization method”. In addition to the features of ”, it has a halogen, which is relatively advantageous for functional group conversion reaction, at the end, and has a high degree of freedom in designing initiators and catalysts, so the production of vinyl polymers having specific functional groups More preferable as a method. As this atom transfer radical polymerization method, for example, Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614, Macromolecules (1995), 28, 7901, Science 1996, 272, 866, WO 96/30421, WO 97/18247 or Sawamoto et al., Macromolecules, 1995, 28, 1721, etc. Is mentioned.

Examples of the initiator in the above “atom transfer radical polymerization method” include organic halides, particularly organic halides having a highly reactive carbon-halogen bond, and sulfonyl halide compounds. Examples of the organic halide having a particularly highly reactive carbon-halogen bond include a carbonyl compound having a halogen at the α-position and a compound having a halogen at the benzyl-position. For example, initiators described in JP-A-11-130931, JP-A-11-158449 and the like can be used. These may be used alone or in combination of two or more.

The transition metal complex used as a catalyst for the above “atom transfer radical polymerization method” is not particularly limited. For example, a complex having a group 7 element, 8 group, 9 group, 10 group, or 11 element of the periodic table as a central metal, etc. Can be mentioned. Preferable examples include a complex having zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, divalent nickel as a central metal. Among these, a copper complex is more preferable. These may be used alone or in combination of two or more.

The monovalent copper compound is not particularly limited. For example, cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. Can be mentioned. When a copper compound is used, 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity A ligand such as polyamine can be added.
A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, aluminum alkoxides can be added as an activator. Furthermore, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine A complex (NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

The polymerization reaction can be carried out without solvent or in various solvents. The solvent is not particularly limited, and examples thereof 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; acetone, methyl ethyl ketone, and methyl isobutyl. Ketone solvents such as ketones; alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile, benzonitrile; ethyl acetate, butyl acetate, etc. Ester carbonate solvents; carbonate solvents such as ethylene carbonate and propylene carbonate. These may be used alone or in combination of two or more.
The above “atom transfer radical polymerization method” can be carried out in the range of 0 to 200 ° C. Preferably, it is the range of room temperature to 150 degreeC.

Next, a method for producing a vinyl polymer (A) having at least one crosslinkable silyl group represented by the general formula (1), that is, a method for introducing a crosslinkable silyl group into a vinyl polymer, In the methods [A] to [E], specific examples are described, but the method is not limited thereto.
[A] A method of adding a hydrosilane compound having a crosslinkable silyl group to a vinyl polymer having at least one alkenyl group in the presence of a hydrosilylation catalyst.
[B] A method of reacting a vinyl polymer having at least one hydroxyl group with a compound having a functional group capable of reacting with a hydroxyl group such as a crosslinkable silyl group and an isocyanate group.
[C] A method of reacting a compound having both a polymerizable alkenyl group and a crosslinkable silyl group together with a predetermined vinyl monomer when a vinyl polymer is synthesized by radical polymerization.
[D] A method of radical polymerization of a vinyl monomer using a chain transfer agent having a crosslinkable silyl group.
[E] A method of reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a stable carbanion having a crosslinkable silyl group.

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

[Aa] When synthesizing a vinyl polymer by radical polymerization, it has a polymerizable alkenyl group represented by the following general formula (2) and the like and a low polymerizable alkenyl group together with a predetermined vinyl monomer. A method in which a compound is also reacted.
_{^{H 2 C = C (R 3}} ) -R 4 -R 5 -C (R 6) = CH 2 (2)
(In the formula, R ³ represents hydrogen or a methyl group. R ⁴ represents —C (O) O—, or o-, m-, or p-phenylene group. R ⁵ represents a direct bond, or one or more groups. represents a divalent organic group having 1 to 20 carbon atoms that may have an ether bond .R ⁶ is hydrogen, an alkyl group having 1 to 10 carbon atoms, 7 to an aryl group or a carbon number of 6 to 10 carbon atoms 10 represents an aralkyl group.)
The time when the compound having both the polymerizable alkenyl group and the low polymerizable alkenyl group is reacted is not particularly limited, but when the obtained crosslinked product is expected to have rubber-like properties, living radical polymerization, It is preferable to react as the second monomer at the end of the polymerization reaction or after completion of the reaction of the predetermined vinyl monomer.

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

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

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

[Ad] A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having an alkenyl group represented by the following general formula (3), etc. Substitution method.
^{M + C - (R 7)} (R 8) -R 9 -C (R 6) = CH 2 (3)
(Wherein, R ⁶ is the same as that described above .R ⁷ and R ⁸ are both carbanion C ^- an electron-withdrawing group, or one of the electron-withdrawing several other is hydrogen or a carbon in the group 1 to 10 for stabilizing R ⁹ represents a direct bond or a divalent organic group having 1 to 10 carbon atoms which may contain one or more ether bonds, M ⁺ represents an alkali metal ion, or Indicates quaternary ammonium ion.)
As the electron withdrawing group for R ⁷ and R ⁸ , —CO ₂ R, —C (O) R and —CN are preferable. Here, R represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

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

[Af] A vinyl polymer having at least one highly reactive carbon-halogen bond is represented by an alkenyl group-containing oxyanion represented by the following general formula (4) or the following general formula (5) or the like. The alkenyl group-containing carboxylate anion is reacted to replace the halogen with an alkenyl group-containing substituent.
_{^{H 2 C = C (R 6}} ) -R 10 -O - M + (4)
(Wherein R ⁶ and M ⁺ are the same as those described above. R ¹⁰ represents a C 1-20 divalent organic group which may contain one or more ether bonds.)
_{^{H 2 C = C (R 6}} ) -R 11 -C (O) O - M + (5)
(Wherein R ⁶ and M ⁺ are the same as those described above. R ¹¹ represents a direct bond or a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds. .)

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

[Ag] A method in which a vinyl polymer having at least one hydroxyl group is allowed to react with a base such as sodium hydroxide or sodium methoxide and then reacted with an alkenyl group-containing halide such as allyl chloride.
[Ah] A method in which a vinyl polymer having at least one hydroxyl group is reacted with an alkenyl group-containing isocyanate compound such as allyl isocyanate.
[Ai] A method of reacting a vinyl polymer having at least one hydroxyl group with an alkenyl group-containing acid halide such as (meth) acrylic acid chloride in the presence of a base such as pyridine.
[Aj] A method in which a vinyl polymer having at least one hydroxyl group is reacted with an alkenyl group-containing carboxylic acid such as acrylic acid in the presence of an acid catalyst.

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

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

It does not specifically limit as a hydrosilane compound which has a crosslinkable silyl group used in the said synthesis method [A], For example, the compound etc. which are shown by following General formula (6) can be mentioned.
^{_{H- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (6)
(Wherein R ¹ , R ² , Y, a, b and m are the same as those described above.)
Among these, from the viewpoint of easy availability, a compound represented by the following general formula (7) is preferably used.
_{^{H-Si (R 2) 3}} -a (Y) a (7)
(Wherein R ² , Y and a are the same as those described above.)

In the synthesis method [A], when the hydrosilane compound having a crosslinkable silyl group is added to the alkenyl group of the polymer, a transition metal catalyst is usually used as a hydrosilylation catalyst.
The transition metal catalyst is not particularly limited. For example, a platinum solid dispersed in a carrier such as platinum alone, alumina, silica, carbon black; chloroplatinic acid; chloroplatinic acid and alcohol, aldehyde, ketone, etc. complex; platinum - olefin complexes, platinum (0) - divinyltetramethyldisiloxane _{complex; RhCl (PPh 3) 3,} RhCl 3, RuCl 3, IrCl 3, FeCl 3, AlCl 3, PdCl 2 · H 2 O, NiCl 2 , TiCl ₄ and other compounds other than platinum compounds. These may be used alone or in combination of two or more.

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

[Ba] When a vinyl polymer is synthesized by radical polymerization, a compound having both a polymerizable alkenyl group and a hydroxyl group represented by the following general formula (8) and the like are reacted with a predetermined vinyl monomer. Method.
_{^{H 2 C = C (R 3}} ) -R 4 -R 5 -OH (8)
(Wherein R ³ , R ⁴ and R ⁵ are the same as described above.)
The timing of reacting the compound having both the polymerizable alkenyl group and the hydroxyl group is not particularly limited. However, when the obtained crosslinked product is expected to have rubber-like properties, it is a living radical polymerization, the end of the polymerization reaction or It is preferable to react as the second monomer after the reaction of the predetermined vinyl monomer.

[Bb] When a vinyl polymer is synthesized by living radical polymerization, an alkenyl alcohol such as 10-undecenol, 5-hexenol or allyl alcohol is reacted at the end of the polymerization reaction or after the completion of the reaction of a predetermined monomer. How to make.
[Bc] A method in which the above-mentioned vinyl monomer is radically polymerized using a large amount of a hydroxyl group-containing chain transfer agent such as a hydroxyl group-containing polysulfide by a method as disclosed in JP-A-5-262808.
[Bd] A method in which the vinyl monomer is radically polymerized using hydrogen peroxide or a hydroxyl group-containing initiator, as disclosed in JP-A-6-239912, JP-A-8-283310, and the like.
[Be] A method in which a vinyl monomer is radically polymerized by using an alcohol excessively by a method disclosed in JP-A-6-116312.

[Bf] Hydrolysis of a vinyl polymer having at least one carbon-halogen bond having high reactivity or reaction with a hydroxyl group-containing compound by the method disclosed in JP-A-4-132706 To introduce a hydroxyl group into the terminal.
[Bg] A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having a hydroxyl group represented by the following general formula (9), etc. A method of substitution with a hydroxyl group-containing substituent.
^{M + C - (R 7)} (R 8) -R 9 -OH (9)
(Wherein R ⁷ , R ⁸ and R ⁹ are the same as described above.)
As the electron withdrawing group for R ⁷ and R ⁸ , —CO ₂ R, —C (O) R and —CN are preferable. Here, R is the same as described above.

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

In the method for synthesizing a vinyl polymer having at least one hydroxyl group, when a halogen atom is not directly involved in introducing a hydroxyl group such as [Ba] to [Be], the living radical polymerization method is used. It is preferable to use it. In this case, the method [Bb] is more preferable because control is easier. Among the living radical polymerization methods, the atom transfer radical polymerization method is more preferable.
In addition, when the hydroxyl group is introduced by converting the halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, such as the methods [Bf] to [Bi] described above. Is obtained by radical polymerization (atom transfer radical polymerization method) using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, and has at least one highly reactive carbon-halogen bond at the terminal. It is preferable to use a vinyl polymer having the same. In this case, the method [Bi] is more preferable because control is easier.

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

The compound having both a polymerizable alkenyl group and a crosslinkable silyl group used in the synthesis method [C] is not particularly limited, and examples thereof include trimethoxysilylpropyl (meth) acrylate and methyldimethoxysilylpropyl (meth) acrylate. The compound etc. which are represented with the following general formula (12) can be mentioned.
_{^{H 2 C = C (R 3}} ) -R 4 -R 12 - [Si (R 1) 2-b (Y) b O] m -Si (R 2) 3-a (Y) a (12)
(Wherein R ¹ , R ² , R ³ , R ⁴ , Y, a, b and m are the same as described above. R ¹² contains a direct bond or one or more ether bonds. A divalent organic group having 1 to 20 carbon atoms.
These may be used alone or in combination of two or more.
In the synthesis method [C], the timing for reacting the compound having the polymerizable alkenyl group and the crosslinkable silyl group is not particularly limited. However, when the obtained crosslinked product is expected to have rubber-like properties, a living radical is used. In the polymerization, it is preferable to react as the second monomer at the end of the polymerization reaction or after completion of the reaction of the predetermined vinyl monomer.

The chain transfer agent having a crosslinkable silyl group used in the synthesis method [D] is not particularly limited, and is disclosed in, for example, Japanese Patent Publication Nos. 3-14068 and 4-55444. , Mercaptans having a crosslinkable silyl group, hydrosilanes having a crosslinkable silyl group, and the like. Furthermore, in order to increase the introduction rate of the crosslinkable silyl group, a radical initiator having a crosslinkable silyl group may be used in combination.

In the synthesis method [E], at least a highly reactive carbon-halogen bond used also in the methods [Ac] to [Af] and [Bf] to [Bi] is used. The method for synthesizing one vinyl polymer is not particularly limited, and examples thereof include the following methods [Ea] and [Eb].
[Ea] Radical polymerization using a halide such as carbon tetrachloride, ethylene chloride, carbon tetrabromide, and methylene bromide as a chain transfer agent by the method disclosed in JP-A-4-132706. Method to perform (chain transfer agent method).
[Eb] An atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst.

It does not specifically limit as a stabilized carbanion which has a crosslinkable silyl group used in the said synthesis method [E], The compound etc. which are represented by following General formula (13) can be mentioned.
^{M + C - (R 7)} (R 8) -R 13 -C (H) (R 14) -CH 2 - [Si (R 1) 2-b (Y) b O] m -Si (R 2) _3-a (Y) _a (13)
(Wherein R ¹ , R ² , R ⁷ , R ⁸ , Y, a, b and m are the same as those described above. R ¹³ contains a direct bond or one or more ether bonds. R ¹⁴ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. .)
As the electron withdrawing group for R ⁷ and R ⁸ , —CO ₂ R, —C (O) R and —CN are preferable. Here, R is the same as described above.

When the foamed product obtained by foaming and curing the curable composition of the present invention is particularly required to have rubbery properties, the crosslinkable silyl group has a large molecular weight between the crosslinking points that greatly affects rubber elasticity. Preferably at least one of is at the end of the molecular chain. More preferably, all the crosslinkable silyl groups have at the molecular chain ends.

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

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

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

Further, in order to obtain a vinyl polymer having a crosslinkable silyl group at both molecular chain ends, an organic halide or sulfonyl halide compound having two starting points as an initiator in the above-mentioned “atom transfer radical polymerization method”, etc. In addition to the method using, a method using an organic halide having a crosslinkable silyl group is also preferred.

It does not specifically limit as said organic halide which has a crosslinkable silyl group, For example, the compound etc. which are represented by following General formula (14) or (15) can be mentioned.
^{R 15 R 16 C (X)} -R 17 -R 18 -C (H) (R 19) CH 2 - [Si (R 1) 2-b (Y) b O] m -Si (R 2) 3- _a (Y) _a (14)
(Wherein R ¹ , R ² , a, b, m, X and Y are the same as those described above. R ¹⁵ and R ¹⁶ are the same or different and each represents hydrogen, an alkyl group having 1 to 20 carbon atoms, Represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, R ¹⁵ and R ¹⁶ may be connected to each other at the other end, R ¹⁷ represents —C (O) O—, -C (O)-or o-, m-, p-phenylene group R ¹⁸ is a direct bond or a divalent C 1-10 which may contain one or more ether bonds. R ¹⁹ represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.
_{^{(R 2) 3-a (}} Y) a Si- [OSi (R 1) 2-b (Y) b] m -CH 2 -C (H) (R 19) -R 18 -C (R 15) ( X) -R ¹⁷ -R ¹⁶ (15)
(Wherein R ¹ , R ² , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , a, b, m, X and Y are the same as those described above.)

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

The crosslinkable silyl group can also be obtained by coupling halogen atoms of the vinyl polymer with a compound having two or more of the same or different functional groups that can replace the halogen atom at the terminal end. Can be obtained at both molecular chain terminals.
The compound having two or more of the same or different functional groups that can replace the halogen atom at the terminal end is not particularly limited. For example, polyol, polyamine, polycarboxylic acid, polythiol, salts thereof; alkali metal sulfide, etc. Can be mentioned.

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

The vinyl polymer having at least one crosslinkable silyl group at the end of the molecular chain can be obtained by combining the above-described methods and the like as needed, and the following synthesis steps a and b are given as typical synthesis steps. it can.

Synthesis process a
(A-1) a step of synthesizing a vinyl polymer having a halogen atom at its terminal by radical polymerization of a vinyl monomer using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst;
(A-2) A vinyl having an alkenyl group at the terminal by reacting the oxyanion having an alkenyl group with the vinyl polymer having a halogen atom at the terminal obtained in the step (a-1). A step of synthesizing a polymer, and
(A-3) A hydrosilane compound having a crosslinkable silyl group represented by the general formula (1) is added to the terminal alkenyl group of the vinyl polymer having an alkenyl group at the terminal obtained in the step (a-2). A synthesis step comprising a step of converting to a substituent containing a crosslinkable silyl group.

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

<< (B) Carboxylic acid metal salt >>
The carboxylic acid metal salt as component (B) is a so-called curing catalyst capable of forming a siloxane bond from a hydroxyl group or hydrolyzable group bonded to a silicon atom contained in the polymer of component (A) and component (F). As compared with other curing catalysts, it is possible to improve the restorability, durability and creep resistance of the resulting cured product.

As the carboxylic acid metal salt as component (B), tin carboxylate, lead carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, titanium carboxylate, zirconium carboxylate, hafnium carboxylate, vanadium carboxylate, carboxyl Manganese acid, iron carboxylate, cobalt carboxylate, nickel carboxylate, and cerium carboxylate are preferable because of their high catalytic activity, and more preferably tin carboxylate, lead carboxylate, titanium carboxylate, iron carboxylate, and zirconium carboxylate. In particular, tin carboxylate is preferable, and divalent tin carboxylate is most preferable.

Here, as the carboxylic acid having an acid group of a carboxylic acid metal salt, a hydrocarbon-based carboxylic acid group-containing compound having 2 to 40 carbon atoms including carbonyl carbon is preferably used, and the number of carbon atoms from the viewpoint of availability. 2-20 hydrocarbon carboxylic acids can be used particularly preferably.

Specific examples of the carboxylic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, 2-ethylhexanoic acid, octylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, Straight-chain saturated fatty acids such as tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicic acid, and laccelic acid; Acid, Linderic acid, Tuzic acid, Fizeteric acid, Myristoleic acid, 2-Hexadecenoic acid, 6-Hexadecenoic acid, 7-Hexadecenoic acid, Palmitoleic acid, Petroceric acid, Oleic acid, Elaidic acid, Asclepic acid, Vaxenoic acid, Gadrain Acid, gondoic acid, cetreic acid, elca Monounsaturated fatty acids such as brassinoic acid, cerakoleic acid, ximenoic acid, lumenic acid, acrylic acid, methacrylic acid, angelic acid, crotonic acid, isocrotonic acid, 10-undecenoic acid; linoelaidic acid, linoleic acid, 10,12 -Octadecadienoic acid, hiragoic acid, α-eleostearic acid, β-eleostearic acid, punicic acid, linolenic acid, 8,11,14-eicosatrienoic acid, 7,10,13-docosatrienoic acid, 4 , 8,11,14-hexadecatetraenoic acid, moloctic acid, stearidonic acid, arachidonic acid, 8,12,16,19-docosatetraenoic acid, 4,8,12,15,18-eicosapentaenoic acid, sardine Polyene unsaturated fatty acids such as acid, nisic acid, docosahexaenoic acid; 1-methylbutyric acid, isobutyric acid, 2-ethylbutyric acid Branched fatty acids such as isovaleric acid, tuberculostearic acid, pivalic acid, neodecanoic acid; fatty acids having triple bonds such as propiolic acid, talylic acid, stearolic acid, crepenic acid, xymenic acid, 7-hexadesinic acid Alicyclic carboxylic acids such as naphthenic acid, malvalic acid, sterlic acid, hydnocarbic acid, sorghumulinic acid, gorulinic acid, etc .; Acid, iprolic acid, 2-hydroxyhexadecanoic acid, yarapinolic acid, uniperic acid, ambretoleic acid, aleurit acid, 2-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid, 9,10-dihydroxyoctadecane acid Ricinoleic acid, Kamuroren acid, licanic, Feron acid, oxygenated fatty acids such as cerebronic acid; chloroacetic acid, 2-chloro-acrylic acid, halogen substitution products of monocarboxylic acids such as chlorobenzoic acid. Examples of aliphatic dicarboxylic acids include adipic acid, azelaic acid, pimelic acid, speric acid, sebacic acid, ethyl malonic acid, glutaric acid, oxalic acid, malonic acid, succinic acid, oxydiacetic acid, and other saturated dicarboxylic acids; maleic acid, Examples thereof include unsaturated dicarboxylic acids such as fumaric acid, acetylenedicarboxylic acid and itaconic acid. Examples of the aliphatic polycarboxylic acid include tricarboxylic acids such as aconitic acid, citric acid, and isocitric acid. Aromatic carboxylic acids include aromatic monocarboxylic acids such as benzoic acid, 9-anthracenecarboxylic acid, atrolactic acid, anisic acid, isopropylbenzoic acid, salicylic acid, toluic acid; phthalic acid, isophthalic acid, terephthalic acid, carboxyphenyl Examples thereof include aromatic polycarboxylic acids such as acetic acid and pyromellitic acid. In addition, amino acids such as alanine, leucine, threonine, aspartic acid, glutamic acid, arginine, cysteine, methionine, phenylalanine, tryptophan, histidine and the like can be mentioned.
Particularly, the carboxylic acid is preferably 2-ethylhexanoic acid, octylic acid, neodecanoic acid, oleic acid, naphthenic acid or the like because it is easily available and inexpensive and has good compatibility with the component (A).

When the melting point of the carboxylic acid is high (crystallinity is high), the carboxylic acid metal salt having the acid group also has a high melting point and tends to be difficult to handle (poor workability). Therefore, the melting point of the carboxylic acid is preferably 65 ° C. or less, more preferably −50 to 50 ° C., and particularly preferably −40 to 35 ° C.

When the carbon number of the carboxylic acid is large (molecular weight is large), the carboxylic acid metal salt having the acid group is in a solid or high-viscosity liquid and is difficult to handle (poor workability). Tend. On the contrary, when the carbon number of the carboxylic acid is small (molecular weight is small), the carboxylic acid metal salt having the acid group contains many components that are easily volatilized by heating, and the catalytic ability of the carboxylic acid metal salt is reduced. There is a case. In particular, when the composition is thinly stretched (thin layer), volatilization by heating is large, and the catalytic ability of the carboxylic acid metal salt may be greatly reduced. Therefore, the carboxylic acid preferably has 2 to 20 carbon atoms including carbon of the carbonyl group, more preferably 6 to 17 and particularly preferably 8 to 12.

From the viewpoint of easy handling (workability and viscosity) of the carboxylic acid metal salt, a metal salt of a dicarboxylic acid or a monocarboxylic acid is preferable, and a metal salt of a monocarboxylic acid is more preferable.

In addition, the carboxylic acid metal salt (B) includes a carboxylic acid metal salt (such as tin 2-ethylhexanoate) in which the carbon atom adjacent to the carbonyl group is tertiary carbon, or a carboxylic acid metal salt (quaternary carbon). Tin neodecanoate, tin pivalate, etc.) are more preferable because of their high curing speed.
Moreover, the carboxylic acid metal salt whose carbon atom adjacent to a carbonyl group is a quaternary carbon is especially preferable. The carboxylic acid metal salt in which the carbon atom adjacent to the carbonyl group is a quaternary carbon is excellent in adhesiveness as compared with other carboxylic acid metal salts.

Thus, in the curable composition of the present invention, it is particularly preferable that the carbon atom adjacent to the carbonyl group constituting the carboxylic acid of the carboxylic acid metal salt of component (B) is a quaternary carbon. The properties and the like are more excellent.

As the carboxylic acid in which the carbon atom adjacent to the carbonyl group is a quaternary carbon, the general formula (16):

(Wherein R ²⁰ , R ²¹ and R ²² are each independently a substituted or unsubstituted monovalent organic group, which may contain a carboxyl group); (17):

(Wherein R ²³ is a substituted or unsubstituted monovalent organic group, R ²⁴ is a substituted or unsubstituted divalent organic group, each of which may contain a carboxyl group) and the general formula (18 ):

(Wherein, R ²⁵ is a substituted or unsubstituted trivalent organic group, and may contain a carboxyl group), and the like, and the like, and the like.

Specific examples of the carboxylic acid having a quaternary carbon atom adjacent to the carbonyl group include pivalic acid, 2,2-dimethylbutyric acid, 2-ethyl-2-methylbutyric acid, 2,2-diethylbutyric acid, 2, 2-dimethylvaleric acid, 2-ethyl-2-methylvaleric acid, 2,2-diethylvaleric acid, 2,2-dimethylhexanoic acid, 2,2-diethylhexanoic acid, 2,2-dimethyloctanoic acid, 2- Chain monocarboxylic acids such as ethyl-2,5-dimethylhexanoic acid, neodecanoic acid, versatic acid, 2,2-dimethyl-3-hydroxypropionic acid; dimethylmalonic acid, ethylmethylmalonic acid, diethylmalonic acid, 2, Chain dicarboxylic acids such as 2-dimethylsuccinic acid, 2,2-diethylsuccinic acid, 2,2-dimethylglutaric acid; 3-methylisocitric acid, 4,4-dimethylaconic acid Linear tricarboxylic acids such as acids; 1-methylcyclopentanecarboxylic acid, 1,2,2-trimethyl-1,3-cyclopentanedicarboxylic acid, 1-methylcyclohexanecarboxylic acid, 2-methylbicyclo [2.2.1 ] -5-heptene-2-carboxylic acid, 2-methyl-7-oxabicyclo [2.2.1] -5-heptene-2-carboxylic acid, 1-adamantanecarboxylic acid, bicyclo [2.2.1] And cyclic carboxylic acids such as heptane-1-carboxylic acid and bicyclo [2.2.2] octane-1-carboxylic acid. Many compounds containing such structures exist in natural products, but of course they can also be used.

In particular, from the viewpoint of good compatibility with the components (A) and / or (F), monocarboxylic acids are more preferable, and chain monocarboxylic acids are more preferable. Furthermore, pivalic acid, neodecanoic acid, versatic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid and the like are particularly preferable because they are easily available.

Moreover, it is preferable that carbon number of such carboxylic acid is 2-20, It is more preferable that it is 6-17, It is especially preferable that it is 8-12. When the number of carbon atoms exceeds 20, it tends to be solid, and it becomes difficult to achieve compatibility with the components (A) and / or (F), and the activity tends to be difficult to obtain. On the other hand, when the number of carbon atoms is less than 2, the volatility increases and the odor tends to increase. From these points, neodecanoic acid, versatic acid, 2,2-dimethyloctanoic acid, and 2-ethyl-2,5-dimethylhexanoic acid are the most preferable carboxylic acids having a quaternary carbon atom adjacent to the carbonyl group. preferable.

Specific examples of the metal carboxylate having a quaternary carbon atom adjacent to the carbonyl group include tin neodecanoate, tin versatate, tin 2,2-dimethyloctanoate, 2-ethyl-2,5- Tin dimethylhexanoate is particularly preferred.

Moreover, each said carboxylic acid metal salt can be used in combination of 2 or more types besides using it individually.
(B) As a compounding quantity of a component, when (A) component 100 weight part or (F) component is contained, it is 0.01 with respect to a total of 100 weight part of (A) component and (F) component. About 20 parts by weight is preferable, and about 0.5 to 10 parts by weight is more preferable. When the blending amount of component (B) is less than 0.01 parts by weight, the curing rate may be slow, and the curing reaction may not proceed sufficiently. On the other hand, when the blending amount of the component (B) exceeds 20 parts by weight, the pot life is shortened, workability may be lowered, and storage stability tends to be lowered.

<< (C) Carboxylic acid and / or carboxylic acid derivative >>
The carboxylic acid and / or carboxylic acid derivative as the component (C) is used as a curing catalyst and has an effect of improving the curing activity of the curable composition of the present invention.
In addition, when the carboxylic acid metal salt of component (B) is used as a curing catalyst, the curability may decrease after storage. In this case, curing after storage by adding component (C) The property becomes better.

The carboxylic acid derivative of component (C) is a compound that generates carboxylic acid by hydrolysis, such as carboxylic acid anhydride, carboxylic acid ester, acyl chloride, carboxylic acid nitrile, and carboxylic acid amide. Various derivatives of acids can be used.

(C) As a component, a fatty acid and its derivative (s) are preferable.
Moreover, as (C) component, carboxylic acid is especially preferable from the height of the curing activity improvement effect.
(C) As carboxylic acid of a component, the various carboxylic acid which has the acid group of the above-mentioned carboxylic acid metal salt which is (B) component can be illustrated.
The carboxylic acid preferably has 2 to 20 carbon atoms, including 6 to 17 carbon atoms, including the carbon of the carbonyl group, like the carboxylic acid having an acid group of the carboxylic acid metal salt of the component (B). Is more preferable, and 8 to 12 is particularly preferable.
Further, from the viewpoint of easy handling (workability and viscosity) of carboxylic acid, dicarboxylic acid or monocarboxylic acid is preferable, and monocarboxylic acid is more preferable.

Furthermore, the carboxylic acid is a carboxylic acid having a tertiary carbon atom adjacent to the carbonyl group (such as 2-ethylhexanoic acid) or a carboxylic acid having a quaternary carbon (such as neodecanoic acid or pivalic acid). Is more preferable because it is fast.
In view of availability, curability, and workability, the carboxylic acid is particularly 2-ethylhexanoic acid, neodecanoic acid, versatic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid. preferable.

In addition, it is particularly preferable that the carbon atom adjacent to the carbonyl group constituting the carboxylic acid of the carboxylic acid and / or carboxylic acid derivative of the component (C) is a quaternary carbon, thereby improving the curability and the like. It becomes.
Examples of the carboxylic acid in which the carbon atom adjacent to the carbonyl group is a quaternary carbon include the same ones as described above.

Furthermore, it is preferable to use the component (B) and the component (C) in combination because quick curability is easily obtained. In that case, it is more preferable that the carbon atoms adjacent to the carbonyl group constituting the carboxylic acid of the component (B) and the component (C) are both quaternary carbons. Furthermore, the components (B) and (C) It is particularly preferable that the acid groups have the same structure.

Moreover, each said carboxylic acid and carboxylic acid derivative can be used in combination of 2 or more type besides using individually.
(C) As a compounding quantity of a component, when it contains 100 weight part of (A) component or (F) component, it is 0.01 with respect to a total of 100 weight part of (A) component and (F) component. About 20 parts by weight is preferable, and about 0.5 to 10 parts by weight is more preferable. When the blending amount of the component (C) is less than 0.01 parts by weight, the curing rate may be slow, and the catalyst activity may decrease after storage. On the other hand, when the blending amount of component (C) exceeds 20 parts by weight, the pot life may be shortened and workability may be reduced.
Moreover, when using together (B) component and (C) component, since adhesiveness may fall when the molar amount of (C) component exceeds the molar amount of (B) component, of (B) component It is particularly preferred to use a component (C) with a molar amount less than the molar amount.

<< (D) Amine Compound >>
The amine compound as the component (D) imparts good resilience and creep resistance, and further uses a primary and / or secondary amine compound having a melting point of 20 ° C. or higher, so that the surface after curing. The tack is improved, the surface is less soiled over a long period of time, and good weather resistance is imparted so that cracks and discoloration do not occur on the surface even when used outdoors for a long time.
Moreover, by including the amine compound of (D) component, compared with the case of only the carboxylic acid metal salt of (B) component, or the case of only the carboxylic acid and / or carboxylic acid derivative of (C) component, High activity and more suitable curability can be obtained.

Specific examples of the amine compound as component (D) are not particularly limited, and examples thereof include primary amine compounds, secondary amine compounds, tertiary amine compounds, and other amine compounds.
Examples of primary amine compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, pentylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, tridecylamine, tetradecylamine, Aliphatic monoamines such as pentadecylamine, hexadecylamine, heptadecylamine, stearylamine, nonadecylamine, cyclohexylamine, oleylamine;
Ethylenediamine, 1,4-diaminobutane, 1,5-diaminopentane, hexamethylenediamine, triethylenediamine, 1,7-diaminoheptane, trimethylhexamethylenediamine, 1,8-diaminooctane, 1,9-diaminononane, 1, 10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1, 17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, 1,2-diaminohenticosane, 1,2-diaminodocosane, 1,23- Diaminotricosane, 1,24-diamy Tetracosane, 4,4'-diaminodicyclohexylmethane aliphatic diamines such as methane;
Aromatic monoamines such as benzylamine;
Examples include aromatic diamines such as phenylenediamine, xylylenediamine, and 3,4-xylidine.

Secondary amine compounds include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, dipentylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine, didecylamine, dilaurylamine, dihexadecylamine. And aliphatic monoamines such as distearylamine, methylstearylamine, ethylstearylamine, and butylstearylamine.

Tertiary amine compounds include aliphatic monoamines such as tripentylamine, trihexylamine, trioctylamine, triallylamine;
And aromatic monoamines such as triphenylamine.

Other amine compounds include monoethanolamine, diethanolamine, triethanolamine, 3-hydroxypropylamine, 3-methoxypropylamine, 3-lauryloxypropylamine, diethylenetriamine, triethylenetetramine, dimethylaminoethylamine, diethylaminoethylamine, 3 -Dimethylaminopropylamine, 3-diethylaminopropylamine, N-methyl-1,3-propanediamine, 3- (1-piperazinyl) propylamine, N-laurylpropylenediamine, N-stearylpropylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 3-morpholinopropylamine, 2-ethyl-4 Methylimidazole, 1,8-diazabicyclo (5,4,0) undecene -7 (DBU), 1,5-diazabicyclo (4,3,0) nonene -5 (DBN), and the like.

As the component (D), the promoter (A) and / or component (F) to be used is greatly different depending on the structure of the component (D) itself and the compatibility with the component (A) and / or (F). It is preferable to select a suitable compound according to the kind of the compound.
From the viewpoint of high cocatalyst ability, primary amines such as octylamine and laurylamine are preferable, and amine compounds having a hydrocarbon group having at least one heteroatom are preferable. Examples of heteroatoms include N, O, S and the like, but are not limited thereto. Examples of such an amine compound include those exemplified above as the diamine and other amine compounds.
Among these, an amine compound having a hydrocarbon group having a hetero atom on the 2nd to 4th carbon atoms is more preferable. Examples of such amine compounds include ethylenediamine, ethanolamine, dimethylaminoethylamine, diethylaminoethylamine, 3-hydroxypropylamine, diethylenetriamine, 3-methoxypropylamine, 3-lauryloxypropylamine, N-methyl-1,3-propane. Examples include diamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 3- (1-piperazinyl) propylamine, and 3-morpholinopropylamine. Among these, 3-diethylaminopropylamine and 3-morpholinopropylamine are more preferable because of their high promoter ability. 3-Diethylaminopropylamine is particularly preferable because it provides a curable composition having good adhesion, workability, and storage stability.

(D) As a compounding quantity of a component, when it contains (A) component 100 weight part or (F) component, it is 0.1 with respect to a total of 100 weight part of (A) component and (F) component. About 20 parts by weight is preferable, and 0.1 to 5 parts by weight is more preferable. When the blending amount of the component (D) is less than 0.1 parts by weight, the curing rate tends to be slow, and the curing reaction tends not to proceed sufficiently. On the other hand, when the blending amount of the component (D) exceeds 20 parts by weight, the pot life is shortened and workability tends to be lowered. On the contrary, the curing speed may be slow.

<Primary and / or secondary amine compound having a melting point of 20 ° C. or higher>
In the curable composition of the present invention, the component (D) consists of at least two types, at least one of which is a primary and / or secondary amine compound having a melting point of 20 ° C. or higher.
Among the above components (D), primary and / or secondary amine compounds having a melting point of 20 ° C. or more have a function of making the cured product surface matt and eliminating residual tack, and good dust adhesion. Used to realize the sex.

Examples of the primary and / or secondary amine compound having a melting point of 20 ° C. or higher include the following among the components (D).
Examples of primary amine compounds include aliphatic monoamines such as laurylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, stearylamine, and nonadecylamine;
1,4-diaminobutane, 1,5-diaminopentane, hexamethylenediamine, 1,7-diaminoheptane, trimethylhexamethylenediamine, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, 1,21-diaminohenticosane, 1,2-diaminodocosane, 1,23-diaminotricosane, , 24-diaminotetracosane, 4,4'-diaminodicyclo Aliphatic diamines such as hexylmethane;
Examples thereof include aromatic diamines such as phenylenediamine and 3,4-xylidine.
Examples of the secondary amine compound include aliphatic monoamines such as dilaurylamine and distearylamine.
Examples of other amines include N-lauryl propylene diamine and N-stearyl propylene diamine.

Of these, laurylamine, pentadecylamine, hexadecylamine, stearylamine, hexamethylenediamine, which are primary amine compounds, and dilaurylamine and distearylamine, which are secondary amine compounds, are particularly preferable.

The melting point of the primary and / or secondary amine compound is 20 ° C. or higher, preferably 30 to 100 ° C. Those having a melting point of less than 20 ° C. tend to soften at heat resistance, particularly at high temperatures in summer, and are not easily exerted by matting and dust adhesion suppressing effects due to evaporation. When the melting point exceeds 100 ° C., the surface of the sealing material is hard and easily brittle, and the elasticity, which is a basic characteristic of the sealing material, is easily lost.

Examples of the primary and / or secondary amine compound having a melting point of 20 ° C. or higher also include compounds that react with water to produce primary and / or secondary amines.
Specific examples of the compound that reacts with water to produce primary and / or secondary amines include primary and secondary compounds from the viewpoints of ease of raw materials, storage stability, and reactivity with water. Preferred examples include secondary amine ketimine compounds, enamine compounds, aldimine compounds and the like. These ketimine compounds, enamine compounds, and aldimine compounds can be obtained by dehydration reaction of ketones or aldehydes with the primary and / or secondary amine compounds, respectively.

The ketones are not particularly limited, and examples thereof include methyl ethyl ketone, methyl isopropyl ketone, methyl tert-butyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 4-methyl-2-pentanone, 2-heptanone, 4 -Aliphatic ketones such as heptanone, diisopropyl ketone and diisobutyl ketone; cyclic ketones such as cyclopentanone, cyclohexanone and methylcyclohexanone; and β-dicarbonyl compounds such as ethyl acetoacetate.
The aldehyde is not particularly limited, and examples thereof include butyraldehyde, isobutyraldehyde, hexyl aldehyde, and the like.
Of these, 4-methyl-2-pentanone is preferred from the same points as described above.

The melting point of the compound that reacts with water to produce a primary and / or secondary amine is not particularly limited, but the melting point of the primary and / or secondary amine produced by reaction with water is 20 The surface gloss of the curable composition is reduced and the surface matting ability is large, so that when used for sealing an outer wall material with a matte surface, the sealing joints are not noticeable and the outer wall material Does not spoil the beauty of
Even if a compound that reacts with water to produce a primary and / or secondary amine is used, the curable composition is similar to the primary and / or secondary amine compound having a melting point of 20 ° C. or higher. This has the effect of eliminating the adhesion of the surface after curing, and preventing contamination due to adhesion of dust or the like.

The primary and / or secondary amine compounds having a melting point of 20 ° C. or higher may be used alone or in combination of two or more.
As the compounding amount of the primary and / or secondary amine compound having a melting point of 20 ° C. or higher, (A) component 100 parts by weight, or (F) when component (A) and (F) 0.1-20 weight part is preferable with respect to a total of 100 weight part of a component, and 0.5-10 weight part is more preferable. When the blending amount of the primary and / or secondary amine compound having a melting point of 20 ° C. or higher is less than 0.1 part by weight, it takes time for the cured product surface to be matte and the residual tack to disappear. The effect of improving dust adhesion tends to be small. On the other hand, when the amount exceeds 20 parts by weight, the viscosity during storage tends to increase, and when used as a sealing material, the work time actually required when constructing the sealing material is shortened, It may be difficult.

<< (F) Polyether Polymer >>
The curable composition of the present invention may further contain a polyether polymer having at least one crosslinkable silyl group represented by the general formula (1) as the component (F).
(F) By containing a polyether polymer, a rubber-like cured product having a low modulus and a high elongation can be realized, but a rubber-like cured product having a high modulus and a low elongation can be provided depending on the application. . That is, in the curable composition of the present invention, the addition amount, type, and the like of the (F) polyether polymer can be appropriately set so as to give a cured product having desired rubber properties according to the use.

(F) The main chain of the polyether polymer is not particularly limited, and examples thereof include polyethylene oxide, polypropylene oxide, polybutylene oxide, polyphenylene oxide, and the like. Of these, it is preferably essentially polyoxyalkylene, more preferably essentially polypropylene oxide, which may contain ethylene oxide, butylene oxide, phenylene oxide and the like in addition to propylene oxide. The polyether polymer may or may not contain a urethane bond in the main chain.
Here, “the main chain is essentially polypropylene oxide” means that propylene oxide units occupy 50% or more of the repeating units constituting the main chain, preferably 70% or more, more preferably 90%. % Or more.
The lower the viscosity, the better the handleability, so that the molecular weight distribution (Mw / Mn) of the polypropylene oxide polymer is more preferably 1.5 or less.

The crosslinkable silyl group in the component (F) is the one represented by the above general formula (1), but the symbols in the formula are the same as those described above. The crosslinkable silyl group in component (F) may have the same structure as the crosslinkable silyl group in component (A) or may have a different structure.
(F) The number of crosslinkable silyl groups possessed by the polyether-based polymer is at least one per molecule, but from the viewpoint of curability of the curable composition, it is preferable to have more than one on average. More preferably, it is 1.1 to 4.0 on average, and more preferably 1.5 to 2.5 on average.
Moreover, from the viewpoint of rubber elasticity of the cured product, the crosslinkable silyl group is preferably at the end of the polyether polymer, and more preferably at both ends of the polymer.

(F) The method for producing the polyether polymer is not particularly limited, and may be a conventionally known method, for example, described in JP-A-50-156599, JP-A-55-125121, and the like. The manufacturing method currently used is mentioned.

Examples of the component (F) include, but are not limited to, MS polymer-S-203, S-303, Silyl SAX220 (manufactured by Kaneka Corporation) and the like in terms of trade names.

When the component (F) is contained, the mixing ratio of the component (A) and the component (F) is preferably in the range of 99/1 to 1/99 by weight, and 95/5. More preferably, it is in the range of ˜5 / 95, more preferably in the range of 70/30 to 30/70. When the blend ratio of the component (A) is within the above range, the weather resistance is more excellent.

<< Curable composition >>
As described above, the curable composition of the present invention comprises (A) a vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1), (D) an amine compound (melting point of 20 ° C. or higher). And (B) a carboxylic acid metal salt and / or (C) a carboxylic acid and / or a carboxylic acid derivative. It is. Further, if necessary, (F) a polyether polymer having at least one crosslinkable silyl group represented by the general formula (1) can be contained.
Furthermore, in the curable composition of this invention, you may add various compounding agents according to the target physical property.

<Curing catalyst>
In the present invention, (B) a carboxylic acid metal salt and / or (C) a carboxylic acid and / or a carboxylic acid derivative is used as a curing catalyst. A catalyst can also be used in combination.
Specific examples of other curing catalysts include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonato) diisopropoxytitanium; dibutyltin dilaurate, dibutyltin maleate, dibutyl Tin phthalate, dibutyl tin dioctate, dibutyl tin bis (2-ethylhexanoate), dibutyl tin bis (methyl maleate), dibutyl tin bis (ethyl maleate), dibutyl tin bis (butyl maleate), dibutyl tin bis ( Octyl maleate), dibutyl tin bis (tridecyl maleate), dibutyl tin bis (benzyl maleate), dibutyl tin diacetate, dioctyl tin bis (ethyl maleate), dioctyl tin bis (octyl maleate), dibutyl tin dimeth Side, dibutyltin bis (nonylphenoxide), dibutenyltin oxide, dibutyltin bis (acetylacetonate), dibutyltin bis (ethylacetoacetonate), reaction product of dibutyltin oxide and silicate compound, dibutyltin oxide and phthalate Tetravalent organotin compounds such as reactants with acid esters; organoaluminum compounds such as aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), diisopropoxyaluminum ethylacetoacetate; zirconium tetrakis (acetylacetate) And zirconium compounds such as natto.

By using these curing catalysts in combination, the catalytic activity becomes higher, and the deep part curability, the thin layer curability, the adhesiveness and the like are further improved. However, it is preferable to add an appropriate amount of the organic tin compound because the restoration property, durability, and creep resistance of the cured product of the resulting curable composition may be lowered depending on the addition amount.
When using a curing catalyst, the amount used thereof is 100 parts by weight of component (A), or when it contains component (F), with respect to a total of 100 parts by weight of component (A) and component (F), The amount is preferably 1 to 10,000 parts by weight, more preferably 10 to 1000 parts by weight.

<Silicate>
Silicates can also be added to the curable composition of the present invention.
The silicate acts as a cross-linking agent and has a function of improving the restoring property, durability, and creep resistance of the component (A) or component (F) of the present invention. Furthermore, it also has the effect of improving adhesion and water-resistant adhesion and adhesion durability under high temperature and high humidity conditions. As the silicate, tetraalkoxysilane or a partial hydrolysis condensate thereof can be used.
When the silicate is used, the amount used is 0.1 parts by weight with respect to 100 parts by weight of the component (A) or 100 parts by weight of the total of the components (A) and (F) when the component (F) is contained. 1-20 weight part is preferable, More preferably, it is 0.5-10 weight part.

Specific examples of the silicate include, for example, tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxy. Examples thereof include tetraalkoxysilanes (tetraalkyl silicates) such as silane, tetra-i-butoxysilane, and tetra-t-butoxysilane, and partial hydrolysis condensates thereof.
The partial hydrolysis-condensation product of tetraalkoxysilane is more preferable because the restoring effect, durability, and creep resistance improvement effect of the present invention are greater than those of tetraalkoxysilane.
Examples of the partially hydrolyzed condensate of tetraalkoxysilane include those obtained by adding water to tetraalkoxysilane and condensing it by partial hydrolysis using a conventional method. Moreover, the commercially available thing can be used for the partial hydrolysis-condensation product of an organosilicate compound. Examples of such condensates include methyl silicate 51 and ethyl silicate 40 (both manufactured by Colcoat Co., Ltd.).

<Filler>
A filler can be added to the curable composition of the present invention.
Fillers include reinforcing silica such as fume silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid and carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, Diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, shirasu balloon, glass microballoon, phenol resin and vinylidene chloride resin Organic micro balloons, fillers such as resin powders such as PVC powder and PMMA powders; fibrous fillers such as asbestos, glass fibers and filaments.
These fillers may be used alone or in combination of two or more.
When using a filler, the amount used is 100 parts by weight of component (A), or 1 part with respect to a total of 100 parts by weight of component (A) and component (F) when component (F) is contained. -250 weight part is preferable, More preferably, it is 10-200 weight part.

When you want to obtain a hardened material with high strength by using these fillers, mainly fume silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid and carbon black, surface treatment fine A filler selected from calcium carbonate, calcined clay, clay, activated zinc white and the like is preferable. When the component (A) contains 100 parts by weight or the component (F), the component (A) and the component (F) When the total amount is 100 parts by weight, a preferable result can be obtained by using in the range of 1 to 200 parts by weight.
When it is desired to obtain a cured product having low strength and large elongation at break, mainly calcium carbonate such as titanium oxide and heavy calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon The filler selected from, for example, 100 parts by weight of the component (A), or 5 to 200 parts by weight with respect to the total of 100 parts by weight of the component (A) and the component (F) when the component (F) is contained. If it is used within the range, preferable results can be obtained.
In general, calcium carbonate has a greater effect of improving the breaking strength, breaking elongation, and adhesiveness of the cured product as the value of the specific surface area increases. When calcium carbonate is used, it is desirable to use a combination of surface-treated fine calcium carbonate and heavy calcium carbonate such as heavy calcium carbonate. The particle diameter of the surface-treated fine calcium carbonate is preferably 0.5 μm or less, and the surface treatment is preferably treated with a fatty acid or a fatty acid salt. Further, the particle size of calcium carbonate having a large particle size is preferably 1 μm or more, and those having no surface treatment can be used.

In order to improve the workability (such as sharpness) of the composition and to make the surface of the cured product matt, it is preferable to add an organic balloon or an inorganic balloon. These fillers can be surface-treated, and may be used alone or in combination of two or more. In order to improve workability (such as sharpness), the balloon particle size is preferably 0.1 mm or less. In order to make the surface of the cured product matt, 5-300 μm is preferable.

The composition of the present invention is a sizing board, particularly a ceramic sizing board, etc., because of the good chemical resistance of the cured product. However, it is preferably used for an adhesive in which the adhesive remains as it is, but it is desirable that the design of the outer wall and the design of the sealing material are harmonized. In particular, high-quality outer walls are used as outer walls due to spatter coating, mixing of colored aggregates, and the like. When a scaly or granular substance having a diameter of 0.1 mm or more, preferably about 0.1 to 5.0 mm, is blended in the composition of the present invention, the cured product is in harmony with such a high-quality outer wall. In addition, since the chemical resistance is excellent, the appearance of the cured product is an excellent composition that lasts for a long time. When a granular material is used, the surface becomes sandy or sandstone-like rough, and when a scaly material is used, the surface becomes uneven.

As described in JP-A-9-53063, preferable diameters, blending amounts, materials, and the like of the scaly or granular substance are as follows.
The diameter is 0.1 mm or more, preferably about 0.1 to 5.0 mm, and a material having an appropriate size is used according to the material and pattern of the outer wall. The thing of about 0.2 mm-5.0 mm and about 0.5 mm-5.0 mm can also be used. In the case of a scaly substance, the thickness is about 1/10 to 1/5 of the diameter (about 0.01 to 1.00 mm). The scale-like or granular substance is mixed in advance in the main sealing material and transported to the construction site as a sealing material, or mixed in the main sealing material at the construction site when used.
It is preferable that about 1 to 200 parts by weight of the scale-like or granular substance is blended with respect to 100 parts by weight of a composition such as a sealing material composition or an adhesive composition. The blending amount is appropriately selected according to the size of each scale-like or granular substance, the material of the outer wall, the pattern, and the like.
As the scale-like or granular substance, natural substances such as silica sand and mica, synthetic rubber, synthetic resin, and inorganic substances such as alumina are used. In order to enhance the designability when filling the joint, it is colored in an appropriate color according to the material and pattern of the outer wall.
A preferable finishing method and the like are described in JP-A-9-53063.

Further, if a balloon (preferably having an average particle size of 0.1 mm or more) is used for the same purpose, the surface becomes sandy or sandstone-like, and the weight can be reduced. As described in JP-A-10-251618, preferred diameters, blending amounts, materials, and the like of the balloon are as follows.
The balloon is a spherical filler with a hollow inside. Examples of the balloon material include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenol resin, urea resin, polystyrene, and saran, but are not limited thereto. In addition, an inorganic material and an organic material can be combined, or a plurality of layers can be formed by stacking. An inorganic or organic balloon or a combination of these can be used. The balloons used may be the same balloon or a mixture of different types of balloons. Furthermore, the balloon can be used by processing or coating the surface thereof, or can be used by treating the surface with various surface treatment agents. For example, an organic balloon may be coated with calcium carbonate, talc, titanium oxide or the like, or an inorganic balloon may be surface treated with a silane coupling agent.

The balloon preferably has a particle size of 0.1 mm or more in order to obtain a surface having a sandy or sandstone texture. The thing of about 0.2 mm-5.0 mm and about 0.5 mm-5.0 mm can also be used. If it is less than 0.1 mm, even if it is blended in a large amount, it may only increase the viscosity of the composition and the rough feeling may not be exhibited. The blending amount of the balloon can be easily determined according to the desired degree of sanding tone or sandstone tone. In general, it is desirable to blend those having a particle size of 0.1 mm or more in a ratio of 5 to 25 vol% in terms of volume concentration in the composition. When the volume concentration of the balloon is less than 5 vol%, there is no feeling of roughness, and when the volume concentration exceeds 25 vol%, the viscosity of the sealing material and the adhesive increases, the workability decreases, the modulus of the cured product also increases, the sealing material, The basic performance of the adhesive tends to be impaired. The volume concentration with a particularly preferable balance with the basic performance of the sealing material is 8 to 22 vol%.

When using a balloon, an anti-slip agent as described in JP-A No. 2000-154368 can be added.
Specific examples of the balloons are disclosed in JP-A-2-129262, JP-A-4-8788, JP-A-4-173867, JP-A-5-1225, JP-A-7-113033, JP-A-9-53063, JP-A-10-10. -251618, JP-A No. 2000-154368, JP-A No. 2001-164237, WO 97/05201, and the like.

Also when the composition of this invention contains sealing material hardened | cured material particle | grains, hardened | cured material can form an unevenness | corrugation on the surface and can improve the designability. Preferred diameters, blending amounts, materials, and the like of the cured sealant particles are as follows as described in JP-A No. 2001-115142. The diameter is preferably about 0.1 mm to 1 mm, more preferably about 0.2 to 0.5 mm. The blending amount is preferably 5 to 100% by weight, more preferably 20 to 50% by weight in the curable composition. Examples of the material include urethane resin, silicone, modified silicone, polysulfide rubber, and the like. The material is not limited as long as it is used for a sealing material, but a modified silicone-based sealing material is preferable.

<Plasticizer>
A plasticizer can be added to the curable composition of the present invention. By adding the plasticizer, the viscosity and slump property of the curable composition and the mechanical properties such as tensile strength and elongation of the cured product obtained by curing the composition can be adjusted.
Examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, and butyl benzyl phthalate; non-aromatic secondary compounds such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, and isodecyl succinate. Basic acid esters; Aliphatic esters such as butyl oleate and methyl acetylricinoleate; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Chlorinated paraffins; Hydrocarbon oils such as hydrogenated terphenyl; process oils; epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate.

Moreover, a polymeric plasticizer can be used. When a high-molecular plasticizer is used, the initial physical properties can be maintained over a long period of time compared to the case where a low-molecular plasticizer that is a plasticizer that does not contain a polymer component in the molecule is used. Furthermore, the drying property (also called paintability) when an alkyd paint is applied to the cured product can be improved.
Specific examples of the polymer plasticizer include vinyl polymers obtained by polymerizing vinyl monomers by various methods; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; Polyester plasticizer obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; Is a polyether polyol of 1000 or more polyethylene glycol, polypropylene glycol, polytetramethylene glycol or the like, or the hydroxyl group of these polyether polyols is an ester group, Examples include polyethers such as derivatives converted to thiol groups; polystyrenes such as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, and the like. It is not a thing.

Among these polymer plasticizers, those compatible with the component (A) or the component (F) are preferable. From this point, polyethers and vinyl polymers are preferable. Moreover, a vinyl polymer is preferable from the viewpoint of compatibility, weather resistance, and heat resistance. Among vinyl polymers, acrylic polymers and / or methacrylic polymers are preferable, and acrylic polymers such as polyacrylic acid alkyl esters are more preferable. The polymer synthesis method is preferably a living radical polymerization method and more preferably an atom transfer radical polymerization method because the molecular weight distribution is narrow and viscosity can be lowered. Further, it is preferable to use a polymer obtained by so-called SGO process obtained by continuous bulk polymerization of an alkyl acrylate monomer as described in JP-A-2001-207157 at high temperature and high pressure.

The number average molecular weight of the polymer plasticizer is preferably 500 to 15000, more preferably 800 to 10000, still more preferably 1000 to 8000, particularly preferably 1000 to 5000, and most preferably 1000 to 3000. . If the molecular weight is too low, the plasticizer will flow out over time due to heat and rain, and it will be difficult to maintain the initial physical properties over a long period of time, and it will be difficult to sufficiently improve the alkyd coating properties. Moreover, when molecular weight is too high, a viscosity will become high and workability | operativity will fall. The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow, preferably less than 1.80, more preferably 1.70 or less, still more preferably 1.60 or less, and even more preferably 1.50 or less. .40 or less is particularly preferable, and 1.30 or less is most preferable.
The number average molecular weight is measured by a GPC method in the case of a vinyl polymer and by a terminal group analysis method in the case of a polyether polymer. Moreover, molecular weight distribution (Mw / Mn) is measured by GPC method (polystyrene conversion).

The polymer plasticizer may not have a reactive silicon group, but may have a reactive silicon group. When it has a reactive silicon group, it acts as a reactive plasticizer and can prevent migration of the plasticizer from the cured product. In the case of having a reactive silicon group, the average number per molecule is preferably 1 or less, more preferably 0.8 or less. When using the plasticizer which has a reactive silicon group, especially the oxyalkylene polymer which has a reactive silicon group, the number average molecular weight needs to be lower than (A) component or (F) component.
A plasticizer may be used independently and may use 2 or more types together. Further, a low molecular plasticizer and a high molecular plasticizer may be used in combination. These plasticizers can also be blended at the time of polymer production.

When a plasticizer is used, the amount used is 5 parts by weight with respect to 100 parts by weight of component (A) or 100 parts by weight in total of component (A) and component (F) when component (F) is contained. -200 weight part is preferable, More preferably, it is 10-120 weight part, More preferably, it is 20-100 weight part. If it is less than 5 parts by weight, the effect as a plasticizer is not sufficiently exhibited, and if it exceeds 200 parts by weight, the mechanical strength of the cured product is insufficient.

<Adhesive agent>
To the curable composition of the present invention, a silane coupling agent, a reaction product of the silane coupling agent, or a compound other than the silane coupling agent can be added as an adhesion promoter.
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-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) Aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) amino Propylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- (2- (2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane, γ- (6-aminohexyl) Aminopropyltrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane Amino group-containing silanes such as N-benzyl-γ-aminopropyltrimethoxysilane and N-vinylbenzyl-γ-aminopropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ -Mercaptopropyl methyl Mercapto group-containing silanes such as dimethoxysilane and γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β -Epoxy group-containing silanes such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis Carboxysilanes such as (2-methoxyethoxy) silane and N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyl Vinyl-type unsaturated group-containing silanes such as tildimethoxysilane and γ-acryloyloxypropylmethyltriethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurates such as tris (trimethoxysilyl) isocyanurate Silanes etc. can be mentioned. In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, and the like, which are derivatives of these, can also be used as silane coupling agents. .

When using the silane coupling agent used for this invention, the usage-amount is 100 weight part of (A) component normally, or when it contains (F) component, it is the sum total of (A) component and (F) component. 0.1-20 weight part is preferable with respect to 100 weight part, and 0.5-10 weight part is more preferable.

The effects of the silane coupling agent added to the curable composition of the present invention are various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, mortar, vinyl chloride, acrylic, polyester, When used for organic base materials such as polyethylene, polypropylene, polycarbonate, etc., it exhibits a remarkable adhesive improvement effect under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving adhesion to various adherends is particularly remarkable.
Specific examples other than the silane coupling agent are not particularly limited, and examples thereof include epoxy resins, phenol resins, sulfur, alkyl titanates, and aromatic polyisocyanates.
The adhesiveness-imparting agent may be used alone or in combination of two or more.

<Physical property modifier>
You may add the physical property modifier which adjusts the tensile characteristic of the hardened | cured material produced | generated as needed to the curable composition of this invention. By using a physical property modifier, the hardness when the composition of the present invention is cured can be increased, or conversely, the hardness can be decreased and elongation at break can be produced.
Although it does not specifically limit as a physical property modifier, For example, alkyl alkoxysilanes, such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy Silanes, alkyl isopropenoxy silanes such as γ-glycidoxypropylmethyldiisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxy Silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxy Alkoxysilanes having a functional group such as a silane; silicone varnishes; polysiloxanes and the like. The said physical property modifier may be used independently and may be used together 2 or more types.

In particular, a compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis has an action of reducing the modulus of the cured product without deteriorating the stickiness of the surface of the cured product. Particularly preferred are compounds that produce trimethylsilanol. As a compound which produces | generates the compound which has a monovalent silanol group in a molecule | numerator by hydrolysis, the compound described in Unexamined-Japanese-Patent No. 5-117521 can be mentioned. Further, compounds that are derivatives of alkyl alcohols such as hexanol, octanol, decanol, and the like that generate a silicon compound that generates R ₃ SiOH such as trimethylsilanol by hydrolysis, and trimethylol described in JP-A-11-241029 Examples thereof include compounds that are derivatives of polyhydric alcohols having 3 or more hydroxyl groups such as propane, glycerin, pentaerythritol, sorbitol, etc., and that generate silicon compounds that generate R ₃ SiOH such as trimethylsilanol by hydrolysis.

The can also include compounds that produce a silicon compound that produces R ₃ SiOH such as trimethyl silanol a derivative of oxypropylene polymer as described in JP-A-7-258534 by hydrolyzing. Furthermore, a polymer having a crosslinkable hydrolyzable silicon-containing group and a silicon-containing group that can be converted into a monosilanol-containing compound by hydrolysis described in JP-A-6-279893 can also be used.
When using physical property modifiers, the amount used is 100 parts by weight of component (A), or when component (F) is contained, the total amount of component (A) and component (F) is 100 parts by weight. 0.1-20 weight part is preferable, More preferably, it is 0.5-10 weight part.

<Thixotropic agent (anti-sagging agent)>
A thixotropic agent (anti-sagging agent) may be added to the curable composition of the present invention as necessary to prevent sagging and improve workability.
The thixotropic agent (anti-sagging agent) is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These thixotropic agents may be used alone or in combination of two or more.
When using a thixotropic agent, the amount used is 100 parts by weight of component (A), or when it contains component (F), 100 parts by weight in total of component (A) and component (F). 0.1 to 20 parts by weight is preferable.

<Compound containing epoxy group>
In the curable composition of the present invention, a compound containing an epoxy group in one molecule can be used. When a compound having an epoxy group is used, the restorability of the cured product can be improved.
Examples of the compound containing an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, An epoxy butyl stearate etc. are mentioned. Of these, E-PS is particularly preferred.
When a compound containing an epoxy group is used, the amount used is 100 parts by weight of component (A), or when component (F) is included, the amount used is 100 parts by weight in total of component (A) and component (F). On the other hand, 0.5-50 weight part is preferable.

<Photo-curing substance>
A photocurable substance can be used for the curable composition of this invention.
When a photocurable material is used, a film of the photocurable material is formed on the surface of the cured product, and the stickiness and weather resistance of the cured product can be improved. The photo-curing substance is a substance in which the molecular structure undergoes a chemical change in a considerably short time by the action of light, resulting in a change in physical properties such as curing. Many compounds such as organic monomers, oligomers, resins and compositions containing them are known as this type of compound, and any commercially available compound can be adopted. Typical examples include unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, and the like.

Unsaturated acrylic compounds include monomers, oligomers and mixtures thereof having one or several acrylic or methacrylic unsaturated groups, including propylene (or butylene, ethylene) glycol di (meth) acrylate, neopentyl glycol Examples thereof include monomers such as di (meth) acrylate and oligoesters having a molecular weight of 10,000 or less. Specifically, for example, special acrylate (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; (Trifunctional) Aronix M -305, Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, and (Multifunctional) Aronix M-400 can be exemplified, but particularly contain an acrylic functional group. The compound which contains 3 or more same functional groups on average in 1 molecule is preferable. (All Aronix is a product of Toa Gosei Chemical Co., Ltd.)

Examples of the polyvinyl cinnamates include photosensitive resins having a cinnamoyl group as a photosensitive group, and those obtained by esterifying polyvinyl alcohol with cinnamic acid, as well as many polyvinyl cinnamate derivatives.
The azide resin is known as a photosensitive resin having an azide group as a photosensitive group. Usually, in addition to a rubber photosensitive solution in which a diazide compound is added as a photosensitive agent, “photosensitive resin” (March 17, 1972). There are detailed examples in Publishing, Publishing Society of Printing Press, page 93-, page 106-, page 117-), these may be used alone or in combination, and a sensitizer may be added as necessary. Can do. Note that the addition of a sensitizer such as ketones or nitro compounds or an accelerator such as amines may enhance the effect.

When using a photocurable material, the amount used is 100 parts by weight of component (A), or when it contains component (F), it is 100 parts by weight in total of component (A) and component (F). 0.1 to 20 parts by weight is preferable, and 0.5 to 10 parts by weight is more preferable. If the amount is less than 0.1 part by weight, the effect of further improving the weather resistance cannot be exhibited sufficiently. If the amount exceeds 20 parts by weight, the cured product tends to be too hard and tends to crack.

<Oxygen curable substance>
In the curable composition of the present invention, an oxygen curable substance can be used.
Examples of the oxygen curable substance include unsaturated compounds that can react with oxygen in the air, react with oxygen in the air to form a cured film near the surface of the cured product, It works to prevent dust and dust from adhering.

Specific examples of the oxygen curable substance include drying oils typified by drill oil and linseed oil, various alkyd resins obtained by modifying the compounds; acrylic polymers and epoxy resins modified by drying oils , Silicone resins; 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymers obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc. Liquid polymers, liquid copolymers such as NBR and SBR obtained by copolymerizing monomers such as acrylonitrile and styrene copolymerizable with these diene compounds so that the main component is a diene compound, Further, various modified products thereof (maleinized modified products, boiled oil modified products, etc.) and the like can be mentioned. These may be used alone or in combination of two or more. Of these, drill oil and liquid diene polymers are particularly preferable.
Moreover, the effect may be enhanced if a catalyst for promoting the oxidative curing reaction or a metal dryer is used in combination. Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, zirconium octylate, and amine compounds.

When an oxygen curable substance is used, the amount used is 100 parts by weight of component (A), or when it contains component (F), 100 parts by weight in total of component (A) and component (F). 0.1 to 20 parts by weight is preferable, and 0.5 to 10 parts by weight is more preferable. If the amount used is less than 0.1 parts by weight, the contamination is not improved sufficiently, and if it exceeds 20 parts by weight, the tensile properties of the cured product tend to be impaired.
As described in JP-A-3-160053, the oxygen curable substance is preferably used in combination with a photocurable substance.

<Antioxidant (Anti-aging agent)>
An antioxidant (antiaging agent) can be used in the curable composition of the present invention. When antioxidant is used, the heat resistance of hardened | cured material can be improved.
Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred.
Similarly, Tinuvin 622LD, Tinuvin 144; CHIMASSORB944LD, CHIMASSORB119FL (all of which are manufactured by Ciba Geigy Japan); MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-63, MARK LA-68 Also manufactured by Adeka Argus Chemical Co., Ltd.); A hindered amine light stabilizer can also be used. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731.
When using an antioxidant, the amount used thereof is 100 parts by weight of component (A), or when it contains component (F), with respect to a total of 100 parts by weight of component (A) and component (F), 0.1-10 weight part is preferable, More preferably, it is 0.2-5 weight part.

<Light stabilizer>
A light stabilizer can be used in the curable composition of the present invention. Use of a light stabilizer can prevent photooxidation degradation of the cured product.
Examples of the light stabilizer include benzotriazole, hindered amine, and benzoate compounds, with hindered amines being particularly preferred. Specific examples of the light stabilizer are also described in JP-A-9-194731.
When the light stabilizer is used, the amount used thereof is 100 parts by weight of the component (A), or when the component (F) is contained, the total amount of the component (A) and the component (F) is 100 parts by weight. 0.1-10 weight part is preferable, More preferably, it is 0.2-5 weight part.

When a photocurable material is used in combination with the composition of the present invention, particularly when an unsaturated acrylic compound is used, a tertiary amine is contained as a hindered amine light stabilizer as described in JP-A-5-70531. Use of a hindered amine light stabilizer is preferred for improving the storage stability of the composition. As tertiary amine-containing hindered amine light stabilizers, Tinuvin 622LD, Tinuvin 144; CHIMASSORB 119FL (all manufactured by Ciba Geigy Japan); MARK LA-57, LA-62, LA-67, LA-63 (all above) Adeka Argus Chemical Co., Ltd.); light stabilizers such as Sanol LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all of which are manufactured by Sankyo Co., Ltd.).

<Ultraviolet absorber>
An ultraviolet absorber can be used for the curable composition of the present invention. When the ultraviolet absorber is used, the surface weather resistance of the cured product can be enhanced.
Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferable.
When using an ultraviolet absorber, the amount used thereof is 100 parts by weight of component (A), or when it contains component (F), the total amount of component (A) and component (F) is 100 parts by weight, 0.1-10 weight part is preferable, More preferably, it is 0.2-5 weight part.
It is preferable to use a phenolic or hindered phenolic antioxidant, a hindered amine light stabilizer and a benzotriazole ultraviolet absorber in combination.

<Epoxy resin>
An epoxy resin can be added to the curable composition of the present invention. The composition to which the epoxy resin is added is particularly preferable as an adhesive, particularly as an adhesive for exterior wall tiles.
Examples of the epoxy resin include epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame retardant type epoxy resin such as glycidyl ether of tetrabromobisphenol A, novolak type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A glycidyl ether type epoxy resin of propylene oxide adduct, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol epoxy resin, diaminodiphenylmethane epoxy resin, urethane-modified epoxy resin, various alicyclic epoxy resins, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether Examples include glycidyl ethers of polyhydric alcohols such as glycerin, hydantoin type epoxy resins, epoxidized products of unsaturated polymers such as petroleum resins, etc., but are not limited thereto, and generally used epoxy resins Can be used.
Those containing at least two epoxy groups in the molecule are preferred because they are highly reactive during curing and the cured product easily forms a three-dimensional network. More preferable examples include bisphenol A type epoxy resins or novolac type epoxy resins.

When these epoxy resins are used, the use ratio of the epoxy resin and the component (A) or the sum of the components (A) and (F) when the component (F) is contained is a weight ratio, Component (A) or the sum of components (A) and (F) / epoxy resin = 100/1 to 1/100.
When the ratio of the component (A) or the sum of the components (A) and (F) / epoxy resin is less than 1/100, it is difficult to obtain the effect of improving the impact strength and toughness of the cured epoxy resin. When the ratio of component (A) or the sum of components (A) and (F) / epoxy resin exceeds 100/1, the strength of the organic polymer cured product tends to be insufficient.
The preferred use ratio varies depending on the use of the curable composition, etc., and thus cannot be determined unconditionally. For example, when improving the impact resistance, flexibility, toughness, peel strength, etc. of the cured epoxy resin, When 100 parts by weight of the epoxy resin contains the component (A) or the component (F), the total of the component (A) and the component (F) is 1 to 100 parts by weight, more preferably 5 to 100 parts. It is better to use parts by weight.
On the other hand, when improving the strength of the cured product of the composition containing the component (A) or the components (A) and (F), 100 parts by weight of the component (A) or the component (F) When it contains, it is good to use 1-200 weight part of epoxy resins with respect to a total of 100 weight part of (A) component and (F) component, More preferably, 5-100 weight part is used.

When an epoxy resin is added, it is natural that the composition of the present invention can be used in combination with a curing agent that cures the epoxy resin.
There is no restriction | limiting in particular as an epoxy resin hardening | curing agent which can be used, The epoxy resin hardening | curing agent generally used can be used. Specifically, for example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperidine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, amine-terminated poly Primary and secondary amines such as ether; tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol and tripropylamine, and salts of these tertiary amines; polyamide resins; imidazole Dicyandiamides; boron trifluoride complex compounds, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecynyl succinic anhydride, pyromellitic anhydride, chlorenic anhydride, etc .; alcohols ; Fe Lumpur acids; carboxylic acids; but the compound of diketone complex compounds of aluminum or zirconium, or the like can be exemplified, but the invention is not limited thereto. Further, the curing agents may be used alone or in combination of two or more.
When an epoxy resin curing agent is used, the amount used is preferably 0.1 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin.

Ketimine can also be used as a curing agent for the epoxy resin. Ketimine is stably present in the absence of moisture, and is decomposed into primary amines and ketones by moisture, and the resulting primary amine becomes a room temperature curable curing agent for the epoxy resin. When ketimine is used, a one-component composition can be obtained. Such a ketimine can be obtained by a condensation reaction between an amine compound and a carbonyl compound.

A known amine compound or carbonyl compound may be used for the synthesis of ketimine.
Examples of amine compounds include ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane, 2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, p. -Diamines such as phenylenediamine and p, p'-biphenylenediamine; polyvalent amines such as 1,2,3-triaminopropane, triaminobenzene, tris (2-aminoethyl) amine, tetra (aminomethyl) methane; Polyalkylene polyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; polyoxyalkylene polyamines; γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, An aminosilane such as N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane;

Examples of carbonyl compounds include aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, diethylacetaldehyde, glyoxal, and benzaldehyde; cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone, and trimethylcyclohexanone; acetone, Aliphatic ketones such as methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone; acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate, Β-dicarbonyl compounds such as diethyl malonate, methyl ethyl malonate and dibenzoylmethane; etc. It can be used.

When an imino group is present in the ketimine, the imino group may be reacted with styrene oxide; glycidyl ether such as butyl glycidyl ether or allyl glycidyl ether; glycidyl ester or the like.
These ketimines may be used alone or in combination of two or more.
When using ketimine, the usage-amount is preferable with respect to 100 weight part of epoxy resins, 1-100 weight part, The usage-amount changes with the kind of epoxy resin and ketimine.

<Other additives>
Various additives may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product.
Examples of such additives include, for example, flame retardants, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, Examples include solvents and fungicides. These various additives may be used alone or in combination of two or more. Specific examples other than the specific examples of the additives listed in the present specification include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-62-2904, It is described in Japanese Laid-Open Patent Publication No. 2001-72854.

<Preparation of curable composition>
The curable composition of the present invention can be prepared as a one-component type in which all the blending components are blended and stored in advance and cured by moisture in the air after construction. Moreover, it can also prepare as a two-component type which mix | blends components, such as a curing catalyst, a filler, a plasticizer, and water, separately as a hardening | curing agent, and mixes this compounding material and a polymer composition before use. From the viewpoint of workability, a one-component type is preferable.
When the curable composition is of a one-component type, all the ingredients are pre-blended, so the water-containing ingredients are dehydrated and dried before use, or dehydrated during mixing and kneading. Is preferred.
When the curable composition is a two-component type, it is not necessary to add a curing catalyst to the main component containing the component (A) or the component (A) and the component (F). Although there is little concern about gelation even if this amount of water is contained, it is preferable to perform dehydration drying when long-term storage stability is required.

As the dehydration and drying method, a heat drying method is preferable in the case of a solid material such as a powder, and a dehydration method using a reduced pressure dehydration method or a synthetic zeolite, activated alumina, silica gel or the like is preferable in the case of a liquid material. Alternatively, a small amount of an isocyanate compound may be blended and the isocyanate group and water reacted to dehydrate. In addition to the dehydration drying method, lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, The storage stability is further improved by adding an alkoxysilane compound such as γ-glycidoxypropyltrimethoxysilane.
The amount of silicon compound that can react with water such as dehydrating agent, especially vinyltrimethoxysilane, is 100 parts by weight of component (A), or component (A) and component (F) when component (F) is contained. The range of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, is based on the total of 100 parts by weight.

The method for preparing the curable composition of the present invention is not particularly limited. For example, the above-described components are blended and kneaded using a mixer, roll, kneader or the like at room temperature or under heating, or a small amount of a suitable solvent is used. Then, usual methods such as dissolving and mixing the components may be employed.

When exposed to the atmosphere, the curable composition of the present invention forms a three-dimensional network structure by the action of moisture, and cures to a solid having rubbery elasticity.

<< Usage >>
The curable composition of the present invention can be used as a sealing material and an adhesive.
Specifically, the curable composition of the present invention includes, for example, pressure-sensitive adhesives, sealants for buildings, ships, automobiles, roads, adhesives, mold preparations, vibration-proofing materials, vibration-damping materials, sound-proofing materials, foams, and the like. Can be used for materials, paints, spraying materials, etc. Also, electrical and electronic parts materials such as solar cell backside sealing materials, electrical insulation materials such as insulation coating materials for electric wires and cables, elastic adhesives, powder coating materials, casting materials, medical rubber materials, medical adhesives , Medical equipment sealing materials, food packaging materials, sealing materials for joints of exterior materials such as sizing boards, coating materials, primers, conductive materials for shielding electromagnetic waves, thermal conductive materials, hot melt materials, potting agents for electrical and electronic equipment, films , Gaskets, various molding materials, and anti-rust / waterproof sealing materials for meshed glass and laminated glass end faces (cut parts), liquid sealants used in automobile parts, electrical parts, various machine parts, etc. It can be used for various purposes. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, resin molding, etc. alone or with the help of a primer, it can also be used as various types of sealing compositions and adhesive compositions. .

Further, since the curable composition of the present invention is excellent in resilience, durability and creep resistance, it can be used for interior panel adhesives, exterior panel adhesives, tile tensioning adhesives, stone tensioning adhesives, ceilings. Finishing adhesives, floor finishing adhesives, wall finishing adhesives, vehicle panel adhesives, electrical / electronic / precision equipment assembly adhesives, direct glazing sealants, multi-layer glass sealants, SSG construction It is particularly preferable when used as a sealing material, a sealing material for a working joint of a building, or the like.

According to the present invention, it is possible to provide a curable composition that can realize good restorability and creep resistance, and has greatly improved surface tack, dust adhesion, and weather resistance under outdoor use over a long period of time. it can.

The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
In the following synthesis examples, “number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column packed with polystyrene cross-linked gel (shodex GPC K-804; manufactured by Showa Denko) and chloroform as a GPC solvent were used.
Moreover, the viscosity of the polymer prepared in the synthesis example was measured at a temperature of 23 ° C. and 2 rpm using a BS viscometer manufactured by Tokimec Co., Ltd.

(Synthesis Example 1)
Synthesis of poly (n-butyl acrylate) having halogen at the terminal In a 50 ml flask, cuprous bromide 0.63 g (4.4 mmol), pentamethyldiethylenetriamine 0.76 g (4.4 mmol), acetonitrile 5 ml, 2, 5 -1.6 g (4.4 mmol) of diethyl dibromoadipate and 44.7 g (349 mmol) of n-butyl acrylate were charged, freeze degassed, and then reacted at 70 ° C for 7 hours in a nitrogen atmosphere. By removing and purifying the copper catalyst through an activated alumina column, a polymer having a Br group at the end was obtained. The number average molecular weight of the obtained polymer was 10700, and the molecular weight distribution was 1.15.

Synthesis of poly (n-butyl acrylate) having an alkenyl group at the end 35 g of poly (n-butyl acrylate) having a Br group at the end obtained above in a 200 ml flask under nitrogen atmosphere, pentenoic acid Potassium 2.2 g (16.1 mmol) and dimethylacetamide (DMAc) 35 mL were charged and reacted at 70 ° C. for 4 hours. Unreacted potassium pentenoate and produced potassium bromide in the reaction mixture were removed by water extraction purification to obtain a polymer having an alkenyl group at the terminal. The number average molecular weight of the obtained polymer was 11300, and the molecular weight distribution was 1.12. The number of alkenyl groups per molecule of polymer determined from ¹ H-NMR analysis was 1.82.

Synthesis of poly (acrylic acid-n-butyl) having a crosslinkable silyl group at its terminal In a 200 mL pressure resistant reaction tube, 15 g of the polymer having an alkenyl group at the terminal obtained above, 1.8 mL (14.5 mmol) of methyldimethoxysilane , 0.26 mL (2.4 mmol) of methyl orthoformate and 10 ⁻⁴ mmol of platinum bis (divinyltetramethyldisiloxane), reacted at 100 ° C. for 4 hours, and a polymer having a crosslinkable silyl group at the terminal (A- 1) was obtained. The viscosity of the obtained polymer was 44 Pa · s, the number average molecular weight was 11900, and the molecular weight distribution was 1.12. The number of crosslinkable silyl groups per polymer molecule was 1.46 by ¹ H-NMR analysis.

(Synthesis Example 2)
Synthesis of hydroxyl-terminated polypropylene oxide 0.04 g of zinc hexacyanocobaltate-glyme complex, 2.0 g of dipropylene glycol in THF and 9.6 g of propylene oxide were added to the autoclave and reacted at 76 ° C. in a nitrogen atmosphere. I let you. Thereafter, 145.2 g of propylene oxide was added to the reaction system. Unreacted monomer and solvent were recovered and purified to obtain 150 g of oily product. The obtained product showed a single peak by GPC analysis, and the molecular weight distribution (Mw / Mn) was 1.14. Its hydroxyl value was 11.8 mgKOH / g.

Synthesis of unsaturated group- terminated polypropylene oxide To 120 g of the hydroxyl-terminated polypropylene oxide obtained above, 5.8 g (30.2 mmol) of a methanol solution of sodium methoxide (28 wt%) was added, and the mixture was heated at 130C in an autoclave. And then devolatilized under reduced pressure. It returned to nitrogen atmosphere, 2.8 g (36.2 mmol) of allyl chloride was added, and it was made to react for 2 hours.
The reaction mixture was dissolved in hexane, adsorbed with aluminum silicate, and then hexane was distilled off under reduced pressure to obtain unsaturated group-terminated polypropylene oxide.

Synthesis of crosslinkable silyl group- terminated polypropylene oxide 120 g of unsaturated group-terminated polypropylene oxide obtained by the above synthesis was charged into a pressure-resistant glass reaction vessel, and an isopropanol solution of chloroplatinic acid (25 g of H ₂ PtCl _6. (6H ₂ O dissolved in 500 g of isopropanol) After adding 0.02 g, the mixture was stirred for 30 minutes. Methyldimethoxysilane (2.1 g, 20.2 mmol) was added dropwise and reacted at 90 ° C. for 2 hours. Volatile components were removed by reducing the pressure to obtain a crosslinkable silyl group-terminated polypropylene oxide (F-1). The polymer had a viscosity of 6 Pa · s, a number average molecular weight of 17,300, and a molecular weight distribution of 1.14.

(Examples 1-3, 5-6, Comparative Example 1)
As the component (A), the vinyl polymer (A-1) having at least one crosslinkable silyl group obtained in Synthesis Example 1 was used, and the filler, plasticizer, thixotropy was prepared according to the formulation shown in Table 1. Each of the imparting agent, ultraviolet absorber and antioxidant was weighed and kneaded well with three paint rolls to obtain a main agent.
Next, with the composition shown in Table 1, the carboxylic acid metal salt of the component (B), the carboxylic acid of the component (C), and the amine compound of the component (D) are weighed against the main agent, and a spatula is used. After mixing by hand mixing for 3 minutes, a two-component curable composition was obtained.

Example 4
A curable composition was prepared in the same manner as in Example 1 except that 30 parts by weight of the polymer in Example 1 was obtained using the polyether polymer (F-1) obtained in Synthesis Example 2. Obtained.

(Comparative Example 2)
A curable composition was obtained in the same manner as in Example 1 except that Neostan U-220, which is organic tetravalent tin, was used as a curing catalyst.

Using the curable compositions obtained in the above Examples and Comparative Examples, each physical property was measured and evaluated by the following methods. The results are shown in Table 1.
(Skinning time)
23 ° C., 55% R.D. H. Under the conditions, the curable composition is stretched to a thickness of about 3 mm, and the surface of the curable composition is sometimes lightly touched with a microspatula until the composition does not come into contact with the microspatula. It was measured.

(Restoration rate)
The curable composition was cured at 23 ° C. × 3 days + 50 ° C. × 4 days to prepare a sheet having a thickness of 3 mm. This sheet was punched out into a No. 3 dumbbell mold, and fixed at 100 ° C. for 24 hours in a state where 20 mm between the marked lines was pulled until it became 40 mm (100% elongation). This was opened at 23 ° C., and the restoration rate (%) was measured from the rate at which the marked line was restored after 1 hour. A larger restoration rate indicates better restoration.

(Creep characteristics)
In the same manner as described above, a sheet formed by curing the curable composition was punched into a dumbbell shape to prepare a dumbbell-shaped cured product. One end of this dumbbell piece was fixed in an oven at 60 ° C., and the dumbbell piece was suspended. On the lower end of the suspended dumbbell piece, a load 0.4 times the M50 value obtained by the above-described measurement of tensile properties of the cured product was applied. The displacement difference of the distance between marked lines was measured immediately after applying the load and after 200 hours. The smaller the displacement difference, the better the creep resistance.

(Residual tack)
A sheet-like test body having a thickness of about 3 mm was prepared using the curable composition, and was attached to an aluminum plate and exposed outdoors (Takasago City, Hyogo Prefecture) with a 45 ° inclination on the north surface. After 7 days, the cured surface was touched with a finger to evaluate stickiness. > ◎ is a state without stickiness at all, and ◎, ○, ○ △, △, △ ×, × indicate bad states in this order.

(Contamination (dust adhesion))
A sheet-like test body having a thickness of about 3 mm was prepared using the curable composition, and was attached to an aluminum plate and exposed outdoors (Takasago City, Hyogo Prefecture) with a 45 ° inclination on the north surface. After 2 weeks and 1 month, the degree of adhesion of dust, sand, etc. to the surface of the cured product was visually evaluated. ◎ is the same state as before exposure, indicating bad state in order of ○, ○ △, △, △ ×, ×.

(Weatherability)
An ISO H type test piece having a thickness of about 12 mm was prepared using the curable composition, and after curing at 23 ° C. for 7 days and 50 ° C. for 7 days, it was attached to an aluminum plate, and a suga test machine ( An accelerated weather resistance test was conducted using a sunshine weatherometer manufactured by Co., Ltd. (conditions: black panel 63 ° C., rainfall 18 minutes / 120 minutes cycle). Those whose surface is in the same state as the initial state are indicated by ◯, and those whose surface is cracked are indicated by ×.

From the above results, as shown in Comparative Example 2 of Table 1, when Neostan U-220, which is organic tetravalent tin, is used as a curing catalyst, the restoration rate and creep resistance are poor. On the other hand, as shown in Examples 1 to 6, when using a carboxylic acid tin and an amine compound, or a carboxylic acid and an amine compound, the recovery rate and creep resistance are excellent, and surface tack, dust adhesion, and weather resistance are excellent. Is also excellent. It can be seen that the use of a carboxylic acid metal salt in which the carbon atom adjacent to the carbonyl group is a quaternary carbon can further improve the curability.

According to the curable composition of the present invention, it has excellent resilience and creep resistance, there is almost no surface tack after curing in a short period, there is little surface contamination over a long period of time, and cracks on the surface even under long-term use outdoors. Further, it is possible to provide a cured product that does not cause discoloration and has excellent weather resistance. Therefore, the curable composition of this invention is suitable for a sealing material, an adhesive agent, etc.

Claims (25)

(A) Vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1)-[Si (R ¹ ) _2-b (Y) _b O] _m -Si (R ² ) _3-a (Y) _a (1)
{Wherein R ¹ and R ² are the same or different and are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) _3. A triorganosiloxy group represented by SiO- (R 'represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different); When two or more R ¹ or R ² are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2 or 3, and b represents 0, 1 or 2. m shows the integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. },
(B) a carboxylic acid metal salt, and
(D) An amine compound is contained, and the (D) amine compound is composed of at least two kinds, at least one of which is a primary and / or secondary amine compound having a melting point of 20 ° C. or higher. A curable composition characterized. (B) Component carboxylate metal salt is tin carboxylate, lead carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, titanium carboxylate, zirconium carboxylate, hafnium carboxylate, vanadium carboxylate, manganese carboxylate The curable composition according to claim 1, wherein the curable composition is at least one selected from iron carboxylate, cobalt carboxylate, nickel carboxylate, and cerium carboxylate. The curable composition according to claim 1 or 2, wherein the component (B) is tin carboxylate. (B) The curable composition of any one of Claims 1-3 whose component is divalent tin carboxylate. The curable composition of any one of Claims 1-4 whose carbon atom adjacent to the carbonyl group which comprises the carboxylic acid of (B) component is a quaternary carbon. Furthermore, (C) Carboxylic acid and / or a carboxylic acid derivative are contained, The curable composition of any one of Claims 1-5 characterized by the above-mentioned. (A) Vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1)-[Si (R ¹ ) _2-b (Y) _b O] _m -Si (R ² ) _3-a (Y) _a (1)
{Wherein R ¹ and R ² are the same or different and are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) _3. A triorganosiloxy group represented by SiO- (R 'represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different); When two or more R ¹ or R ² are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2 or 3, and b represents 0, 1 or 2. m shows the integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. },
(C) a carboxylic acid and / or a carboxylic acid derivative, and
(D) An amine compound is contained, and the (D) amine compound is composed of at least two kinds, at least one of which is a primary and / or secondary amine compound having a melting point of 20 ° C. or higher. A curable composition characterized. The curable composition of Claim 6 or 7 whose carbon atom adjacent to the carbonyl group which comprises the carboxylic acid of (C) component is quaternary carbon. The curing according to any one of claims 1 to 8, further comprising (F) a polyether polymer having at least one crosslinkable silyl group represented by the general formula (1). Sex composition.
_{^{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
{Wherein R ¹ and R ² are the same or different and are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) _3. A triorganosiloxy group represented by SiO- (R 'represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different); When two or more R ¹ or R ² are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2 or 3, and b represents 0, 1 or 2. m shows the integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. } The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography of the vinyl polymer of the component (A) is less than 1.8. The curable composition of any one of these. The curable composition according to any one of claims 1 to 10, wherein the main chain of the vinyl polymer (A) is a (meth) acrylic polymer. The curable composition according to any one of claims 1 to 11, wherein the main chain of the vinyl polymer (A) is produced by a living radical polymerization method. The curable composition according to any one of claims 1 to 12, wherein the main chain of the vinyl polymer (A) is produced by an atom transfer radical polymerization method. The curable composition according to any one of claims 1 to 13, wherein the vinyl polymer of the component (A) has at least one crosslinkable silyl group represented by the general formula (1) at the molecular chain terminal. . The vinyl polymer as the component (A) has the following steps:
(1) An organic halide or a sulfonyl halide compound is used as an initiator, and a vinyl monomer is radically polymerized using a transition metal complex as a catalyst to produce a vinyl polymer having a halogen at its terminal,
(2) A vinyl polymer having an alkenyl group at the terminal is produced by reacting an oxyanion having an alkenyl group to replace halogen.
(3) reacting a hydrosilane compound having a crosslinkable silyl group represented by the general formula (1);
The curable composition of any one of Claims 1-14 which is a polymer obtained by these. (C) The curable composition of any one of Claims 6-15 whose component is a fatty acid or its derivative (s). (A) 100 parts by weight of component, or (F) when component is contained 0.01 to 20 parts by weight of component (B) with respect to a total of 100 parts by weight of component (A) and component (F) The curable composition according to any one of claims 1 to 6 and 8 to 16. (A) 100 parts by weight of the component, or (F) when the component is contained, 0.01 to 20 parts by weight of the (C) component with respect to the total of 100 parts by weight of the (A) and (F) components The curable composition according to any one of claims 6 to 17, wherein: The curable composition according to any one of claims 9 to 18, wherein the polyether polymer of component (F) is essentially polypropylene oxide. The amine compound containing a hydrocarbon group having at least one hetero atom as a substituent as the amine compound of component (D) is included, and the curability according to any one of claims 1 to 19 Composition. The amine compound containing a hydrocarbon group having a hetero atom on the 2nd to 4th carbon atoms as the amine compound of component (D) is included in any one of claims 1 to 20, The curable composition as described. 100 parts by weight of component (A) or (F) When component (F) is included, 0.1 to 20 parts by weight of component (D) is added to 100 parts by weight of component (A) and component (F) The curable composition according to any one of claims 1 to 21, wherein: The primary and / or secondary amine compound having a melting point of 20 ° C. or higher is a compound that reacts with water to form a primary and / or secondary amine. The curable composition according to any one of 22 above. The sealing material which uses the curable composition of any one of Claims 1-23. The adhesive agent using the curable composition of any one of Claims 1-23.