WO2019058794A1 - Curable composition, sealing material composition, and adhesive composition - Google Patents

Abstract

[Problem] To provide a curable composition, a sealing material composition, and an adhesive composition having excellent workability and providing a cured product with excellent mechanical properties and weather resistance. [Solution] Disclosed is a curable composition comprising: an oxyalkylene-based polymer (A) including a reactive silyl group; and a (meth)acrylic polymer (B). The (meth)acrylic polymer (B) includes, in the molecule thereof, from 0.01 meq/g to 1.0 meq/g double bonds. The (meth)acrylic polymer (B) may include, in the molecule thereof, from 0.1 to 2.2 reactive silyl groups.

Description

Curable composition, sealing material composition, and adhesive composition

The present invention relates to a curable composition, and more specifically, a curable composition which can be cured at room temperature by moisture such as in the air to form a cured product exhibiting excellent mechanical properties, and the curable composition The present invention relates to a sealant composition of the composition and an adhesive composition containing the curable composition.

Examples of the curable composition containing a polymer having a room temperature curing type reactive group include compositions containing various polymers such as modified silicones, urethanes, polysulfides and acrylics, and are used for construction applications, electricity, and so on. It is widely used as an adhesive, sealing material, paint, etc. in electronics related applications, automotive related applications etc. For example, although a modified silicone polymer is a curable composition based on an oxyalkylene polymer having a hydrolyzable silyl group, it has good workability and mechanical properties such as elongation at break and strength at break. It is widely used as a base polymer for adhesives and sealants because it is a well-balanced material.
However, it is known that a curable composition containing a modified silicone polymer as a base polymer has a problem that the resulting cured product has insufficient weather resistance. For this reason, curable compositions comprising an acrylic polymer have been proposed.

Patent Document 1 discloses a specific vinyl polymer having an alkoxysilyl group, a polyoxyalkylene compound having an alkoxysilyl group at an end, and a specific vinyl polymer having no polypropylene glycol having a specific molecular weight or an alkoxysilyl group. Disclosed is a sealant composition containing the same. Patent Document 2 discloses a sealing material composition including 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. It is disclosed that such a curable resin composition can be suitably used as a sealing material and an adhesive for exterior tiles.

JP 2004-18748 A WO 2008/059872 JP, 2014-118502, A

The cured products obtained from the compositions described in Patent Documents 1 to 3 exhibit good mechanical properties and also have improved weatherability. However, the demand for improving the weatherability is high, and a further improvement of the weatherability has been required for the curable composition. In general, the weatherability tends to be improved by increasing the molecular weight of the polymer, but it is known that problems occur in terms of coatability and handling because the composition has a high viscosity.

The present invention has been made in view of the above-mentioned circumstances, and has a low viscosity and is excellent in workability, and a curable composition, a sealing material composition, and an adhesive which are also excellent in mechanical properties and weather resistance of a cured product. It is an object of the present invention to provide a composition.

As a result of intensive studies to solve the above problems, the present inventor has found that the curable composition comprises an oxyalkylene polymer having a reactive silyl group and a (meth) acrylic polymer, which is (meth) It has been found that when the acrylic polymer has a specific amount of double bonds, the weatherability of the cured product and the sealing material and adhesive containing the cured product is improved. The present invention has been completed based on the findings. According to the present specification, the following means are provided.

[1] A curable composition comprising an oxyalkylene polymer (A) having a reactive silyl group and a (meth) acrylic polymer (B),
The curable composition in which the said (meth) acrylic-type polymer (B) has a double bond in a molecule of 0.01 meq / g or more and 1.0 meq / g or less.
[2] The curable composition according to [1], wherein the (meth) acrylic polymer (B) has a weight average molecular weight of 1,000 or more and 50,000 or less.
[3] The curable composition according to the above [1] or [2], wherein the (meth) acrylic polymer (B) has a viscosity of 1,000 mPa · s or more and 300,000 mPa · s or less at 25 ° C. object.
[4] The (meth) acrylic polymer (B) according to any one of the above [1] to [3], having 0.1 or more and 2.2 or less reactive silyl groups in the molecule. Curable composition.
[5] The curable composition according to [4], wherein the (meth) acrylic acid polymer (B) has a dialkoxysilyl group as a reactive silyl group.
[6] 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 the above [1] to [5], which contains 5% by mass or more.
[7] The curable composition according to any one of the above [1] to [6], wherein the oxyalkylene polymer (A) has a number average molecular weight of 22,000 or more.
[8] The amount of the oxyalkylene polymer (A) and the (meth) acrylic polymer (B) used is 10 to 90/90 to 10 in mass ratio, in the above [1] to [7] The curable composition as described in any.
[9] The curable composition according to any one of the above [1] to [8], which comprises one or more compounds selected from the group consisting of tin-based catalysts, titanium-based catalysts and tertiary amines as a curing accelerator. object.
[10] A sealing material composition comprising the curable composition according to any one of the above [1] to [9].
[11] An adhesive composition comprising the curable composition according to any one of the above [1] to [9].

The curable composition of the present invention is low in viscosity and excellent in workability. In addition, a cured product having excellent strength, elongation, and weather resistance can be obtained from the composition. For this reason, it is used suitably for adhesives, such as a sealing material in which excellent mechanical physical property and high weather resistance are calculated | required, and an adhesive agent for exterior tiles.

Hereinafter, the present invention will be described in detail. In the present specification, "(meth) acrylic" means acrylic and / or methacrylic, and "(meth) acrylate" means acrylate and / or methacrylate. Moreover, "(meth) acryloyl group" means an acryloyl group and / or a methacryloyl group.

The curable composition of the present invention contains an oxyalkylene polymer having a reactive silyl group which is the component (A) and a (meth) acrylic polymer which is the component (B) as essential components. Below, the detail of each component is demonstrated.

<Component (A): Oxyalkylene-Based Polymer Having 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 (1).
-O-R ^2- (1)
(Wherein, 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 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 one or more of the above repeating units in combination. Among these, CH (CH ₃ ) CH ₂ is preferable in terms of excellent workability.

The reactive silyl group contained in the oxyalkylene polymer containing a reactive silyl group is not particularly limited, and examples thereof include alkoxysilyl group, halogenosilyl group and silanol group, but from the viewpoint of easy control of reactivity, alkoxysilyl 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 method for producing the oxyalkylene polymer is not particularly limited. For example, a polymerization method using an alkali catalyst such as KOH, a heavy metal using a transition metal compound-porphyrin complex catalyst, using the corresponding epoxy compound or diol as a raw material A legal method, a polymerization method using a complex metal cyanide complex catalyst, a polymerization method using phosphazene, and the like can be mentioned.
The oxyalkylene polymer may be either 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 oxyalkylene polymer molecule is preferably in the range of 1 to 4 from the viewpoint of performance such as adhesiveness and tensile properties of the cured product, and more preferably The range is 1.5 to 3.
The position of the reactive silyl group contained in the above-mentioned oxyalkylene polymer is not particularly limited, and can be a side chain and / or an end 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, and still more preferably 15,000, from the viewpoint of mechanical properties. It is above. 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 still more preferably 40,000 or less from the viewpoint of workability (viscosity) at the time of coating of the curable composition. . The range of Mn can be set by combining the above upper limit value and lower limit value, but, for example, is 5,000 or more and 60,000 or less, and may be 15,000 or more and 60,000 or less, 18 It may be 1,000 or more and 50,000 or less, or 22,000 or more and 50,000 or less.

A commercial item may be used as an oxyalkylene polymer having a reactive silyl group. As a specific example, Kaneka Co., Ltd. "MS polymer S203", "MS polymer S303", "MS polymer S810", "Syryl SAT 200", "Syryl SAT 350", "Syryl EST 280" and "Syryl SAT 30", and Asahi Glass Exexer's "Exester S2410", "Exester S2420" and "Exester S3430" (all trade names) are exemplified.

<(B) component: (meth) acrylic polymer>
The (meth) acrylic polymer is a polymer having a structural unit derived from a (meth) acrylic monomer, and, for example, by polymerizing a monomer mixture containing the (meth) acrylic monomer You can get it. The (meth) acrylic monomer is a monomer having a (meth) acryloyl group in the molecule, and (meth) acrylic acid, (meth) acrylic acid alkyl ester, (meth) acrylic acid alkoxyalkyl ester, etc. It can be mentioned. The amount of the (meth) acrylic monomer used is preferably in the range of 10 to 100% by mass, more preferably 30 to 100% by mass, based on the total constituent monomers of the (meth) acrylic polymer. It is preferably in the range of 50 to 100% by mass.

Specific examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n (meth) acrylate -Butyl, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-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) acrylate Tridecyl acid, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, stearyl (meth) acrylate, nonadecyl (meth) acrylate, (meth) acrylate Eicosyl, helicosyl (meth) acrylate, behenyl (meth) acrylate, tetracosyl (meth) acrylate, hexacosyl (meth) acrylate, octacosyl (meth) acrylate, tricontyl (meth) acrylate, dotriacontyl (meth) acrylate , (Meth) acrylate tetratriacontyl, (meth) acrylate hexatriacontyl, (meth) acrylate octatriacontyl, (meth) acrylate tetracontyl, (meth) acrylate isodecyl, (meth) acrylate Iso Ndecyl, Isolauryl (meth) acrylate, Isotridecyl (meth) acrylate, Isotetradecyl (meth) acrylate, Isopentadecyl (meth) acrylate, Isohexadecyl (meth) acrylate, Isoheptadecyl (meth) acrylate (Meth) acrylic acid isostearyl, (meth) acrylic acid isononadecyl, (meth) acrylic acid isoeicosyl, (meth) acrylic acid isohenicosyl, (meth) acrylic acid isobehenyl, (meth) acrylic acid isotetrakosyl, (meth) acrylic acid isohexacosyl, (Meth) acrylate isooctacosyl, (meth) acrylate isotriacontyl, (meth) acrylate isodotriacontyl, (meth) acrylate isotetratriacontyl, (meth) acrylate isohexatriacontyl (, Examples thereof include (meth) acrylic acid alkyl esters having a linear or branched aliphatic alkyl group or alicyclic alkyl group such as isooctatriacontol acrylate, and isotetracontyl (meth) acrylate. One or more of these can be used. Among these, (meth) acrylic acid alkyl esters having an alkyl group having 1 to 8 carbon atoms are preferable from the viewpoint of mechanical properties of a 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 (meth) acrylic polymer, and more preferably It is 30% by mass or more, more preferably 50% by mass or more. In addition, an upper limit is 100 mass%, may be 90 mass%, may be 80 mass%, and may be 50 mass%.

Further, among the above, when (meth) acrylic acid alkyl ester having an alkyl group having 10 or more carbon atoms is used, good compatibility with the oxyalkylene polymer is ensured, and mechanical properties and weather resistance become good. It is preferable in point. The carbon number of the alkyl group is preferably 10 to 20, more preferably 12 to 20. The amount of the (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% by mass, based on the total constituent monomers of the (meth) acrylic polymer. It is not less than mass%, more preferably not less than 20 mass%. In addition, an upper limit is 100 mass% or less, may be 90 mass% or less, may be 80 mass% or less, and may be 50 mass% or less.

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) acrylate Examples thereof include butoxybutyl and butoxyhexyl (meth) acrylate, and one or more of these 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 a cured product, and (meth) acrylic acid having an alkoxyalkyl group having 2 to 4 carbon atoms Acid alkoxy alkyl 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, and further preferably, with respect to the total constituent monomers of the (meth) acrylic polymer. Is 50% by mass or more. In addition, an upper limit is 100 mass% or less, may be 90 mass% or less, may be 80 mass% or less, and may be 50 mass% or less.

The (meth) acrylic polymer may have a reactive silyl group in the molecule. When the (meth) acrylic polymer has a reactive silyl group, the mechanical properties of the cured product tend to be good. The type of reactive silyl group is not particularly limited, and examples thereof include an alkoxysilyl group, a halogenosilyl group, and a silanol group. However, an alkoxysilyl group is preferable from the viewpoint of easily controlling the 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 group And dialkoxysilyl groups such as ethyldiethoxysilyl group; and 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 resistance stability.

When the (meth) acrylic polymer has a reactive silyl group, the average value of the number of reactive silyl groups contained in one polymer molecule is preferably 0.1 or more from the viewpoint of the tensile strength of the cured product. More preferably, it is 0.2 or more. The average value of the 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 still more preferably 2 .5 or less, more preferably 2.2 or less. Although 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, 0.1 or more and 5.0 or less, and 0.1 or more It may be 3.0 or less, may be 0.1 or more and 2.2 or less, and may be 0.2 or more and 2.2 or less.
The position of the reactive silyl group contained in the (meth) acrylic polymer is not particularly limited, and can be the side chain and / or the end 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 vinyl monomers having a reactive silyl group, vinylsilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, etc .; trimethoxysilylpropyl (meth) acrylate ( Silyl group-containing (meth) acrylic esters such as triethoxysilylpropyl acrylate, dimethylmethoxysilylpropyl (meth) acrylate and methyldimethoxysilylpropyl methacrylate (meth) acrylate; silyl groups such as trimethoxysilylpropyl vinyl ether Containing vinyl ethers; silyl group-containing vinyl esters such as vinyl trimethoxysilyl undecanoate and the like are exemplified, and one or more of them may be used.

The (meth) acrylic polymer may be copolymerized with other monomers copolymerizable therewith, in addition to the above-mentioned 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, ethylene oxide adduct of (meth) acrylic acid;
(Meth) acrylic acid aromatic esters such as phenyl (meth) acrylate, toluyl (meth) acrylate, and benzyl (meth) acrylate;
(Meth) acrylic acid trifluoromethylmethyl, (meth) acrylic acid 2-trifluoromethylethyl, (meth) acrylic acid 2-perfluoroethyl ethyl, (meth) acrylic acid 2-perfluoroethyl 2-perfluorobutyl Ethyl, 2-Perfluoroethyl (meth) acrylate, Perfluoromethyl (meth) acrylate, Diperfluoromethylmethyl (meth) acrylate, 2-Perfluoromethyl-2-perfluoroethyl methyl (meth) acrylate And fluorine-containing (meth) acrylic esters such as 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate and 2-perfluorohexadecylethyl (meth) acrylate;
Fluorine-containing olefins such as perfluoroethylene, perfluoropropylene and vinylidene fluoride;
Aromatic monomers such as styrene, vinyl toluene, α-methylstyrene, chlorostyrene, styrene sulfonic acid and salts thereof;
Maleic anhydride; unsaturated dicarboxylic acids such as maleic acid and fumaric acid, and monoalkyl esters and dialkyl esters thereof;
Maleimide compounds such as maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, phenyl maleimide, cyclohexyl maleimide and the like;
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 and 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, allyl alcohol and the like. Moreover, 1 type or 2 types or more of these can be used.

The weight average molecular weight (Mw) of the (meth) acrylic polymer is a polystyrene equivalent molecular weight by gel permeation chromatography (hereinafter, also referred to as "GPC"), and preferably from the viewpoint of strength and weatherability of a cured product. It is 1,000 or more, more preferably 2,000 or more, further preferably 5,000 or more, more preferably 10,000 or more, and still more preferably 15,000 or more. On the other hand, from the viewpoint of workability (low viscosity), the upper limit value of Mw is preferably 50,000 or less, more preferably 45,000 or less, still more preferably 40,000 or less, more preferably 35 Is 1,000 or less, more preferably 30,000 or less. Mw may be 20,000 or less, or 15,000 or less. Although the range of Mw can be set combining said upper limit and lower limit, it is 1,000-50,000, for example, may be 2,000-45,000, 3 It may be between 4,000 and 40,000.

The molecular weight distribution of the (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, still more preferably 3.0 or less, and still more preferably 2., from the viewpoint of the balance between tensile physical properties and workability. It is 5 or less, more preferably 2.0 or less. The lower limit of Mw / Mn is usually 1.0.

The viscosity of the (meth) acrylic polymer is preferably 1,000 mPa · s or more at 25 ° C., and more preferably 2,000 mPa · s or more. 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 viscosity is preferably 300,000 mPa · s or less, more preferably 180,000 mPa · s or less, still more preferably 100,000 mPa · s or less, and still more preferably 60,000 mPa · s or less is there. If the viscosity is 1,000 mPa · s or more, it is preferable in order to suppress sag when applied to a vertical surface, and by setting the viscosity to 300,000 mPa · s or less, the workability of the curable composition becomes good. . Although the range of the viscosity can be set by combining the above upper limit value and the lower limit value, for example, it is 1,000 mPa · s or more and 300,000 mPa · s or less, and 2,000 mPa · s or more and 180,000 mPa · s. Or less and may be 3,000 mPa · s or more and 60,000 mPa · s or less.

In the present invention, the (meth) acrylic polymer has a double bond in the molecule. When the (meth) acrylic polymer has an appropriate amount of double bonds, for example, the double bonds react during the period when the cured product is exposed to the outdoors, etc., and the molecular weight is appropriately increased, so that the weather resistance is improved. Improve. For this reason, in the present invention, the cured product can exhibit excellent weather resistance while suppressing the viscosity of the (meth) acrylic polymer to ensure the workability. The above mechanism is an assumption and does not limit the scope of the present invention.

The amount of double bonds contained in the (meth) acrylic polymer is required to have 0.01 meq / g or more from the viewpoint of exhibiting the effect on the above-mentioned 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, 0.30 meq / g or more. May be On the other hand, if the amount of double bonds is too large, the degree of crosslinking of the cured product becomes too high during exposure, and as a result, the flexibility tends to be insufficient, so that cracking tends to occur. For this reason, the amount of double bonds is 1.0 meq / g or less, preferably 0.50 meq / g or less, and 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, and is, for example, 0.01 meq / g or more and 1.0 meq / g or less, and 0.05 meq / g or more 1 It may be not more than 0 meq / g, and not less than 0.10 meq / g and not more than 0.50 meq / g.

There is no particular limitation on the method of 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, or a functional group and a double bond capable of reacting with the functional group after producing a (meth) acrylic polymer having a functional group And the like.

The double bond can also be introduced by carrying out the production of the (meth) acrylic acid polymer under high temperature conditions. For example, if the polymerization temperature is 100 ° C. or higher, a cleavage reaction starting from the hydrogen abstraction reaction from the polymer chain occurs for high temperature polymerization, so the ethylenic unsaturation represented by the following general formula (2) at the molecular terminal A polymer with bonds is obtained. The polymerization temperature is preferably 120 ° C. or more, more preferably 150 ° C. or more. The higher the polymerization temperature, the higher the double bond concentration in the polymer. According to the above method, it is possible to obtain a (meth) acrylic polymer having a double bond simply and with good productivity. Furthermore, it becomes possible to manufacture easily, without containing impurities, such as a large amount of initiator and chain transfer agent, in molecular weight control. Chain transfer agents such as mercaptans are preferably not used because they lead to a decrease in weatherability. On the other hand, it is preferable to set the upper limit of the polymerization temperature to 350 ° C. or less, from the viewpoint of eliminating the possibility of the coloring of the polymerization liquid due to the decomposition reaction or the molecular weight decrease. By polymerizing in the above temperature range, a copolymer having an appropriate molecular weight, a low viscosity, no coloring, and few impurities can be efficiently produced. 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 copolymer with high purity can be obtained. .

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

As R ¹ in the above general formula (2), 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 It is an alkyl group, a trialkoxysilylalkyl group, an alkyldialkoxysilylalkyl group or a hydrogen atom.

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

In general, when a crosslinkable functional group is uniformly introduced into a polymer, physical properties such as the curability of a curable composition containing the polymer and the weather resistance of a cured product to be obtained become good. In this respect, when a stirred tank type reactor is used for the reactor, a (meth) acrylic polymer having a relatively narrow distribution of composition (distribution of crosslinkable functional groups) and molecular weight distribution can be obtained, which is preferable. Moreover, the process using a continuous stirring tank type reactor is more preferable at the point which narrows 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, etc. may be used. For example, after filling a pressurizable reactor with a solvent and setting the temperature to a predetermined temperature under pressure, a reactor containing a monomer mixture comprising each monomer and, if necessary, a polymerization solvent at a constant feed rate And the polymerization liquid is withdrawn in an amount corresponding to the supply amount of the monomer mixture. Moreover, a polymerization initiator can also be mix | blended with a monomer mixture as needed. The amount to be blended 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 and the boiling point of the monomer mixture and solvent used, and does not affect the reaction, but may be a 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 monomers may not react sufficiently, and if the unreacted monomers exceed 60 minutes, the productivity may be deteriorated. The preferred residence time is 2 to 40 minutes.

As an example of a polymerization initiator used to obtain a (meth) acrylic polymer, any initiator may be used as long as it generates radicals at a predetermined reaction temperature. Specifically, di-t-butyl peroxide, di-t-hexyl peroxide, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, cumene hydroperoxide Oxides, organic peroxides such as t-butyl hydroperoxide, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), azobiscyclohexacarbonitrile, Azo compounds such as azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-amidinopropane) dihydrochloride, and 4,4′-azobis (4-cyanovaleric acid) can be mentioned. One of these polymerization initiators may be used alone, or two or more thereof may be used in combination. When one having a high hydrogen abstraction ability is used as the polymerization initiator, the double bond concentration of the obtained polymer tends to be high. For example, using an organic peroxide rather than an azo compound tends to give a polymer having a high double bond concentration.
The amount of the polymerization initiator used can be appropriately adjusted according to the types of the polymerization initiator and the monomer, the desired molecular weight, the polymerization conditions and the like, but in general, based on 100 parts by mass of the monomer used The amount is 0.001 to 10 parts by mass. When polymers of the same molecular weight are obtained, the smaller the amount of polymerization initiator used, the higher the double bond concentration in the obtained polymer tends to be.

When an organic solvent is used for producing a (meth) acrylic polymer, an organic hydrocarbon compound is suitable, and cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, ethyl acetate And esters such as butyl acetate, ketones such as acetone, methyl ethyl ketone and cyclohexanone, and alcohols such as methanol, ethanol, and isopropanol. These may be used alone or in combination of two or more. If the solvent does not dissolve the (meth) acrylic acid ester copolymer well, the scale tends to grow on the wall of the reactor, which tends to cause production problems in the washing step and the like. In addition, when an organic solvent having a high chain transfer ability such as isopropanol is used, the double bond concentration in the obtained polymer tends to be low.
The amount of the solvent used is preferably 80 parts by mass or less with respect to 100 parts by mass of all vinyl monomers. By setting the amount to 80 parts by mass or less, high conversion can be obtained in a short time. More preferably, it is 1 to 50 parts by mass. In addition, dehydrating agents such as trimethyl orthoacetate and trimethyl orthoformate can also be added.

Known chain transfer agents may be used for the production of the (meth) acrylic polymer. When a chain transfer agent is used, the double bond concentration in the resulting polymer tends to be low. Also, in general, the double bond concentration is reduced by increasing the amount of chain transfer agent used.

The reaction liquid withdrawn from the reactor can be carried on to the next step as it is, or the polymer can be isolated by distilling off volatile components such as unreacted monomers, solvents and low molecular weight oligomers by distillation or the like. It can be released. It is also possible to return some of the unreacted monomers, solvents, and volatile components such as low molecular weight oligomers distilled off from the reaction solution back to the raw material tank or directly back to the reactor and use them again for the polymerization reaction.
Thus, the method of recycling unreacted monomers and solvents is a preferable method from the economical point of view. 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 post treatment under heating conditions by adding a radical generator. Although the addition amount of the radical generating agent is about 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer, the reduction effect of the double bond concentration is larger as the addition amount is larger.
The heating temperature in the heat treatment is about 50 to 130 ° C., but the lower the temperature, the larger the reduction effect of 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 it is preferable to set the amount of the remaining radical generator to be less than 1% by mass with respect to the polymer. Those skilled in the art can calculate the remaining radicals 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 post-treatment. The hydrogenation can be carried out by any known method.
That is, after adding a homogeneous system catalyst or a heterogeneous system catalyst to the polymer reaction solution, the system is made 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 it is for 2 to 20 hours. Let it react. Specific examples of homogeneous catalysts include rhodium complexes such as chlorotris (triphenylphosphine) rhodium, ruthenium complexes such as dichlorotris (triphenylphosphine) ruthenium and chlorohydrocarbonyltris (triphenylphosphine) ruthenium, and dichlorobis (triphenylphosphine). And platinum complexes such as platinum, and iridium complexes such as carbonyl bis (triphenylphosphine) iridium and the like. On the other hand, examples of heterogeneous catalysts include solid catalysts in which transition metals such as nickel, rhodium, ruthenium, palladium and platinum are supported on carbon, silica, alumina, fibers, organic gel-like substances and the like. Heterogeneous catalysts are preferable in that the catalyst can be easily removed by filtration or the like, so that the quality is stable and expensive catalysts can be reused. The amount of catalyst 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.

<Curable composition>
As described above, the curable composition of the present invention contains the (A) component and the (B) component as essential components. Here, the ratio of the component (A) and the component (B) ((A) / (B)) is preferably 10 to 10 by mass ratio in that the weatherability and mechanical properties of the resulting cured product are good. It is 90/90 to 10, more preferably 20 to 60/80 to 40.

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

As the filler, light calcium carbonate having an average particle diameter of about 0.02 to 2.0 μm, heavy calcium carbonate having an average particle diameter of about 1.0 to 5.0 μm, titanium oxide, carbon black, synthetic silicic acid, talc, zeolite Mica, silica, calcined clay, kaolin, bentonite, aluminum hydroxide and barium sulfate, glass balloon, silica balloon, polymethyl methacrylate balloon are exemplified. These fillers can improve the mechanical properties of the cured product and improve the strength and elongation.
Among these, light calcium carbonate, ground calcium carbonate and titanium oxide, which are highly effective in improving physical properties, are preferable, and a mixture of light calcium carbonate and ground calcium carbonate is more preferable. The amount of the filler added is preferably 20 to 300 parts by mass, more preferably 50 to 200 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). When a mixture of light calcium carbonate and heavy calcium carbonate is used as described above, the weight ratio of light calcium carbonate / heavy calcium carbonate is preferably in the range of 90/10 to 50/50.

Examples of plasticizers include liquid polyurethane resins, polyester plasticizers obtained from dicarboxylic acids and diols; ethers or esters of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; and sugar polyalcohols such as sucrose, etc. Polyether plasticizers such as saccharide-based polyethers obtained by addition-polymerizing alkylene oxides such as oxide and propylene oxide and then etherifying or esterifying them; polystyrene-based plasticizers such as poly-α-methylstyrene; crosslinkability Poly (meth) acrylate etc. which do not have a functional group are mentioned. Among these, poly (meth) acrylates having no crosslinkable functional group are preferable in terms of durability such as weather resistance of the cured product. Among them, those having a Mw of 1,000 to 7,000 and a glass transition temperature of −30 ° C. or less 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, based on 100 parts by mass of the total amount including the components (A) and (B). And may be in the range of 0 to 50 parts by mass.

Examples of 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, thermal stabilizers, or An anti-aging agent which is a mixture of these can be used.
As an ultraviolet absorber, the brand names "tinuvin 571", "tinuvin 1130", and "tinuvin 327" made from BASF are illustrated. As a light stabilizer, the brand name "tinuvin 292", "tinuvin 144", "tinuvin 123" by the company, and the brand name "Sanol 770" by a Sanko company are illustrated, for example. As a heat stabilizer, brand names "Irganox 1135", "Irganox 1520", and "Irganox 1330" manufactured by BASF Corp. are exemplified. A trade name "Tinuvin B75" manufactured by BASF, which is a mixture of UV absorber / light stabilizer / heat stabilizer may be used.

As the curing accelerator, known compounds such as tin-based catalysts, titanium-based catalysts and tertiary amines can be used.
Examples of tin-based catalysts include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetonate, dioctyltin dilaurate and the like. Specifically, trade 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. is illustrated.
Examples of titanium-based catalysts include tetraisopropyl titanate, tetra n-butyl titanate, titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethyl acetylacetonate, dibutoxy titanium diacetyl acetonate, diisopropoxy titanium diacetyl acetonate, Titanium octylene glycolate, titanium lactate and the like can be mentioned.
Examples of tertiary amines include triethylamine, tributylamine, triethylenediamine, hexamethylenetetramine, 1,8-diazabicyclo [5,4,0] undecen-7 (DBU), diazabicyclononene (DBN), N- Methyl morpholine, N-ethyl morpholine and the like can be mentioned.

The amount of the curing accelerator used is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 2 parts by mass with respect to 100 parts in total of the components (A) and (B).

As an anti-tack agent, trade name “Alonix M 8030”, “M 8100”, “M 309” or a mixture with an optical polymerization initiator manufactured by Toagosei Co., Ltd. which is an acrylic oligomer, saturated fatty acid oil such as soy sauce or linseed oil, A trade name "R15HT" manufactured by Idemitsu Sekiyu Co., Ltd., a trade name "PBB 3000" manufactured by Nippon Soda Co., Ltd., a trade name "Goselac 500B" manufactured by Nippon Gohsei Kagakusha, and the like are exemplified.

Examples of the adhesion imparting agent include aminosilanes such as trade names "KBM602", "KBM603", "KBE602", "KBE603", "KBM902" and "KBM903" manufactured by Shin-Etsu Silicone Co., Ltd.
In addition, dehydrating agents such as methyl orthoformate, methyl orthoacetate, and vinylsilane, organic solvents and the like may be blended.

The curable composition of the present invention can be adjusted as a one-component type in which all the compounding components are compounded and stored in advance, and are hardened by absorbing moisture in the air after application. Moreover, components such as a curing catalyst, a filler, a plasticizer, water and the like may be separately blended as a curing agent, and it may be adjusted as a two-component type in which the compounding material and the polymerization composition are mixed before use. More preferable is a one-component type which is easy to handle and has few mistakes in mixing and mixing at the time of application.

The curable composition of the present invention cures at normal temperature, and a cured product excellent in weatherability and mechanical properties is obtained. For this reason, it can be suitably used as a sealant composition in which high durability is required. The sealant composition of the present invention contains the above-mentioned curable composition, and, if necessary, other components are compounded according to a conventional method.

Moreover, the said curable composition can be suitably utilized for an adhesive agent. In the field of adhesives for building materials, high weatherability and durability are required to ensure 10 years or more, and the adhesive composition of the present invention can satisfy the requirements. In particular, in the case of tile adhesion of the outer wall, maintenance of the appearance and adhesion is required for a long time and can be met. The adhesive composition of the present invention contains the above-mentioned curable composition, and, if necessary, other components are blended in accordance with a conventional method.

The adhesive composition of the present invention may be one to which an epoxy resin is added. As such an epoxy resin, for example, epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, p -Hydroxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol epoxy resin, diaminodiphenylmethane epoxy resin, urethane modified epoxy resin, various alicyclic epoxy resins, N, N-diglycidyl aniline, N, N-diglycidyl Examples thereof include -o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, hydantoin type epoxy resin and the like. Further, flame-retardant epoxy resins such as glycidyl ether of tetrabromobisphenol A, glycidyl ethers of polyhydric alcohols such as glycerin, epoxidates of unsaturated polymers such as petroleum resin, etc. are exemplified, but these are limited thereto. In general, epoxy resins that are commonly used can be used. Among these epoxy resins, those containing at least two epoxy groups in the molecule are particularly preferable in view of high reactivity during curing and that the cured product is likely to form a three-dimensional network. Among these, bisphenol A epoxy resins and novolac epoxy resins are more preferable.

The epoxy resin is 1 to 100 parts by weight based on 100 parts by mass of the total polymers of the present invention (total mass of the oxyalkylene polymer (A) having a reactive silyl group and the (meth) acrylic polymer (B)). It is preferable to use it so that it may become a mass part. When the amount of the epoxy resin exceeds 100 parts by mass, the weather resistance may be lowered.

Moreover, when using an epoxy resin, it is preferable to use the hardening | curing agent of an epoxy resin together. As curing agents for epoxy resins, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, diethylaminopropylamine, N-aminoethylpiperazine, isophoronediamine, diaminodicyclohexylmethane, m-xylenediamine, m-phenylene Primary amines such as diamine, diaminodiphenylmethane, diaminodiphenyl sulfone, etc., linear diamines represented by (CH ₃ ) ₂ N (CH ₂ ) _n N (CH ₃ ) ₂ (wherein n is an integer of 1 to 10), A linear tertiary amine represented by (CH ₃ ) ₂ -N (CH ₂ ) _n -CH ₃ (wherein n is an integer of 0 to 10), tetramethyl guanidine, N {(CH ₂ ) n CH ₃ } ₃ (In the formula, n is an integer of 1 to 10) alkyl tertiary monoamines, trie Tanolamine, piperidine, N, N'-dimethylpiperazine, triethylenediamine, pyridine, picoline, diazabicycloundecene, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol ) Phenol, LAFILON C-260 manufactured by BASF, Araldit HY-964 manufactured by CIBA, and a secondary or tertiary amine such as mensens diamine manufactured by Rohm and Haas, 1,2-ethylene bis (isopentylideneimine) 1,2-Hexylene bis (isopentylidene imine), 1,2-propylene bis (isopentylidene imine), p, p′-biphenylene bis (isopentylidene imine), 1,2-ethylene bis (isopropylidene imine) ), 1,3-propylene bis (isopropylide) Imines), ketimines such as p-phenylene bis (isopentylidene imine), acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, various polyamide resins, dicyandiamide and derivatives thereof And various imidazoles and the like. The amount of the curing agent used is preferably 5 parts by mass to 100 parts by mass with respect to 100 parts by mass of the epoxy resin.

Since the adhesive composition provided in the present invention has a reactive silyl group, when using the above epoxy resin, it is possible to add a compound having a group capable of reacting to both the reactive silyl group and the epoxy group. The strength of the cured adhesive composition can also be improved. Specific examples of the compound having a group capable of reacting to both a reactive silyl group and an epoxy group are, for example, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)- Examples thereof include γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane.

The adhesive composition provided by the present invention contains the above-mentioned curable composition. Therefore, while being able to exhibit the effect of the said curable composition in the use of an adhesive agent, adhesiveness with a top coat can be improved. Moreover, especially in the exterior tile adhesive, the effect of the said curable composition can be exhibited highly.

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

<Method of quantifying double bond amount>
^{According to} the measurement of ¹ H-NMR, the integral value of the signal derived from the hydrogen bonded to the double bond at around 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 under 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 the alkoxysilyl group which is a reactive silyl group is represented by the following formula from the mass part of the monomer having a reactive silyl group when the total constituent monomer is 100 parts by mass: Calculated using.
f (Si) = {mass part of silyl group monomer / (molecular weight of silyl group monomer x 100 / Mn)}

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

<Weatherability test (1)>
Each curable composition was applied to a sheet of Teflon (registered trademark) with a thickness of 2 mm, and cured for 1 week under conditions of 23 ° C. and 50% RH to form a cured sheet. The resulting cured product was placed in a metalling weather meter ("DAIPLA METAL WEATHER KU-R5NCI-A" manufactured by Daipra Wintess Co., Ltd.) and subjected to an accelerated weathering test. The conditions were irradiation 63 ° C., 70% RH, and illuminance 80 mW / cm ^2, and the test was carried out with a shower for 2 minutes once every 2 hours. The time when abnormalities such as cracks and bleeding started to occur was recorded.

<Weatherability test (2)>
Each curable composition was applied to a sheet of Teflon (registered trademark) with a thickness of 2 mm, and cured for 1 week under conditions of 23 ° C. and 50% RH to prepare a cured sheet. The resulting cured product was placed in a metalling weather meter ("DAIPLA METAL WEATHER KU-R5NCI-A" manufactured by Daipra Wintess Co., Ltd.) and subjected to an accelerated weathering test. The conditions were irradiation 63 ° C., 70% RH, and illuminance 80 mW / cm ^2, and a test of a shower for 2 minutes was carried out every 2 hours for 1000 hours. After 1000 hours, the surface condition was visually confirmed (presence or absence of cracks) and the color difference (ΔE) was determined using a color difference meter (Nippon Denshoku Co., Ltd. spectral colorimeter SE-2000), and weatherability was evaluated from the degree of fading. The The color difference (ΔE) is the lightness (L ^* ) measured by the spectrocolorimeter.
Red - determined by substituting the values of the blue direction chromaticity (b ^*) in the formula - green direction chromaticity (a ^*) and yellow.

<Tension test>
Each curable composition was applied to a sheet of Teflon (registered trademark) with a thickness of 2 mm, and cured for 1 week under conditions of 23 ° C. and 50% RH to form a cured sheet. A dumbbell for tensile test (JIS K 6251 type 3) is prepared from the obtained cured product, and a tensile tester (Autograph AGS-J, manufactured by Shimadzu Corporation) is used under a condition of a tensile speed of 200 mm / min. Elongation at break and breaking strength were measured.

<Adhesive strength test>
According to the adhesive strength test method in JIS A5557 (2006) organic adhesive for exterior tile application, the test was performed using a mortar board and an exterior mosaic tile.
An adhesive is applied in a thickness of about 5 mm to a mortar board (TP Giken Co., Ltd., 10 × 50 × 50 mm), and after drawing with a comb, a commercially available exterior mosaic tile (45 ×) conforming to JIS A5209. 45 mm) was attached. After curing for 4 weeks under conditions of 23 ° C and 50% RH, a dedicated jig is attached to the tile side and the mortar side, and using a tensile tester (Autograph AGS-J, manufactured by Shimadzu Corporation), the condition at 23 ° C. The adhesion strength was measured by conducting a tensile test at a tensile speed of 3 mm / min.

<< (A) component: Production of oxyalkylene polymer >>
Synthesis Example 1 (Production of Oxyalkylene Polymer A-1)
Zinc hexacyanocobaltate glyme complex (0.05 g), polypropylene glycol (Mn: 2000, 50 g), propylene glycol (520 g) were placed in a 1000 mL pressure-type stirred tank reactor equipped with an oil jacket, and heated to 120 ° C. It was heated and allowed to react until the pressure change disappeared. Then, vacuum heating was performed at 120 ° C. for 1 hour to evaporate the volatile component. Thereafter, a 28% methanol solution (15.2 g) of sodium methoxide was added, and the pressure was reduced at 100 ° C. for 1 hour to distill off methanol. Then allyl chloride (6.3 g) was added and heating was carried out at 100 ° C. for 2 hours. The reaction was then washed twice with water (300 ml) to remove salts. After dehydration by heating under vacuum at 100 ° C. for 2 hours, chloroplatinic acid hexahydrate (0.02 g) and methyldimethoxysilane (8.3 g) are added and reacted for 4 hours to obtain silylated products of polypropylene glycol at both ends. Obtained. As a result of GPC measurement, it was Mn: 19,000, Mw: 20,700.

Synthesis Example 2 (Production of Oxyalkylene Polymer A-2)
Zinc hexacyanocobaltate glyme complex (0.05 g), polypropylene glycol (Mn: 2000, 50 g), propylene glycol (500 g) are placed in a 1000 mL pressure-type stirred tank reactor equipped with an oil jacket, and heated to 120 ° C. It was heated and allowed to react until the pressure change disappeared. Then, vacuum heating was performed at 120 ° C. for 1 hour to evaporate the volatile component. Thereafter, a 28% methanol solution (10.1 g) of sodium methoxide was added, and the pressure was reduced at 100 ° C. for 1 hour to distil off methanol. Then allyl chloride (4.2 g) was added and heating was carried out at 100 ° C. for 2 hours. The reaction was then washed twice with water (300 ml) to remove salts. After dehydration by heating under vacuum at 100 ° C for 2 hours, chloroplatinic acid hexahydrate (0.02 g) and methyldimethoxysilane (5.6 g) are added, and reaction is performed for 4 hours to obtain silylated products of polypropylene glycol at both ends. Obtained. As a result of GPC measurement, it was Mn: 25800, Mw: 29000.

<< (B) Component: (Meth) Production of Acrylic Polymers >>
Synthesis Example 3 (Production of (Meth) acrylic Polymer B-1)
○ Polymerization process The temperature of a 1000 mL capacity pressure type stirred tank reactor equipped with an oil jacket was maintained at 265 ° C. Then, while maintaining the pressure of the reactor constant, as a monomer, 3-methacryloxypropylmethyldimethoxysilane (made by Toray Dow Corning, trade name "Z6033," hereinafter "DMS") is 3.3. Parts, 10 parts of tetradecyl acrylate (hereinafter referred to as "TDA"), 66.7 parts of 2-ethylhexyl acrylate (hereinafter referred to as "HA"), and 20 methyl methacrylate (hereinafter referred to as "MMA") Parts, 20 parts of methyl ethyl ketone (hereinafter referred to as "MEK"), and 0.2 parts of di-t-butyl peroxide (manufactured by NOF, trade name "Perbutyl D", hereinafter referred to as "DTBP") as a polymerization initiator Continuous feed from the raw material tank to the reactor at a constant feed rate (48 g / min, residence time: 12 minutes), and feeding of the monomer mixture The corresponding reaction was continuously extracted from the outlet. Immediately after the start of the reaction, the reaction temperature was once lowered, and a temperature rise due to 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 point at which the temperature is stabilized from the start of supply of the monomer mixture is taken as the collection start point of the reaction solution, and as a result of continuing the reaction for 25 minutes, 1.2 kg of the monomer mixture is supplied, 1.2 kg of the reaction. The solution was collected. Thereafter, the reaction solution was introduced into a thin-film evaporator, and volatile components such as unreacted monomers were separated to obtain a concentrated solution.

○ Post-Treatment Step Next, 100 parts of the concentrate obtained in the above polymerization step was put into a nitrogen-substituted flask, and heated and stirred while flowing nitrogen until the liquid temperature reached 90 ° C. At 90 ° C., 0.5 part of a radical generator t-butylperoxy-2-ethylhexanoate (manufactured by NOF Corporation, trade name “Perhexyl O”) is added, and kept at 90 ° C. By stirring for 16 hours, a (meth) acrylic polymer B-1 was obtained. The properties of the polymer are shown in Table 1.

Synthesis Examples 4 to 8 (Production of (Meth) acrylic Polymers B-2 to B-6)
By the same operation as in Synthesis Example 3 except that the concentrate obtained after the polymerization step of Synthesis Example 3 is used, and the addition amount of the radical generator (Perhexyl O) and the treatment conditions in the post-treatment step are changed as shown in Table 1. And (meth) acrylic polymers B-2 to B-6 were obtained. The properties of each polymer are shown in Table 1.

Synthesis Examples 9 to 19 (Production of (meth) acrylic polymers B-7 to B-17)
By the same operation as in Synthesis Example 3 except that the raw materials used in the polymerization step and the temperature in the reactor, the addition amount of the radical generator (Perhexyl O) in the post-treatment step, and the treatment conditions were changed as shown in Tables 1 to 3. And (meth) acrylic polymers B-7 to B-17 were obtained. In Synthesis Example 16 ((meth) acrylic polymer B-14), post-treatment of the concentrate obtained after the polymerization step was not performed. The properties of each polymer are shown in Tables 1 to 3.

Synthesis example 20 (Production of (meth) acrylic polymer B-18)
In a flask equipped with a reflux condenser, butyl acetate (100 parts) was added, and stirring was performed by maintaining the internal temperature at 122 ° C. with an oil bath. In a dropping funnel, a mixture of DMS (3 parts), BA (57 parts), HA (20 parts), TDA (10 parts), MMA (10 parts), ABN-E (4 parts) for 4 hours It dripped over. The mixture was further stirred for 2 hours while maintaining the temperature at 122 ° C. Thereafter, the solvent was removed from the reaction solution under conditions of 90 ° C. and 10 mmHg with an evaporator, and the volatile component was separated to obtain a (meth) acrylic polymer B-18. The properties of the polymer are shown in Table 3.

Synthesis example 21 (Production of (meth) acrylic polymer B-19)
In Synthesis Example 3, the concentrate before the post-treatment step was taken as a (meth) acrylic polymer B-19. The properties of the polymer are shown in Table 3.

Synthesis Examples 22 to 23 (Production of (Meth) acrylic Polymers B-20 to B-21)
(Meth) acrylic polymers B-20 to B-21 were obtained by the same operation as in Synthesis Example 20 except that the raw materials used in the polymerization step and the temperature in the reactor were changed as shown in Table 3. The properties of each polymer are shown in Table 3.

The 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-methacryloxypropyl methyl dimethoxysilane TMS: 3-methacryloxypropyl trimethoxysilane IPA: isopropyl alcohol MOA: ortho acetic 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-butylperoxy-2-ethylhexanoate (manufactured by NOF Corporation, trade name "Perhexyl O")
AIBN: 2,2'-azobis (isobutyronitrile)

<< Preparation and evaluation of curable composition >>
Examples 1 to 26, Comparative Examples 1 to 3
The oxyalkylene polymer (component A) and (meth) acrylic polymer (component B) obtained in the above synthesis example and a commercially available raw material are compounded in the proportions shown in Tables 4 to 6, and a planetary mixer is used. Then, a curable composition was obtained by mixing for 1 hour under conditions of a temperature of 60 ° C. and 10 Torr. The cured product obtained from each composition was subjected to a weathering test and a tensile test, and the results are shown in Tables 4 to 6.

The details of the compounds shown in Tables 4 to 6 are as follows.
PPG: Exenol 2020 (manufactured by Asahi Glass Co., Ltd.)
CCR: Light calcium carbonate (manufactured by Shiroishi Calcium Co., Ltd., trade name "Shiroka Hana CCR")
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 Ltd.)
U220H: Dibutyltin diacetylacetonate (manufactured by Nitto Kasei Co., Ltd.)
Narsem titanium: Dibutoxy titanium diacetylacetonate (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name "Narsem titanium")
DBU: 1,8-Diazabicyclo [5,4,0] undecene-7
SH6020: 3- (2-aminoethyl) aminopropyltrimethoxysilane (made by Toray Dow Corning)
SZ6030: Vinyltrimethoxysilane (made by Toray Dow Corning)

Examples 1 to 26 are the evaluations of the curable composition of the present invention, and show good results in both weather resistance and mechanical properties. Moreover, in the weather resistance test and the tension test, the workability (applicability of application) when each curable composition was applied to a sheet of Teflon (registered trademark) with 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, Comparative Examples 1 to 3 are experimental examples of a curable composition in which the double bond concentration of the (meth) acrylic polymer is outside the range defined in the present invention. Both the (meth) acrylic polymer having a high double bond concentration (Comparative Example 1) and the (meth) acrylic polymer having a low double bond concentration (Comparative Examples 2 and 3) have sufficient weatherability of the cured product obtained. It was not a thing.

<< Preparation and Evaluation of Adhesive Composition >>
Examples 27 to 30, Comparative Examples 4 to 5
Ratios shown in Table 7 using the (meth) acrylic polymer (component B) obtained in the above synthesis example as the oxyalkylene polymer (component A) and Exester S-3430 manufactured by Asahi Glass Co., Ltd., and commercially available materials An adhesive composition was obtained by mixing at a temperature of 60.degree. C. and 10 Torr for 1 hour using a planetary mixer. The weather resistance test (2) and the adhesive strength test were conducted for each composition, and the results are shown in Table 7.

The details of the compounds shown in Table 7 are as follows.
PPG: Exenol 2020 (manufactured by Asahi Glass Co., Ltd.)
jER 828: Epoxy resin (made by Mitsubishi Chemical Corporation)
jER Cure H30: Epoxy curing agent (made by Mitsubishi Chemical Corporation)
CCR: Light calcium carbonate (manufactured by Shiroishi Calcium Co., Ltd., trade name "Shiroka Hana CCR")
Super SS: Heavy calcium carbonate (Maruo Calcium Co., Ltd., trade name "Super SS")
# 45: Carbon black (made by Mitsubishi Chemical Corporation)
R820: Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd.)
Tinuvin B75: anti-aging agent (manufactured by BASF Japan Ltd.)
U220H: Dibutyltin diacetylacetonate (manufactured by Nitto Kasei Co., Ltd.)
S340: Ketimine based silane coupling agent Thyra Ace (JNC)
SZ6030: Vinyltrimethoxysilane (made by Toray Dow Corning)

As a result of the adhesive strength test, it was found that all of Examples 27 to 30 and Comparative Examples 4 to 5 had no problem in both the strength and the fracture state, and were at levels usable as an adhesive. Moreover, in the weather resistance test (2), the workability (application ease) when each curable composition is applied to a sheet of Teflon (registered trademark) with a thickness of 2 mm is good in each of the examples and comparative examples. Met. In addition, in the adhesive strength test, the workability of each process during a series of bonding operations is to apply the adhesive with a thickness of about 5 mm to the mortar board, pull it with a comb, and then bond the exterior mosaic tile. All were good.
On the other hand, as a result of the weathering test (2), Examples 27 to 30 in which the (meth) acrylic polymer (component B) has a proper amount of double bonds in the molecule show no change in the surface state, and the color difference It was found that (ΔE) was also small. On the other hand, in Comparative Example 4 using a (meth) acrylic polymer (component B) containing an excessive amount of double bonds, it was found that a crack was generated on the surface and the weather resistance was insufficient. The As one reason, it is presumed that the flexibility of the surface is lost, etc., because the reaction of the double bond has proceeded in excess of the appropriate amount. In addition, Comparative Example 5 using a (meth) acrylic polymer (component B) not having a double bond was found to be remarkably discolored and to have insufficient weatherability. One reason is that since there is no increase in molecular weight due to double bond reaction, the ability to hold calcium carbonate inside the adhesive is insufficient and calcium carbonate is exposed on the adhesive surface to cause discoloration (whitening). Things etc. are estimated.
From the results of the adhesive strength test and the weather resistance test (2), it is understood that the adhesive composition provided by the present invention is excellent in adhesive strength, weather resistance and workability.

The curable composition of the present invention is cured at normal temperature by moisture and the like in the atmosphere, and a cured product having excellent weather resistance and mechanical properties is obtained. Moreover, since it has a suitable viscosity, it is excellent also in workability. Therefore, it is suitable as a curable composition for adhesives, such as a sealing material and an adhesive agent for exterior tiles.

Claims (11)

1. A curable composition comprising an oxyalkylene polymer (A) having a reactive silyl group and a (meth) acrylic polymer (B),
   The curable composition in which the said (meth) acrylic-type polymer (B) has a double bond in a molecule of 0.01 meq / g or more and 1.0 meq / g or less.
2. The curable composition according to claim 1, wherein the (meth) acrylic polymer (B) has a weight average molecular weight of 1,000 or more and 50,000 or less.
3. The curable composition according to claim 1 or 2, wherein the (meth) acrylic polymer (B) has a viscosity of 1,000 mPa · s or more and 300,000 mPa · s or less at 25 ° C.
4. The curable composition according to any one of claims 1 to 3, wherein the (meth) acrylic polymer (B) has 0.1 or more and 2.2 or less of reactive silyl groups in the molecule. .
5. The curable composition according to claim 4, wherein the (meth) acrylic acid polymer (B) has a dialkoxysilyl group as a reactive silyl group.
6. The (meth) acrylic polymer (B) contains 5 mass 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 5, containing at least%.
7. The curable composition according to any one of claims 1 to 6, wherein the oxyalkylene polymer (A) has a number average molecular weight of 22,000 or more.
8. The amount of the oxyalkylene polymer (A) and the (meth) acrylic polymer (B) used is 10 to 90/90 to 10 in mass ratio, according to any one of claims 1 to 7. Curable composition.
9. The curable composition according to any one of claims 1 to 8, which contains, as a curing accelerator, one or more compounds selected from the group consisting of tin-based catalysts, titanium-based catalysts and tertiary amines.
10. A sealant composition comprising the curable composition according to any one of claims 1 to 9.
11. An adhesive composition comprising the curable composition according to any one of claims 1 to 9.