JP6376303B1 - Curable composition and sealing material composition - Google Patents

Abstract

Provided are a curable composition and a sealing material composition that are excellent in workability and excellent in mechanical properties and weather resistance of a cured product. A (meth) acrylic polymer (A) having a weight average molecular weight of 500 or more and less than 10,000, and a (meth) acrylic weight having a weight average molecular weight of 10,000 or more and 100,000 or less. A curable composition containing a combination (B), wherein the (meth) acrylic polymer (A) has a double bond in the molecule of 0.01 meq / g or more and 1.0 meq / g or less, The (meth) acrylic polymer (B) has a reactive silyl group in the molecule. [Selection figure] None

Description

  The present invention relates to a curable composition, and more specifically, a curable composition capable of forming a cured product that exhibits excellent mechanical properties by curing at room temperature with moisture such as in the air, and the curable composition. The present invention relates to the use of the composition as a sealant composition.

Examples of the curable composition containing a room temperature-curable polymer having a reactive group include compositions containing various polymers such as modified silicone, urethane, polysulfide, and acrylic. Widely used as adhesives, sealing materials, paints, etc. in applications related to the electronic field and automobiles. For example, a modified silicone polymer is a curable composition based on an oxyalkylene polymer having a hydrolyzable silyl group, but has good workability and mechanical properties such as elongation at break and strength at break. Since it is a well-balanced material, it is widely used as a base polymer for adhesives and sealants.
However, it is known that a curable composition having a modified silicone-based polymer as a base polymer has a problem that the resulting cured product has insufficient weather resistance. For this reason, a curable composition containing an acrylic polymer has been proposed.

  Patent Document 1 discloses a specific vinyl polymer having an alkoxysilyl group, a polyoxyalkylene compound having an alkoxysilyl group at the terminal, and a specific vinyl polymer having a specific molecular weight and having no polypropylene glycol or alkoxysilyl group. A containing sealant composition is disclosed. Patent Document 2 discloses a sealing material composition containing an oxyalkylene polymer having a hydrolyzable silyl group and a specific vinyl polymer having a crosslinkable functional group. Patent Document 3 includes a specific vinyl polymer containing a (meth) acrylic acid ester monomer having a hydrolyzable silyl group as a constituent monomer, and a hydrolyzable silyl group-containing oxyalkylene polymer. A curable resin composition is disclosed.

JP 2004-18748 A International Publication No. 2008/059872 JP 2014-118502 A

  Cured products obtained from the compositions described in Patent Documents 1 to 3 exhibit good mechanical properties and improved weather resistance. However, the request | requirement regarding a weather resistance improvement is high, and the further weather resistance improvement was calculated | required also with respect to the curable composition. In general, the weather resistance tends to be improved by increasing the molecular weight of the polymer. However, since the composition has a high viscosity, it is known that problems arise in terms of coating properties and handling.

  The present invention has been made in view of the above circumstances, and provides a curable composition and a sealing material composition that are excellent in workability because of low viscosity and excellent in mechanical properties and weather resistance of a cured product. It is intended.

  As a result of diligent studies to solve the above problems, the present inventor has found that a curable composition containing a low molecular weight (meth) acrylic polymer based on a (meth) acrylic polymer having a reactive silyl group as a base resin. And it discovered that the weather resistance of hardened | cured material improved because the said low molecular (meth) acrylic-type polymer has a specific amount of double bonds. This invention is completed based on the said knowledge. According to the present specification, the following means are provided.

[1] A (meth) acrylic polymer (A) having a weight average molecular weight of 500 or more and less than 10,000, and a (meth) acrylic polymer having a weight average molecular weight of 10,000 or more and 100,000 or less. A curable composition comprising (B),
The (meth) acrylic polymer (A) has a double bond in the molecule of 0.01 meq / g or more and 1.0 meq / g or less,
The (meth) acrylic polymer (B) is a curable composition having a reactive silyl group in the molecule.
[2] The curable composition according to [1], wherein the (meth) acrylic polymer (A) has a viscosity at 25 ° C. of 1,000 mPa · s or more and 100,000 mPa · s or less.
[3] The curable composition according to [1] or [2], wherein the (meth) acrylic polymer (B) has a viscosity at 25 ° C. of 5,000 mPa · s or more and 300,000 mPa · s or less. .
[4] The curable composition according to any one of [1] to [3], wherein the (meth) acrylic polymer (A) has a reactive silyl group in the molecule.
[5] The (meth) acrylic polymer (B) according to any one of [1] to [4], wherein the molecule has 0.1 to 2.2 reactive silyl groups. Curable composition.
[6] The curable composition according to any one of [1] to [5], wherein the (meth) acrylic acid polymer (B) has a dialkoxysilyl group as a reactive silyl group.
[7] The (meth) acrylic polymer (B) is a (meth) acrylic acid alkyl ester having an alkyl group having 10 or more carbon atoms in all monomer units constituting the (meth) acrylic polymer. The curable composition according to any one of [1] to [6], containing 5% by mass or more.
[8] The double bond concentration contained in the entire (meth) acrylic polymer (A) and the (meth) acrylic polymer (B) is 0.01 meq / g or more and 0.50 meq / g or less. The curable composition according to any one of [1] to [7].
[9] The [1] to [8], wherein the (meth) acrylic polymer (A) and the (meth) acrylic polymer (B) are used in a mass ratio of 10 to 90/90 to 10. ] The curable composition in any one of.
[10] The curable composition according to any one of [1] to [9], further including an oxyalkylene polymer.
[11] The curable composition according to any one of [1] to [10], wherein the curing accelerator includes one or more compounds selected from the group consisting of a tin-based catalyst, a titanium-based catalyst, and a tertiary amine. object.
[12] A sealing material composition comprising the curable composition according to any one of [1] to [11].

  The curable composition of the present invention has low viscosity and excellent workability. In addition, a cured product having excellent strength and elongation and weather resistance can be obtained from the composition. For this reason, it is suitably used for sealing materials, adhesives for exterior tiles, and the like that require excellent mechanical properties and high weather resistance.

  The present invention will be described in detail below. In the present specification, “(meth) acryl” means acryl and / or methacryl, and “(meth) acrylate” means acrylate and / or methacrylate. The “(meth) acryloyl group” means an acryloyl group and / or a methacryloyl group.

  The curable composition of the present invention is a (meth) acrylic polymer having a weight average molecular weight of 500 or more and less than 10,000 (hereinafter referred to as “low molecular weight (meth) acrylic polymer”) as the component (A). And (B) component (meth) acrylic polymer having a weight average molecular weight of 10,000 or more and 100,000 or less (hereinafter referred to as “high molecular weight (meth) acrylic polymer”). If necessary, an oxyalkylene polymer having a reactive silyl group may be included as the component (C), and the curable composition of the present invention will be described below including details of each component. .

<(A) component: Low molecular weight (meth) acrylic polymer>
The low molecular weight (meth) acrylic polymer is a polymer having a structural unit derived from a (meth) acrylic monomer, for example, a monomer mixture containing a (meth) acrylic monomer is polymerized. Can be obtained. The (meth) acrylic monomer is a monomer having a (meth) acryloyl group in the molecule, such as (meth) acrylic acid, (meth) acrylic acid alkyl ester and (meth) acrylic acid alkoxyalkyl ester. Can be mentioned. The amount of the (meth) acrylic monomer used is preferably in the range of 10 to 100% by weight, more preferably 30 to 100% by weight, based on the total constituent monomers of the (meth) acrylic polymer. It is a range, More preferably, it is the range of 50-100 mass%.

  Specific examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic acid n. -Butyl, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, methyl (meth) acrylate Cyclohexyl, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, (meth) acrylic acid Decyl, undecyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic Tridecyl, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, stearyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate Henicosyl (meth) acrylate, behenyl (meth) acrylate, tetracosyl (meth) acrylate, hexacosyl (meth) acrylate, octacosyl (meth) acrylate, triacontyl (meth) acrylate, dotriacontyl (meth) acrylate, (Meth) acrylic acid tetratriacontyl, (meth) acrylic acid hexatriacontyl, (meth) acrylic acid octatriacontyl, (meth) acrylic acid tetracontylyl, (meth) acrylic acid isodecyl, (meth) acrylic acid isotope Decyl, isolauryl (meth) acrylate, isotridecyl (meth) acrylate, isotetradecyl (meth) acrylate, isopentadecyl (meth) acrylate, isohexadecyl (meth) acrylate, isoheptadecyl (meth) acrylate, (Meth) isostearyl acrylate, isononadecyl (meth) acrylate, isoeicosyl (meth) acrylate, isohenicosyl (meth) acrylate, isobehenyl (meth) acrylate, isotetracosyl (meth) acrylate, isohexacosyl (meth) acrylate, (Isooctacosyl (meth) acrylate, isotriacontyl (meth) acrylate, isodotriaconyl (meth) acrylate, isotetratriaconyl (meth) acrylate, isohexatriacontyl (meth) acrylate, ( Me (I) (meth) acrylic acid alkyl ester having a linear or branched aliphatic alkyl group or alicyclic alkyl group such as isooctacontyl acrylate, isotetracontyl (meth) acrylate, etc. One or more of these can be used. Among these, (meth) acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms is preferable from the viewpoint of mechanical properties of the cured product. The amount of the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms is preferably 10% by mass or more, more preferably based on the total constituent monomers of the (meth) acrylic polymer. It is 30 mass% or more, More preferably, it is 50 mass% or more. In addition, an upper limit is 100 mass%, 90 mass% may be sufficient, 80 mass% may be sufficient, and 50 mass% may be sufficient.

  In addition, when a (meth) acrylic acid alkyl ester having an alkyl group having 10 or more carbon atoms is used, when the curable composition contains an oxyalkylene polymer, the oxyalkylene polymer is good. It is preferable in terms of ensuring compatibility and improving mechanical properties and weather resistance. Preferably carbon number of an alkyl group is 10-20, More preferably, it is 12-20. The amount of (meth) acrylic acid alkyl ester having an alkyl group having 10 or more carbon atoms is preferably 5% by mass or more, more preferably 10%, based on all constituent monomers of the (meth) acrylic polymer. It is at least 20% by mass, more preferably at least 20% by mass. In addition, an upper limit is 100 mass% or less, 90 mass% or less may be sufficient, 80 mass% or less may be sufficient, and 50 mass% or less may be sufficient.

  Specific examples of (meth) acrylic acid alkoxyalkyl esters include methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, methoxyhexyl (meth) acrylate, (meth) Ethoxymethyl acrylate, ethoxyethyl (meth) acrylate, ethoxybutyl (meth) acrylate, ethoxyhexyl (meth) acrylate, butoxymethyl (meth) acrylate, butoxyethyl (meth) acrylate, (meth) acrylic acid Examples thereof include butoxybutyl and butoxyhexyl (meth) acrylate, and one or more of them can be used. Among these, (meth) acrylic acid alkoxyalkyl ester having an alkoxyalkyl group having 2 to 8 carbon atoms is preferable from the viewpoint of mechanical properties of the cured product, and (meth) acrylic having an alkoxyalkyl group having 2 to 4 carbon atoms. Acid alkoxyalkyl esters are more preferred. The amount of (meth) acrylic acid alkoxyalkyl ester used is preferably 10% by mass or more, more preferably 30% by mass or more, based on the total constituent monomers of the low molecular weight (meth) acrylic polymer. More preferably, it is 50 mass% or more. In addition, an upper limit is 100 mass% or less, 90 mass% or less may be sufficient, 80 mass% or less may be sufficient, and 50 mass% or less may be sufficient.

  The low molecular weight (meth) acrylic polymer may have a reactive silyl group in the molecule. When the low molecular weight (meth) acrylic polymer has a reactive silyl group, the mechanical properties of the cured product tend to be good. The type of the reactive silyl group is not particularly limited, and examples thereof include an alkoxysilyl group, a halogenosilyl group, and a silanol group, but an alkoxysilyl group is preferable from the viewpoint of easy control of reactivity. Specific examples of the alkoxysilyl group include trialkoxysilyl groups such as trimethoxysilyl group, triethoxysilyl group, dimethoxyethoxysilyl group and methoxydiethoxysilyl group; methyldimethoxysilyl group, methyldiethoxysilyl group, ethyldimethoxysilyl And dialkoxysilyl groups such as ethyldiethoxysilyl group; monoalkoxysilyl groups such as dimethylmethoxysilyl group, dimethylethoxysilyl group, diethylmethoxysilyl group and diethylethoxysilyl group. Among these, a dialkoxysilyl group is preferable in that the cured product exhibits good elongation and is excellent in heat stability.

When the low molecular weight (meth) acrylic polymer has a reactive silyl group, the average value of the number of reactive silyl groups contained in one molecule of the polymer is preferably 0.1 from the viewpoint of the tensile strength of the cured product. Or more, more preferably 0.2 or more. The average number of reactive silyl groups may be 0.3 or more, 0.5 or more, or 1.0 or more. From the viewpoint of securing the elongation of the cured product, the upper limit value is preferably 5.0 or less, more preferably 4.0 or less, still more preferably 3.0 or less, and even more preferably 2 .5 or less, and more preferably 2.2 or less. The range of the average value of the number of reactive silyl groups can be set by combining the above upper limit value and lower limit value. For example, it is 0.1 or more and 5.0 or less, and 0.1 or more 3.0 or less, 0.1 or more and 2.2 or less, or 0.2 or more and 2.2 or less may be sufficient.
The position of the reactive silyl group contained in the (meth) acrylic polymer is not particularly limited, and can be a side chain and / or a terminal of the polymer.

The reactive silyl group can be obtained, for example, by polymerizing a monomer mixture containing a (meth) acrylic monomer and a vinyl monomer having a reactive silyl group.
Examples of vinyl monomers having a reactive silyl group include vinyl silanes such as vinyl trimethoxy silane, vinyl triethoxy silane, vinyl methyl dimethoxy silane, and vinyl dimethyl methoxy silane; trimethoxysilylpropyl (meth) acrylate, ( Silyl group-containing (meth) acrylates such as (meth) acrylic acid triethoxysilylpropyl, (meth) acrylic acid dimethylmethoxysilylpropyl and (meth) acrylic acid methyldimethoxysilylpropyl; silyl groups such as trimethoxysilylpropyl vinyl ether Included vinyl ethers; silyl group-containing vinyl esters such as vinyl trimethoxysilylundecanoate are exemplified, and one or more of them can be used.

The low molecular weight (meth) acrylic polymer may be copolymerized with other monomers copolymerizable with these in addition to the above monomers.
Examples of the other monomers include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, (meth) Functional group-containing monomers such as 2-aminoethyl acrylate and ethylene oxide adduct of (meth) acrylic acid;
(Meth) acrylic acid aromatic esters such as phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate;
(Meth) acrylic acid trifluoromethyl methyl, (meth) acrylic acid 2-trifluoromethyl ethyl, (meth) acrylic acid 2-perfluoroethyl ethyl, (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutyl Ethyl, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethyl methyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethyl methyl (meth) acrylate Fluorine-containing (meth) acrylic acid esters such as 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate;
Fluorine-containing olefins such as perfluoroethylene, perfluoropropylene, vinylidene fluoride;
Aromatic monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof;
Maleic anhydride; unsaturated dicarboxylic acids such as maleic acid and fumaric acid, and their monoalkyl and dialkyl esters;
Maleimide compounds such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, phenylmaleimide, cyclohexylmaleimide;
Nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile;
Amide group-containing vinyl monomers such as acrylamide and methacrylamide;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate;
Alkenes such as ethylene and propylene;
Conjugated dienes such as butadiene and isoprene;
Examples include, but are not limited to, vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. Moreover, 1 type, or 2 or more types of these can be used.

  The weight average molecular weight (Mw) of the low molecular weight (meth) acrylic polymer is a molecular weight in terms of polystyrene by gel permeation chromatography (hereinafter also referred to as “GPC”), and is 500 from the viewpoint of the strength and weather resistance of the cured product. It is above, Preferably it is 1,000 or more, More preferably, it is 2,000 or more. Mw may be 3,000 or more. On the other hand, from the viewpoint of workability (low viscosity), the upper limit value of Mw is less than 10,000, may be 9,500 or less, may be 9,000 or less, and may be 8,000 or less. May be. The range of Mw is 500 or more and less than 10,000, but can be set by combining the above upper limit value and lower limit value. The range of Mw is, for example, 1,000 or more and less than 10,000, 2,000 or more and less than 10,000, or 3,000 or more and 90,000 or less.

  The molecular weight distribution of the low molecular weight (meth) acrylic polymer is calculated as a value (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn). Mw / Mn is preferably 5.0 or less, more preferably 4.0 or less, even more preferably 3.0 or less, and still more preferably 2. or less, from the viewpoint of the balance between tensile properties and workability. 5 or less, and even more preferably 2.0 or less. The lower limit value of Mw / Mn is usually 1.0.

  The viscosity of the low molecular weight (meth) acrylic polymer is preferably 1,000 mPa · s or more, more preferably 2,000 mPa · s or more at 25 ° C. The viscosity may be 3,000 mPa · s or more, 5,000 mPa · s or more, or 10,000 mPa · s or more. The upper limit of the viscosity is preferably 100,000 mPa · s or less, more preferably 80,000 mPa · s or less, and still more preferably 60,000 mPa · s or less. If the viscosity is 1,000 mPa · s or more, it is preferable because dripping is suppressed when applied to a vertical surface. By making the viscosity 100,000 or less, workability of the curable composition is improved. . The viscosity range can be set by combining the above upper limit value and lower limit value. For example, the viscosity range is 1,000 mPa · s or more and 100,000 mPa · s or less, and 2,000 mPa · s or more and 80,000 mPa · s. Or 3,000 mPa · s or more and 60,000 mPa · s or less.

  In the present invention, the low molecular weight (meth) acrylic polymer has a double bond in the molecule. When the low molecular weight (meth) acrylic polymer has an appropriate amount of double bonds, for example, the double bond reacts during a period in which the cured product is exposed to the outdoors, etc. Weather resistance is improved. For this reason, in this invention, the hardened | cured material can show the outstanding weather resistance, suppressing the viscosity of a low molecular weight (meth) acrylic-type polymer, ensuring workability | operativity. In addition, the said mechanism is inference and does not limit the scope of the present invention.

  The amount of double bonds contained in the low molecular weight (meth) acrylic polymer is required to be 0.01 meq / g or more from the viewpoint of expressing the effect on the weather resistance. The amount of double bonds may be 0.05 meq / g or more, 0.10 meq / g or more, 0.20 meq / g or more, or 0.30 meq / g or more. May be. On the other hand, if the amount of double bonds is too large, the degree of cross-linking of the cured product becomes too high during exposure, resulting in insufficient flexibility, and cracks tend to occur. For this reason, the amount of double bonds is 1.0 meq / g or less, preferably 0.50 meq / g or less, more preferably 0.30 meq / g or less. The range of the amount of double bonds can be set by combining the above upper limit value and lower limit value. For example, it is 0.01 meq / g or more and 1.0 meq / g or less, and 0.05 meq / g or more and 1 0.0 meq / g or less, or 0.10 meq / g or more and 0.50 meq / g or less.

  There are no particular limitations on the method for introducing a double bond, and methods known to those skilled in the art can be employed. For example, a method of copolymerizing a monomer having a plurality of double bonds in the molecule, a functional group and a double bond that can react with the functional group after producing a (meth) acrylic polymer having a functional group And a method of reacting with a compound having the following.

  Moreover, a double bond can also be introduce | transduced by manufacturing a (meth) acrylic-acid type polymer on high temperature conditions. For example, at a polymerization temperature of 100 ° C. or higher, a cleavage reaction starting from a hydrogen abstraction reaction from a polymer chain occurs due to high temperature polymerization, and therefore, ethylenic unsaturation represented by the following general formula (1) at the molecular end. A polymer having a bond is obtained. The polymerization temperature is preferably 120 ° C. or higher, more preferably 150 ° C. or higher. The higher the polymerization temperature, the higher the double bond concentration in the polymer. According to the said method, the (meth) acrylic-type polymer which has a double bond simply and with sufficient productivity can be obtained. Furthermore, it is possible to easily produce the molecular weight control without containing a large amount of impurities such as an initiator and a chain transfer agent. It is preferable not to use a chain transfer agent such as mercaptan because it leads to a decrease in weather resistance. On the other hand, the upper limit of the polymerization temperature is preferably 350 ° C. or less from the viewpoint that there is no possibility of coloring of the polymerization solution or molecular weight reduction due to the decomposition reaction. By polymerizing in the above temperature range, it is possible to efficiently produce a copolymer having an appropriate molecular weight, low viscosity, no coloration and little impurities. That is, according to the polymerization method, a very small amount of polymerization initiator may be used, and it is not necessary to use a chain transfer agent such as mercaptan or a polymerization solvent, and a highly pure copolymer can be obtained. .

〔式中、Ｍは単量体単位を表し、ｎは重合度を表す自然数である。Ｒ¹は一価の有機基を表す。〕

[In the formula, M represents a monomer unit, and n is a natural number representing the degree of polymerization. R ¹ represents a monovalent organic group. ]

R ¹ in the general formula (1) is an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkyl group which may have other substituents, a phenyl group, a benzyl group, a polyalkylene glycol group, a dialkylamino group. An alkyl group, a trialkoxysilylalkyl group, an alkyldialkoxysilylalkyl group, or a hydrogen atom.

  The low molecular weight (meth) acrylic polymer can be produced by ordinary radical polymerization. Any of solution polymerization, bulk polymerization, and dispersion polymerization may be employed, and a living radical polymerization method may be used. The reaction process may be any of batch, semi-batch and continuous polymerization. Among these, a high temperature continuous polymerization method at 100 to 350 ° C. is preferable.

  Generally, when a crosslinkable functional group is uniformly introduced into a polymer, physical properties such as curability of a curable composition containing the polymer and weather resistance of a cured product obtained are improved. In this regard, when a stirred tank reactor is used as the reactor, a (meth) acrylic polymer having a relatively narrow composition distribution (crosslinkable functional group distribution) and molecular weight distribution can be obtained. In addition, a process using a continuous stirred tank reactor is more preferable in terms of narrowing the composition distribution and molecular weight distribution.

  As the high-temperature continuous polymerization method, known methods disclosed in JP-A-57-502171, JP-A-59-6207, JP-A-60-215007 and the like may be used. For example, after filling a pressurizable reactor with a solvent and setting it to a predetermined temperature under pressure, the reactor is charged with a monomer mixture comprising each monomer and, if necessary, a polymerization solvent at a constant supply rate. And a method of extracting a polymerization solution in an amount commensurate with the supply amount of the monomer mixture. Moreover, a polymerization initiator can also be mix | blended with a monomer mixture as needed. In the case of blending, the blending amount is preferably 0.001 to 2 parts by mass with respect to 100 parts by mass of the monomer mixture. The pressure depends on the reaction temperature, the monomer mixture used and the boiling point of the solvent, and does not affect the reaction, but may be any pressure that can maintain the reaction temperature. The residence time of the monomer mixture is preferably 1 to 60 minutes. If the residence time is less than 1 minute, the monomer may not react sufficiently, and if the unreacted monomer exceeds 60 minutes, the productivity may deteriorate. The preferred residence time is 2 to 40 minutes.

As an example of the polymerization initiator used for obtaining the low molecular weight (meth) acrylic polymer, any initiator that generates radicals at a predetermined reaction temperature may be used. Specifically, di-t-butyl peroxide, di-t-hexyl peroxide, t-hexyl peroxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, cumene hydroper Organic peroxides such as oxide and t-butyl hydroperoxide, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), azobiscyclohexacarbonitrile, Examples include azo compounds such as azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-amidinopropane) dihydrochloride, 4,4′-azobis (4-cyanovaleric acid). One of these polymerization initiators may be used alone, or two or more thereof may be used in combination. When a polymerization initiator having a high hydrogen abstraction ability is used, the double bond concentration of the resulting polymer tends to increase. For example, when an organic peroxide is used rather than an azo compound, a polymer having a high double bond concentration tends to be obtained.
The amount of the polymerization initiator used can be appropriately adjusted depending on the kind of the polymerization initiator and the monomer, the desired molecular weight, the polymerization conditions, etc., but in general, with respect to 100 parts by mass of the monomer used. 0.001 to 10 parts by mass. When obtaining a polymer having the same molecular weight, the smaller the amount of polymerization initiator used, the higher the double bond concentration in the resulting polymer.

When using an organic solvent for the production of a low molecular weight (meth) acrylic polymer, organic hydrocarbon compounds are suitable, cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, Examples include esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and alcohols such as methanol, ethanol, and isopropanol. One or more of these can be used. In a solvent that does not dissolve the (meth) acrylic acid ester copolymer well, scales are likely to grow on the walls of the reactor, and production problems are likely to occur in the cleaning process. In addition, when an organic solvent having a high chain transfer ability such as isopropanol is used, the double bond concentration in the resulting polymer tends to be low.
It is preferable that the usage-amount of a solvent shall be 80 mass parts or less with respect to 100 mass parts of all vinyl monomers. By setting it to 80 parts by mass or less, a high conversion rate can be obtained in a short time. More preferably, it is 1-50 mass parts. A dehydrating agent such as trimethyl orthoacetate or trimethyl orthoformate can also be added.

  A known chain transfer agent may be used for the production of the low molecular weight (meth) acrylic polymer. When a chain transfer agent is used, the double bond concentration in the resulting polymer tends to be low. In general, the double bond concentration is lowered by increasing the amount of the chain transfer agent used.

The reaction solution withdrawn from the reactor proceeds to the next step as it is, or the polymer is simply removed by distilling off volatile components such as unreacted monomers, solvents and low molecular weight oligomers by distillation or the like. Can be separated. A part of volatile components such as unreacted monomers, solvent, and low molecular weight oligomers distilled off from the reaction solution can be returned to the raw material tank or directly returned to the reactor and used again for the polymerization reaction.
Thus, the method of recycling an unreacted monomer and a solvent is a preferable method from an economical viewpoint. In the case of recycling, it is necessary to determine the mixing ratio of the newly supplied monomer mixture so as to maintain the desired monomer ratio and the desired amount of solvent in the reactor.

The amount of double bonds introduced into the polymer can be reduced by adding a radical generator and post-treating under heating conditions. The addition amount of the radical generator is about 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer. The greater the addition amount, the greater the effect of reducing the double bond concentration.
Although the heating temperature in the heat treatment is about 50 to 130 ° C., the lower the temperature, the greater the effect of reducing the double bond concentration. The heating temperature is preferably in the range of 50 to 110 ° C, more preferably in the range of 50 to 100 ° C.
The heat treatment time is not particularly limited, but is preferably set so that the amount of the remaining radical generator is less than 1% by mass with respect to the polymer. A person skilled in the art can calculate the remaining radical from the activation energy, frequency factor and reaction temperature of the radical generator used.

The double bond concentration can also be reduced by hydrogenating the (meth) acrylic polymer as a post-treatment. For hydrogenation, a conventionally known method can be employed.
That is, after adding a homogeneous catalyst or a heterogeneous catalyst to the polymer reaction solution, the inside of the system is put into a hydrogen atmosphere, the pressure is heated to normal pressure to 10 MPa, the temperature is heated to about 20 to 180 ° C., and about 2 to 20 hours. React. Specific examples of homogeneous catalysts include rhodium complexes such as chlorotris (triphenylphosphine) rhodium, ruthenium complexes such as dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorobis (triphenylphosphine) ) Platinum complexes such as platinum, and iridium complexes such as carbonylbis (triphenylphosphine) iridium. On the other hand, examples of the heterogeneous catalyst include solid catalysts in which transition metals such as nickel, rhodium, ruthenium, palladium, and platinum are supported on carbon, silica, alumina, fibers, organic gels, and the like. The heterogeneous catalyst is preferable in that the catalyst can be easily removed by filtration or the like, so that the quality is stable and an expensive catalyst can be reused. The amount of catalyst to be added is about 10 to 1,000 ppm with respect to the vinyl polymer in the case of a homogeneous catalyst. In the case of a heterogeneous catalyst, it is about 1,000 to 10,000 ppm.

<(B) component: high molecular weight (meth) acrylic polymer>
The high molecular weight (meth) acrylic polymer is a polymer having a structural unit derived from a (meth) acrylic monomer, like the low molecular weight (meth) acrylic polymer. Examples of the (meth) acrylic monomer include (meth) acrylic acid and (meth) acrylic acid alkyl ester. The amount of the (meth) acrylic monomer used is preferably in the range of 10 to 100% by weight, more preferably 30 to 100% by weight, based on the total constituent monomers of the (meth) acrylic polymer. It is a range, More preferably, it is the range of 50-100 mass%.

  As the (meth) acrylic acid alkyl ester, the same compounds as those described in the description of the low molecular weight (meth) acrylic polymer can be used. Among these, (meth) acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms is preferable from the viewpoint of mechanical properties of the cured product. The amount of the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms is preferably 10% by mass or more based on the total constituent monomers of the high molecular weight (meth) acrylic polymer. Preferably it is 30 mass% or more, More preferably, it is 50 mass% or more. In addition, an upper limit is 100 mass% or less, 90 mass% or less may be sufficient, 80 mass% or less may be sufficient, and 50 mass% or less may be sufficient.

  In addition, when a (meth) acrylic acid alkyl ester having an alkyl group having 10 or more carbon atoms is used, when the curable composition contains an oxyalkylene polymer, the oxyalkylene polymer is good. It is preferable in terms of ensuring compatibility and improving mechanical properties and weather resistance. Preferably carbon number of an alkyl group is 10-20, More preferably, it is 12-20. The amount of (meth) acrylic acid alkyl ester having an alkyl group having 10 or more carbon atoms is preferably 5% by mass or more, more preferably 10%, based on all constituent monomers of the (meth) acrylic polymer. It is at least 20% by mass, more preferably at least 20% by mass. In addition, an upper limit is 100 mass% or less, 90 mass% or less may be sufficient, 80 mass% or less may be sufficient, and 50 mass% or less may be sufficient.

  The high molecular weight (meth) acrylic polymer has a reactive silyl group in the molecule. For this reason, the hardened | cured material obtained from the curable composition containing the said high molecular weight (meth) acrylic-type polymer shows a favorable mechanical physical property. The type of the reactive silyl group is not particularly limited, and examples thereof include an alkoxysilyl group, a halogenosilyl group, and a silanol group, but an alkoxysilyl group is preferable from the viewpoint of easy control of reactivity. Specific examples of the alkoxysilyl group include trialkoxysilyl groups such as trimethoxysilyl group, triethoxysilyl group, dimethoxyethoxysilyl group and methoxydiethoxysilyl group; methyldimethoxysilyl group, methyldiethoxysilyl group, ethyldimethoxysilyl And dialkoxysilyl groups such as ethyldiethoxysilyl group; monoalkoxysilyl groups such as dimethylmethoxysilyl group, dimethylethoxysilyl group, diethylmethoxysilyl group and diethylethoxysilyl group. Among these, a dialkoxysilyl group is preferable in that the cured product exhibits good elongation and is excellent in heat stability.

From the viewpoint of the tensile strength of the cured product, the average value of the number of reactive silyl groups contained in one molecule of the high molecular weight (meth) acrylic polymer is preferably 0.1 or more, more preferably 0.2. Or more, more preferably 0.3 or more. The average value of the number of reactive silyl groups may be 0.5 or more, 0.8 or more, or 1.0 or more. From the viewpoint of securing the elongation of the cured product, the upper limit value is preferably 5.0 or less, more preferably 4.0 or less, still more preferably 3.0 or less, and even more preferably 2 .5 or less, and more preferably 2.2 or less. The range of the average value of the number of reactive silyl groups can be set by combining the above upper limit value and lower limit value. For example, it is 0.1 or more and 5.0 or less, and 0.1 or more 3.0 or less, 0.1 or more and 2.2 or less, or 0.2 or more and 2.2 or less may be sufficient.
The position of the reactive silyl group is not particularly limited, and can be a side chain and / or a terminal of the polymer.

The reactive silyl group can be obtained, for example, by polymerizing a monomer mixture containing a (meth) acrylic monomer and a vinyl monomer having a reactive silyl group.
As the vinyl monomer having a reactive silyl group, the same compounds as those described in the description of the low molecular weight (meth) acrylic polymer can be used.

In addition to the above monomers, the high molecular weight (meth) acrylic polymer may be copolymerized with other monomers copolymerizable therewith.
Examples of the other monomer include the same compounds as those described in the description of the low molecular weight (meth) acrylic polymer, methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ( Methoxybutyl acrylate, methoxyhexyl (meth) acrylate, ethoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxybutyl (meth) acrylate, ethoxyhexyl (meth) acrylate, (meth) (Meth) acrylic acid alkoxyalkyl esters such as butoxymethyl acrylate, butoxyethyl (meth) acrylate, butoxybutyl (meth) acrylate and butoxyhexyl (meth) acrylate may be mentioned, but are not limited thereto. Moreover, 1 type, or 2 or more types of these can be used.

  The weight average molecular weight (Mw) of the high molecular weight (meth) acrylic polymer is a polystyrene equivalent molecular weight determined by gel permeation chromatography (hereinafter also referred to as “GPC”), and is 10 from the viewpoint of the strength and weather resistance of the cured product. 15,000 or more, preferably 11,000 or more, more preferably 15,000 or more, further preferably 20,000 or more, and further preferably 25,000 or more. Mw may be 30,000 or more, or 40,000 or more. On the other hand, from the viewpoint of workability (low viscosity), the upper limit value of Mw is 100,000, preferably 90,000 or less, more preferably 80,000 or less. The upper limit may be 70,000 or less, 60,000 or less, or 50,000 or less. The range of Mw can be set by combining the above upper limit value and lower limit value. For example, the range is 10,000 to 100,000, and may be 10,000 to 80,000. 5,000 or more and 50,000 or less, or 15,000 or more and 50,000 or less.

  The molecular weight distribution of the high molecular weight (meth) acrylic polymer is calculated as a value (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn). Mw / Mn is preferably 6.0 or less, more preferably 5.0 or less, still more preferably 4.0 or less, and even more preferably 3. from the viewpoint of the balance between tensile properties and workability. 0 or less, and even more preferably 2.0 or less. The lower limit value of Mw / Mn is usually 1.0.

  The viscosity of the high molecular weight (meth) acrylic polymer is preferably 300,000 mPa · s or less, more preferably 200,000 mPa · s or less, more preferably 100,000 mPa · s or less at 25 ° C. More preferably, it is 80,000 mPa · s or less, more preferably 60,000 mPa · s or less, and most preferably 40,000 mPa · s or less. A viscosity of 200,000 mPa · s or less is preferable because the workability of the curable composition is improved. The lower limit of the viscosity may be 5,000 mPa · s or more, 10,000 mPa · s or more, or 20,000 mPa · s.

In the present invention, the high molecular weight (meth) acrylic polymer may have a double bond in the molecule. It is preferable to have a double bond in the molecule because the weather resistance of the resulting cured product tends to improve. The double bond can be introduced by the same method as in the case of the low molecular weight (meth) acrylic polymer.
The amount of the double bond contained in the high molecular weight (meth) acrylic polymer is preferably 0.01 meq / g or more, more preferably 0.03 meq / g or more from the viewpoint of expressing the effect on the weather resistance. More preferably, it is 0.05 meq / g or more. On the other hand, from the viewpoint of weather resistance, the amount of double bonds is preferably 1.0 meq / g or less, more preferably 0.50 meq / g or less, more preferably 0.30 meq / g or less. The range of the amount of double bonds can be set by combining the above upper limit value and lower limit value. For example, it is 0.01 meq / g or more and 1.0 meq / g or less, and 0.05 meq / g or more and 1 0.0 meq / g or less, or 0.10 meq / g or more and 0.50 meq / g or less.

  The high molecular weight (meth) acrylic polymer can be produced by ordinary radical polymerization as in the case of the low molecular weight (meth) acrylic polymer. Any of solution polymerization, bulk polymerization, and dispersion polymerization may be employed, and a living radical polymerization method may be used. The reaction process may be any of batch, semi-batch and continuous polymerization. Among these, a high temperature continuous polymerization method at 100 to 350 ° C. is preferable.

  When the living radical polymerization method is used, there is no particular limitation on the type, and the reversible addition-cleavage chain transfer polymerization method (RAFT method), the nitroxy radical method (NMP method), the atom transfer radical polymerization method (ATRP method) ), A polymerization method using an organic tellurium compound (TERP method), a polymerization method using an organic antimony compound (SBRP method), a polymerization method using an organic bismuth compound (BIRP method), and an iodine transfer polymerization method are employed. be able to. Among these, the RAFT method, the NMP method, and the ATRP method are preferable from the viewpoints of controllability of polymerization and ease of implementation.

In the RAFT method, controlled polymerization proceeds via a reversible chain transfer reaction in the presence of a specific polymerization control agent (RAFT agent) and a general free radical polymerization initiator. As the RAFT agent, various known RAFT agents such as a dithioester compound, a xanthate compound, a trithiocarbonate compound, and a dithiocarbamate compound can be used.
As the RAFT agent, a monofunctional agent having only one active site may be used, or a bifunctional or more functional agent may be used. Moreover, the usage-amount of a RAFT agent is suitably adjusted with the monomer to be used, the kind of RAFT agent, etc.

As the polymerization initiator used in the polymerization by the RAFT method, known radical polymerization initiators such as azo compounds, organic peroxides and persulfates can be used. An azo compound is preferred because side reactions are unlikely to occur.
Specific examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2, 4-dimethylvaleronitrile), dimethyl-2,2′-azobis (2-methylpropionate), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1- Carbonitrile), 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2′-azobis (N-butyl-2-methylpropionamide), and the like.
The radical polymerization initiator may be used alone or in combination of two or more.

  The proportion of the radical polymerization initiator used is not particularly limited, but from the viewpoint of obtaining a polymer having a smaller molecular weight distribution, the amount of the radical polymerization initiator used relative to 1 mol of the RAFT agent is preferably 0.5 mol or less. More preferably, it is 2 mol or less. From the viewpoint of stably performing the polymerization reaction, the lower limit of the amount of the radical polymerization initiator used relative to 1 mol of the RAFT agent is 0.01 mol. Therefore, the amount of radical polymerization initiator used per 1 mol of RAFT agent is preferably in the range of 0.01 mol to 0.5 mol, and more preferably in the range of 0.05 mol to 0.2 mol.

  The reaction temperature in the polymerization reaction by the RAFT method is preferably 40 ° C. or higher and 100 ° C. or lower, more preferably 45 ° C. or higher and 90 ° C. or lower, and further preferably 50 ° C. or higher and 80 ° C. or lower. If reaction temperature is 40 degreeC or more, a polymerization reaction can be advanced smoothly. On the other hand, if reaction temperature is 100 degrees C or less, while being able to suppress a side reaction, the restrictions regarding the initiator and solvent which can be used are eased.

｛式中、Ｒ¹は炭素数１〜２のアルキル基又は水素原子であり、Ｒ²は炭素数１〜２のアルキル基又はニトリル基であり、Ｒ³は−（ＣＨ₂）ｍ−、ｍは０〜２であり、Ｒ⁴、Ｒ⁵は炭素数１〜４のアルキル基である｝ In the NMP method, a specific alkoxyamine compound having nitroxide or the like is used as a living radical polymerization initiator, and polymerization proceeds via a nitroxide radical derived therefrom. In the present disclosure, the type of nitroxide radical to be used is not particularly limited, but from the viewpoint of polymerization controllability when polymerizing an acrylate-containing monomer, a compound represented by the general formula (2) is used as the nitroxide compound. Is preferred.

{In the formula, R ¹ represents an alkyl group having 1 to 2 carbon atoms or a hydrogen atom, R ² represents an alkyl group having 1 to ² carbon atoms or a nitrile group, and R ³ represents — (CH ₂ ) m —, m Are 0 to 2, and R ⁴ and R ⁵ are alkyl groups having 1 to 4 carbon atoms}

The nitroxide compound represented by the general formula (2) is primarily dissociated by heating at about 70 to 80 ° C. and causes an addition reaction with the vinyl monomer. In this case, it is possible to obtain a polyfunctional polymerization precursor by adding a nitroxide compound to a vinyl monomer having two or more vinyl groups. Next, the vinyl monomer can be living polymerized by secondary dissociation of the polymerization precursor under heating.
The amount of the nitroxide compound used is appropriately adjusted depending on the monomer used and the type of nitroxide compound.

｛式中、Ｒ⁴、Ｒ⁵は炭素数１〜４のアルキル基である。｝ When a high molecular weight (meth) acrylic polymer is produced by the NMP method, the nitroxide radical represented by the general formula (3) is 0.001 to 0 per 1 mol of the nitroxide compound represented by the general formula (2). Polymerization may be carried out by adding in a range of .2 mol.

{Wherein R ⁴ and R ⁵ are alkyl groups having 1 to 4 carbon atoms. }

  By adding 0.001 mol or more of the nitroxide radical represented by the general formula (3), the time for the concentration of the nitroxide radical to reach a steady state is shortened. As a result, the polymerization can be controlled to a higher degree, and a polymer with a narrower molecular weight distribution can be obtained. On the other hand, if the amount of the nitroxide radical added is too large, the polymerization may not proceed. A more preferable addition amount of the nitroxide radical to 1 mol of the nitroxide compound is in the range of 0.01 to 0.5 mol, and a more preferable addition amount is in the range of 0.05 to 0.2 mol.

  The reaction temperature in the NMP method is preferably 50 ° C. or higher and 140 ° C. or lower, more preferably 60 ° C. or higher and 130 ° C. or lower, still more preferably 70 ° C. or higher and 120 ° C. or lower, particularly preferably 80 ° C. or higher and 120 ° C. or lower. It is as follows. If reaction temperature is 50 degreeC or more, a polymerization reaction can be advanced smoothly. On the other hand, if the reaction temperature is 140 ° C. or lower, side reactions such as radical chain transfer tend to be suppressed.

  In the ATRP method, a polymerization reaction is generally performed using an organic halide as an initiator and a transition metal complex as a catalyst. As the organic halide as an initiator, a monofunctional one or a bifunctional or higher one may be used. Moreover, bromide and chloride are preferable as the kind of halogen.

  The reaction temperature in the ATRP method is preferably 20 ° C. or higher and 200 ° C. or lower, more preferably 50 ° C. or higher and 150 ° C. or lower. If reaction temperature is 20 degreeC or more, a polymerization reaction can be advanced smoothly.

  Living radical polymerization may be carried out in the presence of a known chain transfer agent.

  Moreover, a well-known polymerization solvent can be used in living radical polymerization. Specifically, aromatic compounds such as benzene, toluene, xylene and anisole; ester compounds such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate; ketone compounds such as acetone and methyl ethyl ketone; dimethylformamide, acetonitrile, dimethyl sulfoxide, Examples include alcohol and water. Moreover, you may carry out by aspects, such as block polymerization, without using a polymerization solvent.

<(C) component: an oxyalkylene polymer having a reactive silyl group>
The oxyalkylene polymer having a reactive silyl group is not particularly limited as long as it contains a repeating unit represented by the following general formula (4).
—O—R ² — (4)
(In the formula, R ² is a divalent hydrocarbon group.)
Examples of R ² in the general formula (1) include the following.
(CH ₂₎ n (n is an integer of from 1 to 10)
CH (CH ₃ ) CH ₂
CH (C ₂ H ₅ ) CH ₂
C (CH ₃ ) ₂ CH ₂
The oxyalkylene polymer may contain the above repeating unit alone or in combination of two or more. Among these, CH (CH ₃ ) CH ₂ is preferable in terms of excellent workability.

  The reactive silyl group contained in the oxyalkylene polymer containing the reactive silyl group is not particularly limited, and examples thereof include an alkoxysilyl group, a halogenosilyl group, and a silanol group. Groups are preferred. Specific examples of the alkoxysilyl group include trimethoxysilyl group, methyldimethoxysilyl group, dimethylmethoxysilyl group, triethoxysilyl group, methyldiethoxysilyl group, dimethylethoxysilyl group and the like.

The production method of the oxyalkylene polymer is not particularly limited, but for example, using a corresponding epoxy compound or diol as a raw material, a polymerization method using an alkali catalyst such as KOH, a heavy compound using a transition metal compound-porphyrin complex catalyst. Examples thereof include a polymerization method, a polymerization method using a double metal cyanide complex catalyst, and a polymerization method using phosphazene.
Further, the oxyalkylene polymer may be a linear polymer or a branched polymer. Moreover, you may use combining these.

The average value of the number of reactive silyl groups contained in one molecule of the oxyalkylene polymer is preferably in the range of 1 to 4, more preferably from the viewpoint of performance such as adhesion and tensile properties of the cured product. The range is 1.5 to 3.
The position of the reactive silyl group contained in the oxyalkylene polymer is not particularly limited, and can be a side chain and / or a terminal of the polymer.
The oxyalkylene polymer may be either a linear polymer or a branched polymer. Moreover, you may use combining these.

  The number average molecular weight (Mn) of the oxyalkylene polymer having a reactive silyl group is preferably 5,000 or more, more preferably 10,000 or more, further preferably 15,000 from the viewpoint of mechanical properties. That's it. Mn may be 18,000 or more, 22,000 or more, or 25,000 or more. The upper limit value of Mn is preferably 60,000 or less, more preferably 50,000 or less, and further preferably 40,000 or less, from the viewpoint of workability (viscosity) during coating of the curable composition. . The range of Mn can be set by combining the above upper limit value and lower limit value. For example, the range is 5,000 or more and 60,000 or less, and may be 15,000 or more and 60,000 or less. 2,000 or more and 50,000 or less, or 22,000 or more and 50,000 or less.

  A commercially available product may be used as the oxyalkylene polymer having a reactive silyl group. Specific examples include “MS polymer S203”, “MS polymer S303”, “MS polymer S810”, “Syryl SAT200”, “Syryl SAT350”, “Syryl EST280” and “Syryl SAT30” manufactured by Kaneka Corporation, and Asahi Glass. “Exestar S2410”, “Exestar S2420”, and “Exestar S3430” (all trade names) manufactured by Co., Ltd. are exemplified.

<Curable composition>
As above-mentioned, the curable composition of this invention uses (A) component and (B) component as an essential component. Here, the ratio of the component (A) and the component (B) ((A) / (B)) is preferably 10 to 10 in terms of mass ratio, in that the weather resistance and mechanical properties of the cured product obtained are good. It is 90 / 90-10, More preferably, it is 30-70 / 70-30.

  The amount of double bonds contained in the curable composition is preferably 0.01 meq / g or more, more preferably 0.05 meq / g or more from the viewpoint of weather resistance. The amount of double bonds may be 0.10 meq / g or more, or 0.15 meq / g or more. On the other hand, if the amount of double bonds is too large, the degree of cross-linking of the cured product becomes too high during exposure, resulting in insufficient flexibility, and cracks tend to occur. For this reason, the amount of double bonds is preferably 1.0 meq / g or less, more preferably 0.80 meq / g or less, still more preferably 0.60 meq / g or less, and still more preferably 0.00. It is 50 meq / g or less, and more preferably 0.40 meq / g or less. The range of the amount of double bonds can be set by combining the above upper limit value and lower limit value. For example, it is 0.01 meq / g or more and 1.0 meq / g or less, and 0.01 meq / g or more and 0 or less. It may be 5.0 meq / g or less, or 0.05 meq / g or more and 0.50 meq / g or less.

  The curable composition of the present invention can contain components other than the component (A) and the component (B) as long as the effects exerted by the present invention are not hindered. Such components include fillers, plasticizers, anti-aging agents, curing accelerators, anti-tack agents, adhesion promoters, and the like.

As the filler, light calcium carbonate having an average particle size of about 0.02 to 2.0 μm, heavy calcium carbonate having an average particle size of about 1.0 to 5.0 μm, titanium oxide, carbon black, synthetic silicic acid, talc, zeolite And mica, silica, calcined clay, kaolin, bentonite, aluminum hydroxide and barium sulfate, glass balloon, silica balloon, and polymethyl methacrylate balloon. With these fillers, the mechanical properties of the cured product are improved, and the strength and elongation can be improved.
Among these, light calcium carbonate, heavy calcium carbonate, and titanium oxide, which are highly effective in improving physical properties, are preferable, and a mixture of light calcium carbonate and heavy calcium carbonate is more preferable. The addition amount of the filler is preferably 20 to 300 parts by mass, more preferably 50 to 200 parts by mass, when the total amount of the components (A) and (B) is 100 parts by mass. When it is set as the mixture of light calcium carbonate and heavy calcium carbonate as mentioned above, it is preferable that the mass ratio of light calcium carbonate / heavy calcium carbonate is in the range of 90/10 to 50/50.

  Examples of the plasticizer include liquid polyurethane resins, polyester plasticizers obtained from dicarboxylic acids and diols; etherified or esterified products of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; sugar polyhydric alcohols such as sucrose, ethylene Polyether plasticizers such as saccharide-based polyethers obtained by addition polymerization of alkylene oxides such as oxide and propylene oxide, followed by etherification or esterification; Polystyrene plasticizers such as poly-α-methylstyrene; Crosslinkability Examples thereof include poly (meth) acrylate having no functional group. Of these, poly (meth) acrylates having no crosslinkable functional groups are preferred in terms of durability such as weather resistance of the cured product. Among these, those having Mw in the range of 1,000 to 7,000 and a glass transition temperature of −30 ° C. or lower are more preferable.

  The amount of the plasticizer used in the curable composition is preferably in the range of 0 to 100 parts by mass and 0 to 80 parts by mass when the total amount including the component (A) and the component (B) is 100 parts by mass. Range may be sufficient and the range of 0-50 mass parts may be sufficient.

Anti-aging agents include UV absorbers such as benzophenone compounds, benzotriazole compounds and oxalic acid anilide compounds, light stabilizers such as hindered amine compounds, antioxidants such as hindered phenols, heat stabilizers, or An anti-aging agent that is a mixture of these can be used.
Examples of the UV absorber include trade names “TINUVIN 571”, “TINUVIN 1130”, and “TINUVIN 327” manufactured by BASF. Examples of the light stabilizer include trade names “Tinuvin 292”, “Tinuvin 144” and “Tinuvin 123” manufactured by the same company, and a trade name “Sanol 770” manufactured by Sankyo. As the heat stabilizer, trade names “Irganox 1135”, “Irganox 1520”, and “Irganox 1330” manufactured by BASF are exemplified. The trade name “Tinuvine B75” manufactured by BASF, which is a mixture of an ultraviolet absorber / light stabilizer / heat stabilizer, may be used.

As a hardening accelerator, well-known compounds, such as a tin-type catalyst, a titanium-type catalyst, and tertiary amines, can be used.
Examples of the tin-based catalyst include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetonate, dioctyltin dilaurate, and the like. Specifically, product names “Neostan U-28”, “Neostan U-100”, “Neostan U-200”, “Neostan U-220H”, “Neostan U-303”, “SCAT-” manufactured by Nitto Kasei Co., Ltd. 24 "etc. are illustrated.
Examples of the titanium-based catalyst include tetraisopropyl titanate, tetra n-butyl titanate, titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethylacetylacetonate, dibutoxytitanium diacetylacetonate, diisopropoxytitanium diacetylacetonate, Examples include titanium octylene glycolate and titanium lactate.
Examples of tertiary amines include triethylamine, tributylamine, triethylenediamine, hexamethylenetetramine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), diazabicyclononene (DBN), N- Examples include methylmorpholine and N-ethylmorpholine.

  The usage-amount of a hardening accelerator becomes like this. Preferably it is 0.1-5 mass parts with respect to a total of 100 mass of (A) component and (B) component, More preferably, it is 0.5-2 mass parts.

  As an anti-tack agent, trade names “Aronix M8030”, “M8100”, “M309” manufactured by Toagosei Co., Ltd., which is an acrylic oligomer, or a mixture with a photopolymerization initiator, saturated fatty acid oils such as paulownia oil and linseed oil, Examples include the product name “R15HT” manufactured by Idemitsu Oil Co., Ltd., the product name “PBB3000” manufactured by Nippon Soda Co., Ltd., and the product name “GOSELAC 500B” manufactured by Nippon Synthetic Chemist.

Examples of the adhesion-imparting agent include aminosilanes such as trade names “KBM602”, “KBM603”, “KBE602”, “KBE603”, “KBM902”, and “KBM903” manufactured by Shin-Etsu Silicone.
In addition, a dehydrating agent such as methyl orthoformate, methyl orthoacetate, and vinylsilane, an organic solvent, and the like may be blended.

  The curable composition of the present invention can be prepared as a one-component type that cures by preliminarily blending and preserving all blending components and absorbing moisture in the air after coating. In addition, a component such as a curing catalyst, a filler, a plasticizer, and water may be added separately as a curing agent, and the two-component type may be prepared by mixing the compounding material and the polymerization composition before use. A one-component type is more preferred because it is easy to handle and has few mistakes in mixing at the time of application.

  The curable composition of the present invention is cured at room temperature, and a cured product having excellent weather resistance and mechanical properties can be obtained. For this reason, it can utilize suitably as a sealing material composition by which high durability is calculated | required. The sealing material composition of the present invention contains the curable composition, and if necessary, other components are blended according to a conventional method.

Hereinafter, the present invention will be specifically described based on examples. In addition, this invention is not limited by these Examples. In the following, “parts” and “%” mean mass parts and mass% unless otherwise specified.
It describes below about the analysis method of the polymer obtained by the manufacture example, the Example, and the comparative example, and the evaluation method of the hardened | cured material obtained from the curable composition.

<Quantification method of double bond amount>
^{As a result of 1} H-NMR measurement, the integrated value of the signal derived from hydrogen bonded to a double bond near 5.5 ppm and the hydrogen bonded to the carbon adjacent to the ester group at 3.0 to 4.5 ppm The double bond concentration per mass of the polymer was calculated from the ratio of the integral value of the derived signal and the composition of the polymer.

<Molecular weight measurement>
Using a gel permeation chromatograph (model name “HLC-8320”, manufactured by Tosoh Corporation), a number average molecular weight (Mn) and a weight average molecular weight (Mw) in terms of polystyrene were obtained from the following conditions. Moreover, molecular weight distribution (Mw / Mn) was computed from the obtained value.
○ Measurement condition column: Tosoh TSKgel SuperMultipore HZ-M × 4 Column temperature: 40 ° C.
Eluent: Tetrahydrofuran Detector: RI

<Average number of reactive silyl groups contained in (meth) acrylic polymer>
The number (average number) f (Si) of alkoxysilyl groups which are reactive silyl groups is expressed by the following formula from the parts by mass of the monomers having reactive silyl groups when all the constituent monomers are 100 parts by mass. Used to calculate.
f (Si) = {part by mass of silyl group monomer / (molecular weight of silyl group monomer × 100 / Mn)}

<Viscosity of (meth) acrylic polymer>
The E-type viscosity was measured under the following conditions using a TVE-20H viscometer (salt water / flat plate system, manufactured by Toki Sangyo Co., Ltd.).
○ Measurement conditions Cone shape: angle 1 ° 34 ', radius 24mm (less than 10000mPa · s)
Angle 3 °, radius 7.7mm (10000mPa · s or more)
Temperature: 25 ° C ± 0.5 ° C

<Weather resistance test>
Each curable composition was applied to a Teflon (registered trademark) sheet having a thickness of 2 mm, and cured at 23 ° C. and 50% RH for 1 week to prepare a cured sheet. The obtained cured product was put into a metalling weather meter ("DAIPLA METAL WEATHER KU-R5NCI-A" manufactured by Daipura Wintes Co., Ltd.) and subjected to an accelerated weathering test. The test was carried out under conditions of irradiation of 63 ° C., 70% RH, and illuminance of 80 mW / cm ^{2 in} a shower for 2 minutes once every 2 hours. The time when abnormalities such as cracks and bleeds began to appear in the appearance was recorded.

<Tensile test>
Each curable composition was applied to a Teflon (registered trademark) sheet having a thickness of 2 mm, and cured at 23 ° C. and 50% RH for 1 week to prepare a cured sheet. A dumbbell for tensile test (JIS K 6251 No. 3 type) is prepared from the obtained cured product, and using a tensile tester (Autograph AGS-J, manufactured by Shimadzu Corporation) under the condition of a tensile speed of 200 mm / min. The elongation at break and the strength at break were measured.

<< (A) component: Production of low molecular weight (meth) acrylic polymer >>
Synthesis Example 1 (Production of (meth) acrylic polymer A-1)
Polymerization process The temperature of a 1000 mL capacity pressurized stirred tank reactor equipped with an oil jacket was maintained at 265 ° C. Next, while maintaining the reactor pressure constant, 10 parts of tetradecyl acrylate (hereinafter referred to as “TDA”), 70 parts of 2-ethylhexyl acrylate (hereinafter referred to as “HA”), and methyl methacrylate (hereinafter referred to as “TDA”). , "MMA") 20 parts, methyl ethyl ketone (hereinafter referred to as "MEK") 20 parts, di-t-butyl peroxide (manufactured by NOF Corporation, trade name "Perbutyl D", hereinafter referred to as "DTBP"). The monomer mixture consisting of 0.2 parts is continuously fed from the raw material tank to the reactor at a constant feed rate (48 g / min, residence time: 12 minutes), and the monomer mixture is fed. The reaction solution corresponding to the amount was continuously extracted from the outlet. Immediately after the start of the reaction, once the reaction temperature decreased, an increase in temperature due to the heat of polymerization was observed, but the reaction temperature was maintained at 264 to 266 ° C. by controlling the temperature of the oil jacket.
The time when the temperature became stable from the start of the supply of the monomer mixture was taken as the reaction liquid collection start point, and the reaction was continued for 25 minutes. As a result, 1.2 kg of the monomer mixture was supplied, and 1.2 kg of reaction was started. The liquid was collected. Thereafter, the reaction solution was introduced into a thin film evaporator to separate volatile components such as unreacted monomers to obtain a concentrated solution.

○ Post-treatment step Next, 100 parts by weight of the concentrated solution obtained in the above polymerization step was placed in a flask purged with nitrogen, and heated and stirred while flowing nitrogen until the liquid temperature reached 90 ° C. At 90 ° C., 0.5 part of t-butyl peroxy-2-ethylhexanoate (trade name “Perhexyl O”, manufactured by NOF Corporation), which is a radical generator, is added and kept at 90 ° C. (Meth) acrylic polymer A-1 was obtained by stirring for 16 hours. The properties of the polymer are shown in Table 1.

Synthesis Examples 2 to 4 (Production of (meth) acrylic polymers A-2 to A-4)
By using the concentrate obtained after the polymerization step of Synthesis Example 1, the procedure was the same as in Synthesis Example 1 except that the amount of radical generator (perhexyl O) added in the post-treatment step and the treatment conditions were changed as shown in Table 1. , (Meth) acrylic polymers A-2 to A-4 were obtained. The properties of each polymer are shown in Table 1.

Synthesis Examples 5 to 10 (Production of (meth) acrylic polymers A-5 to A-10)
According to the same procedure as in Synthesis Example 1, except that the raw materials used in the polymerization step and the reactor internal temperature, and the addition amount and treatment conditions of the radical generator (perhexyl O) in the post-treatment step were changed as shown in Table 1. (Meth) acrylic polymers A-5 to A-10 were obtained. In Synthesis Example 10 ((meth) acrylic polymer A-10), the concentrated solution obtained after the polymerization step was not post-treated. The properties of each polymer are shown in Table 1.

Synthesis Example 11 (Production of (Meth) acrylic polymer A-11)
Butyl acetate (150 parts) was placed in a flask equipped with a reflux condenser, and the internal temperature was kept at 94 ° C. with an oil bath, followed by stirring. With a dropping funnel, a mixed solution of HA (80 parts), TDA (10 parts), MMA (10 parts), and ABN-E (8 parts) was dropped over 4 hours. The mixture was further stirred for 2 hours while maintaining the temperature at 94 ° C. Thereafter, the solvent was removed from the reaction solution by an evaporator at 90 ° C. and 10 mmHg to separate volatile components, thereby obtaining (meth) acrylic polymer A-11. The properties of the polymer are shown in Table 1.

≪ (B) component: Production of high molecular weight (meth) acrylic polymer≫
Synthesis Example 12 (Production of (Meth) acrylic polymer B-1)
Polymerization process The temperature of a 1000 mL capacity pressurized stirred tank reactor equipped with an oil jacket was kept at 184 ° C. Next, while maintaining the reactor pressure constant, 2.8 parts of 3-methacryloxypropyldimethoxysilane (manufactured by Dow Corning Toray, trade name “Z6033”, hereinafter referred to as “DMS”) and 10 parts of TDA are used. , 20 parts of HA, 60.2 parts of n-butyl acrylate (hereinafter referred to as “BA”), 7 parts of MMA, 10 parts of isopropyl alcohol (hereinafter referred to as “IPA”), trimethyl orthoacetate (hereinafter referred to as “BA”). 5 parts of "MOA", 5 parts of MEK, di-t-hexyl peroxide (manufactured by NOF Corporation, trade name "Perhexyl H", hereinafter referred to as "DTHP") as a polymerization initiator from 0.1 part The monomer mixture is continuously supplied from the raw material tank to the reactor at a constant supply rate (48 g / min, residence time: 12 minutes), and a reaction liquid corresponding to the monomer mixture supply amount is discharged. It was continuously withdrawn from. Immediately after the start of the reaction, once the reaction temperature decreased, an increase in temperature due to the heat of polymerization was observed, but the reaction temperature was maintained at 264 to 266 ° C. by controlling the temperature of the oil jacket.
The time when the temperature became stable from the start of the supply of the monomer mixture was taken as the reaction liquid collection start point, and the reaction was continued for 25 minutes. As a result, 1.2 kg of the monomer mixture was supplied, and 1.2 kg of reaction was started. The liquid was collected. Thereafter, the reaction solution was introduced into a thin film evaporator to separate volatile components such as unreacted monomers to obtain a concentrated solution.

○ Post-treatment step The same operation as in Synthesis Example 1 except that the concentrated solution obtained after the polymerization step was used, and the type and amount of radical generator in the post-treatment step and the treatment conditions were changed as shown in Table 2. (Meth) acrylic polymer B-1 was obtained. The properties of the polymer are shown in Table 2.

Synthesis Examples 13 to 22 and 24 (Production of (Meth) acrylic polymers B-2 to B-11 and B-13)
The same as in Synthesis Example 12 except that the raw material and reactor internal temperature used in the polymerization step, the type and amount of radical generator in the post-treatment step, and the treatment conditions were as shown in Table 2 and Table 3. By the operation, (meth) acrylic polymers B-2 to B-11 and B-13 were obtained. In Synthesis Example 18 ((meth) acrylic polymer B-7), the post-treatment of the concentrated liquid obtained after the polymerization step was not performed. The properties of each polymer are shown in Table 2 and Table 3.

Synthesis Example 23 (Production of (meth) acrylic polymer B-12)
Synthesis of RAFT agent (1,4-bis (n-dodecylsulfanylthiocarbonylsulfanylmethyl) benzene) 1-dodecanethiol (42.2 g), 20% aqueous KOH solution (63.8 g), trioctylmethyl in an eggplant type flask Ammonium chloride (1.5 g) was added and cooled in an ice bath, carbon disulfide (15.9 g) and tetrahydrofuran (hereinafter also referred to as “THF”) (38 ml) were added, and the mixture was stirred for 20 minutes. A THF solution (170 ml) of α, α′-dichloro-p-xylene (16.6 g) was added dropwise over 30 minutes. After reacting at room temperature for 1 hour, the mixture was extracted from chloroform, washed with pure water, dried over anhydrous sodium sulfate, and concentrated on a rotary evaporator. The obtained crude product is purified by column chromatography and then recrystallized from ethyl acetate, whereby 1,4-bis (n-dodecylsulfanylthiocarbonylsulfanylmethyl) benzene represented by the following formula (5) is obtained. (Hereinafter also referred to as “DLBTTC”) was obtained in a yield of 80%. ^{From the 1} H-NMR measurement, the peak of the target product was confirmed at 7.2 ppm, 4.6 ppm, and 3.4 ppm.

Production of high molecular weight (meth) acrylic polymer RAFT agent (DLBTC) (9.13 g) obtained in 1 above, 2,2′-azobis-2-methylbutyro in a 1 L flask equipped with a stirrer and a thermometer Nitrile (hereinafter referred to as “ABN-E”) (0.53 g), BA (560 g) and anisole (230 g) were charged, sufficiently deaerated by nitrogen bubbling, and polymerization was started while stirring in a 60 ° C. constant temperature bath. After 3 hours and 30 minutes, the reaction was stopped by cooling to room temperature. The polymer was obtained by reprecipitation purification from methanol and vacuum drying.
Next, the polymer (320 g) was placed in a 1 L flask equipped with a stirrer and a thermometer, and further BA (138.9 g), DMS (5.3 g), ABN-E (0.40 g), and anisole ( 285 g) was thoroughly deaerated by nitrogen bubbling, and the polymerization was restarted while stirring in a thermostatic bath at 60 ° C. After 8 hours, the reaction was stopped by cooling to room temperature. The polymerization solution was purified by reprecipitation from methanol and vacuum dried to obtain (meth) acrylic polymer B-12. The properties of the polymer are shown in Table 3.

Details of the compounds shown in Tables 1 to 3 are as follows.
BA: butyl acrylate HA: 2-ethylhexyl acrylate TDA: tridecyl acrylate MMA: methyl methacrylate DMS: 3-methacryloxypropylmethyldimethoxysilane TMS: 3-methacryloxypropyltrimethoxysilane IPA: isopropyl alcohol MOA: orthoacetic acid Methyl MEK: methyl ethyl ketone BAC: butyl acetate DTBP: di-t-butyl peroxide DTHP: di-t-hexyl peroxide ABN-E: 2,2′-azobis (2-methylbutyronitrile)
PHO: t-butyl peroxy-2-ethylhexanoate (manufactured by NOF Corporation, trade name “Perhexyl O”)
AIBN: 2,2′-azobis (isobutyronitrile)

≪Preparation and evaluation of curable composition≫
Examples 1-28, Comparative Examples 1-4
The low molecular weight (meth) acrylic polymer (A component) and the high molecular weight (meth) acrylic polymer (B component) obtained in the above synthesis examples and commercially available raw materials were blended in the ratios shown in Tables 4-6. Using a planetary mixer, a curable composition was obtained by mixing at a temperature of 60 ° C. and 10 Torr for 1 hour. The cured product obtained from each composition was subjected to a weather resistance test and a tensile test, and the results are shown in Tables 4 to 6.

Details of the compounds shown in Tables 4 to 6 are as follows.
ES-S2420: Modified silicon (Asahi Glass Co., Ltd., trade name “Exstar S2420”)
PPG: Exenol 2020 (Asahi Glass Co., Ltd.)
CCR: Light calcium carbonate
Super SS: Heavy calcium carbonate (Maruo Calcium Co., Ltd., trade name "Super SS")
R820: Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd.)
Tinuvin B75: Anti-aging agent (manufactured by BASF Japan)
U220H: Dibutyltin diacetylacetonate (Nitto Kasei Co., Ltd.)
Nursem Titanium: Dibutoxytitanium Diacetylacetonate (Nippon Chemical Industry Co., Ltd., trade name “Narsem Titanium”)
DBU: 1,8-diazabicyclo [5,4,0] undecene-7
SH6020: 3- (2-aminoethyl) aminopropyltrimethoxysilane (Toray Dow Corning)
SZ6030: Vinyltrimethoxysilane (Toray Dow Corning)

Examples 1 to 28 are evaluations related to the curable composition of the present invention, and good results were shown for both weather resistance and mechanical properties. Moreover, when the ratio of the low molecular weight (meth) acrylic polymer to the high molecular weight (meth) acrylic polymer is in the range of 10/90 to 90/10, a result of excellent weather resistance of the obtained cured product is obtained. (Examples 16, 23-26). Further, in the weather resistance test and the tensile test, the workability (ease of application) when each curable composition was applied to a Teflon (registered trademark) sheet having a thickness of 2 mm was good. Therefore, the curable composition provided by the present invention is excellent in weather resistance, mechanical properties and workability, and can be suitably used as a sealing material composition.
On the other hand, in Comparative Example 1, the high molecular weight (meth) acrylic polymer (component B) did not have a reactive silyl group, and the weather resistance of the cured product was not sufficient. In Comparative Examples 2 and 3, the double bond concentration of the low molecular weight (meth) acrylic polymer (component A) was outside the range specified in the present invention, and both showed results inferior in the weather resistance of the cured product. Similarly, in Comparative Example 4 which does not contain the high molecular weight (meth) acrylic polymer as the component (B), the weather resistance of the cured product was insufficient.

  The curable composition of the present invention is cured at normal temperature with moisture in the atmosphere, and a cured product having excellent weather resistance and mechanical properties can be obtained. Moreover, since it has moderate viscosity, it is excellent also in workability | operativity. Therefore, it is suitable as a curable composition for sealing materials, exterior tile adhesives, and the like.

Claims (11)

(Meth) acrylic polymer (A) having a weight average molecular weight of 500 or more and less than 10,000, and (meth) acrylic polymer (B) having a weight average molecular weight of 10,000 or more and 100,000 or less. A curable composition comprising
The (meth) acrylic polymer (A) has a double bond in the molecule of 0.01 meq / g or more and 1.0 meq / g or less,
The (meth) acrylic polymer (B), have a reactive silyl group in the molecule,
The double bond concentration contained in the entire (meth) acrylic polymer (A) and the (meth) acrylic polymer (B) is 0.01 meq / g or more and 0.50 meq / g or less.
Curable composition.   2. The curable composition according to claim 1, wherein the (meth) acrylic polymer (A) has a viscosity at 25 ° C. of 1,000 mPa · s or more and 100,000 mPa · s or less.   3. The curable composition according to claim 1, wherein the (meth) acrylic polymer (B) has a viscosity at 25 ° C. of 5,000 mPa · s or more and 300,000 mPa · s or less.   The said (meth) acrylic-type polymer (A) is a curable composition of any one of Claims 1-3 which has a reactive silyl group in a molecule | numerator.   The curable composition according to any one of claims 1 to 4, wherein the (meth) acrylic polymer (B) has 0.1 to 2.2 reactive silyl groups in the molecule. .   The curable composition according to any one of claims 1 to 5, wherein the (meth) acrylic acid polymer (B) has a dialkoxysilyl group as a reactive silyl group.   The (meth) acrylic polymer (B) has 5 masses of (meth) acrylic acid alkyl ester having an alkyl group having 10 or more carbon atoms in all monomer units constituting the (meth) acrylic polymer. The curable composition according to any one of claims 1 to 6, comprising at least%. The (meth) the amount of the acrylic polymer (A) and the (meth) acrylic polymer (B), any one of claim 1 to 7 weight ratio is 10-90 / 90-10 The curable composition according to 1. Furthermore, the curable composition of any one of Claims 1-8 containing an oxyalkylene type polymer. The curable composition according to any one of claims 1 to 9 , comprising at least one compound selected from the group consisting of a tin-based catalyst, a titanium-based catalyst, and a tertiary amine as a curing accelerator. A sealing material composition comprising the curable composition according to any one of claims 1 to 10 .