JP7172057B2 - Curable composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a curable composition, and more particularly, it can be cured at room temperature with moisture in the atmosphere to form a cured product exhibiting excellent stain resistance, weather resistance, and water resistance. It relates to curable compositions.

Curable compositions containing a polymer having a room-temperature curing type reactive group include compositions containing various polymers such as modified silicone, urethane, polysulfide and acrylic. Widely used as adhesives, sealants, paints, etc. in electronics-related applications and automobile-related applications. For example, a modified silicone polymer is a curable composition based on an oxyalkylene polymer having a reactive silyl group. Since it is a good material, it is widely used as a base polymer for adhesives and sealants.
As a curable composition based on an oxyalkylene polymer having a reactive silyl group, Patent Document 1 discloses an oxyalkylene polymer containing a reactive silicon functional group and a vinyl polymer having a reactive silicon functional group. A curable composition comprising a polymer is disclosed. Further, Patent Document 2 discloses a curable composition containing a vinyl polymer having a reactive silicon group, a polyoxyalkylene polymer having a reactive silicon group, and a plasticizer having an acrylic component. .

On the other hand, in recent years, there has been a tendency to attract more attention to the design and maintainability of exterior walls, etc., and long-term durability as well as maintenance of appearance, that is, excellent stain resistance, is required. is increasing. Although the cured products obtained from the compositions described in Patent Documents 1 and 2 above exhibit excellent mechanical properties and weather resistance, they are insufficient in stain resistance.
Some sealing materials with excellent stain resistance have also been proposed, and Patent Document 3 discloses a specific sealing material containing 5 to 50% by mass as a monomer unit of an acrylic acid ester monomer having a polyoxyalkylene group in the ester portion. A sealant composition containing a copolymer, Patent Document 4 describes an alkoxysilyl group having a specific weight-average molecular weight and a glass transition temperature obtained by continuously polymerizing a vinyl monomer at a temperature of 150 to 350°C. A sealant composition is disclosed that includes an incorporated vinyl polymer. Further, Patent Document 5 discloses a curable composition comprising a vinyl polymer having reactive silicon, a fluorine-containing nonionic surfactant, and an amine compound. Furthermore, Patent Documents 6 to 8 disclose curable compositions containing (meth)acrylic polymers having alkyl groups of 10 or more carbon atoms.
Further, Patent Document 9 discloses a curable composition containing a polymer having a structure derived from a monomer having a polyoxyethylene chain.

JP-A-59-122541 Japanese Unexamined Patent Application Publication No. 2004-2604 JP-A-2003-129036 JP-A-2004-18748 JP 2008-291159 A JP 2017-88766 A JP 2017-88767 A JP 2017-206610 A JP-A-2003-313419

However, the contamination resistance of the cured products obtained from the sealant compositions described in Patent Documents 3 and 4 and the curable compositions described in Patent Documents 5 and 8 is a demand for long-term appearance maintenance for recent buildings. There was still room for improvement. In addition, the curable composition described in Patent Literature 5 has a problem that the durability of the stain resistance effect is not sufficient.
Further, in Examples of Patent Document 9, 30 to 36% by mass of methacrylic acid ester having a polyoxyethylene chain, 20% by mass of stearyl methacrylate, and 37 to 45% by mass of butyl acrylate are obtained as monomer units. Polymer, reactive silyl group-containing polyoxypropylene, and epoxy resin are exemplified in combination with curable compositions, which have excellent applicability to adherends such as wet slate plates and mortar, and , describes that it has excellent water-resistant adhesiveness, but does not disclose any knowledge about stain resistance and durability as a sealing material.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a cured product having a stain resistance superior to that of conventional products, a long-lasting effect, and a weather resistance. An object of the present invention is to provide a curable composition which is excellent in both toughness and water resistance.

As a result of intensive studies to solve the above problems, the present inventors have found a specific polymer having a reactive silyl group, and a hydrophilic polyoxyalkylene group and a hydrophobic alkyl group having 10 or more carbon atoms. According to the curable composition containing a (meth)acrylic polymer having a specific ratio, it was found that the above problems can be solved. The present invention has been completed based on this finding. According to this specification, the following means are provided.

[1] A curable composition (excluding an aqueous emulsion) containing the following (A) and (B) , wherein the (A) polymer is added to 100 parts by mass of the (B) (meta ) A curable composition containing 1 to 30 parts by mass of an acrylic polymer .
(A) a polymer having a reactive silyl group (excluding a polymer containing 40 to 98% by mass of a monomer represented by the following general formula (1) as a constituent monomer unit);

（Ｒ¹は水素原子又はメチル基、Ｒ²は炭素数２～４のアルキレン基、Ｒ³は、水素原子又は炭素数１～８の直鎖または分岐状アルキル基を、ｎは、２～２５の整数を表す。）
（Ｂ）構成単量体単位として、炭素数１０以上のアルキル基を有する（メタ）アクリル酸アルキルエステル単量体を２～６０質量％、および、前記一般式（１）に示される単量体を４０～９８質量％含む（メタ）アクリル系重合体。
〔２〕前記（Ａ）重合体が、反応性シリル基を有するポリオキシアルキレン重合体を含む前記〔１〕記載の硬化性組成物。
〔３〕前記（Ａ）重合体が、反応性シリル基を有する（メタ）アクリル系重合体を含む前記〔１〕または〔２〕のいずれかに記載の硬化性組成物。
〔４〕前記（Ｂ）（メタ）アクリル系重合体が構成単量体単位として、反応性シリル基を有する（メタ）アクリル酸エステル単量体を含む前記〔１〕～〔３〕のいずれかに記載の硬化性組成物。
〔５〕前記（Ｂ）（メタ）アクリル系重合体が構成単量体単位として、前記一般式（１）におけるｎが９～１２の整数である単量体を含む前記〔１〕～〔４〕のいずれかに記載の硬化性組成物。
〔６〕前記（Ａ）重合体を１００質量部に対して、前記（Ｂ）（メタ）アクリル系重合体を１～３０質量部含むことを特徴とする前記〔１〕～〔５〕のいずれかに記載の硬化性組成物。
〔７〕さらに、可塑剤を含むことを特徴とする前記〔１〕～〔６〕のいずれかに記載の硬化性組成物。
〔８〕可塑剤が、前記一般式（１）に示される単量体を構成単量体単位として含まず、かつ、反応性シリル基を含まない、重量平均分子量が１,０００～６,０００の（メタ）アクリル系重合体であることを特徴とする前記〔７〕記載の硬化性組成物。
〔９〕前記〔１〕～〔８〕のいずれかに記載の硬化性組成物を含有することを特徴とするシーリング材組成物。

(R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 2 to 4 carbon atoms, R ³ is a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, n is 2 to 25 represents an integer of
(B) 2 to 60% by mass of a (meth)acrylic acid alkyl ester monomer having an alkyl group having 10 or more carbon atoms as constituent monomer units, and a monomer represented by the general formula (1) A (meth) acrylic polymer containing 40 to 98% by mass.
[2] The curable composition according to [1], wherein the polymer (A) contains a polyoxyalkylene polymer having a reactive silyl group.
[3] The curable composition according to any one of [1] or [2] above, wherein the polymer (A) comprises a (meth)acrylic polymer having a reactive silyl group.
[4] Any one of the above [1] to [3], wherein the (B) (meth)acrylic polymer contains a (meth)acrylic acid ester monomer having a reactive silyl group as a constituent monomer unit The curable composition according to .
[5] The (B) (meth)acrylic polymer contains, as a constituent monomer unit, a monomer in which n in the general formula (1) is an integer of 9 to 12 [1] to [4 ] The curable composition according to any one of the above.
[6] Any of the above [1] to [5], wherein the (B) (meth) acrylic polymer is contained in an amount of 1 to 30 parts by mass with respect to 100 parts by mass of the polymer (A). The curable composition according to 1.
[7] The curable composition as described in any one of [1] to [6], further comprising a plasticizer.
[8] The plasticizer does not contain a monomer represented by the general formula (1) as a constituent monomer unit and does not contain a reactive silyl group, and has a weight average molecular weight of 1,000 to 6,000. The curable composition according to [7] above, which is a (meth)acrylic polymer of
[9] A sealant composition comprising the curable composition according to any one of [1] to [8].

According to the curable composition of the present invention, it cures at room temperature with moisture in the atmosphere and the like, and a cured product having stain resistance superior to that of conventional compositions can be obtained, and the effect is maintained. In addition, the obtained cured product is excellent in weather resistance and water resistance, and it becomes possible to maintain the aesthetic appearance of the outer wall of a building for a long period of time. Moreover, since the curable composition of the present invention has an appropriate viscosity, it is excellent in workability.

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

The curable composition of the present invention (excluding the aqueous emulsion) comprises a polymer as component (A) and a (meth)acrylic polymer as component (B) as essential components. The (meth)acrylic polymer that is the component (B) is a (meth)acrylic acid alkyl ester monomer (b-1) having an alkyl group having 10 or more carbon atoms, a monomer represented by the general formula (1) A polymer obtained by copolymerizing the monomer (b-2), and when the total amount of constituent monomers of the (meth)acrylic polymer as the component (B) is 100 parts by mass, (b -1) 2 to 60 parts by mass and (b-2) 40 to 98 parts by mass as constituent monomer units. The curable composition of the present invention is described below, including details of each component.

<(A) Component: Polymer>
The polymer as component (A) is a polymer having a reactive silyl group (excluding polymers containing 40 to 98% by mass of a monomer represented by the following general formula (1) as a constituent monomer unit. ), and various polymers such as silicone-based, modified silicone-based, polysulfide-based, (meth)acrylic-based and polyurethane-based polymers can be used. Among these, a (meth)acrylic polymer containing a reactive silyl group or an oxyalkylene polymer containing a reactive silyl group can be used as a one-liquid type, and the mechanical properties of the cured product are also excellent. , or mixtures thereof are preferred.

Among the polymers as the component (A), the (meth)acrylic polymer containing the reactive silyl group is a polymer having a structural unit derived from a (meth)acrylic monomer and a reactive silyl group. It is a coalescence, and can be obtained, for example, by polymerizing a monomer mixture containing a (meth)acrylic monomer and a vinyl monomer having a reactive silyl group. The (meth)acrylic monomer is a monomer having a (meth)acryloyl group in the molecule, and examples thereof include (meth)acrylic acid and (meth)acrylic acid alkyl esters. The amount of the (meth)acrylic monomer used is preferably in the range of 10 to 100% by mass, more preferably in the range of all constituent monomers of the (meth)acrylic polymer containing a reactive silyl group. is in the range of 30 to 100% by mass, more preferably in the range of 50 to 100% by mass.

(Meth)acrylic acid alkyl esters specifically include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and 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 Linear or (Meth)acrylic acid alkyl esters having a branched aliphatic alkyl group or an alicyclic alkyl group are exemplified, and one or more of these may be used. Among these, (meth)acrylic acid alkyl esters having a linear or branched aliphatic alkyl group having 1 to 8 carbon atoms are preferred from the viewpoint of mechanical properties of the cured product.

A compound having a reactive silyl group and a polymerizable vinyl group in the molecule can be used as the vinyl-based monomer having a reactive silyl group. The reactive silyl group is not particularly limited, and includes an alkoxysilyl group, a halogenosilyl group, a silanol group and the like, but an alkoxysilyl group is preferable from the viewpoint of easy control of reactivity. Specific examples of the alkoxysilyl group include trimethoxysilyl group, methyldimethoxysilyl group, dimethylmethoxysilyl group, triethoxysilyl group, methyldiethoxysilyl group, dimethylethoxysilyl group and the like.
Vinyl monomers having a reactive silyl group include vinylsilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, and vinyldimethylmethoxysilane; trimethoxysilylpropyl (meth)acrylate; Silyl group-containing (meth)acrylates such as triethoxysilylpropyl methacrylate, dimethylmethoxysilylpropyl (meth)acrylate and methyldimethoxysilylpropyl (meth)acrylate; silyl groups such as trimethoxysilylpropyl vinyl ether vinyl ethers; silyl group-containing vinyl esters such as vinyl trimethoxysilylundecanoate; and the like, and one or more of these can be used.

The (meth)acrylic polymer containing a reactive silyl group may be copolymerized with other monomers copolymerizable therewith in addition to the above monomers.
Other copolymerizable monomers mentioned above include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glycidyl (meth)acrylate. , functional group-containing monomers such as 2-aminoethyl (meth)acrylate;
(meth)acrylic acid aromatic esters such as phenyl (meth)acrylate, toluyl (meth)acrylate, and benzyl (meth)acrylate;
Alkoxyalkyl (meth)acrylates such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and 3-methoxypropyl (meth)acrylate;
(Meth)trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutyl (meth)acrylate Ethyl, 2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl (meth)acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate , Fluorine-containing (meth)acrylic acid 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, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof;
maleic anhydride; unsaturated dicarboxylic acids such as maleic acid and fumaric acid, and their mono- 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 and vinyl cinnamate;
alkenes such as ethylene, propylene, vinyl chloride, vinylidene chloride, allyl chloride and allyl alcohol; conjugated dienes such as butadiene and isoprene;
etc., but not limited to these. Also, one or more of these can be used.

The average number of reactive silyl groups contained in one molecule of the (meth)acrylic polymer containing reactive silyl groups is preferably 0.05 from the viewpoint of performance such as adhesiveness and tensile properties of the cured product. 0.9, more preferably 0.3 to 0.8.
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 terminal of the polymer.

The weight average molecular weight (Mw) of the (meth)acrylic polymer containing a reactive silyl group is preferably 2,000 in polystyrene equivalent molecular weight by gel permeation chromatography (hereinafter also referred to as "GPC"). ∼50,000, more preferably 8,000 to 25,000. When the Mw is 2,000 or more, the resulting cured product has good weather resistance, and when it is 50,000 or less, the workability of the curable composition is good.

The viscosity of the (meth)acrylic polymer containing a reactive silyl group is preferably in the range of 500 to 100,000 mPa s at 25° C., more preferably in the range of 5,000 to 80,000 mPa s. more preferably in the range of 20,000 to 70,000 mPa·s. A viscosity of 500 mPa·s or more is preferable because dripping when applied to a vertical surface is suppressed, and a viscosity of 100,000 mPa·s or less improves the workability of the curable composition.

A (meth)acrylic polymer containing a reactive silyl group can be produced by ordinary radical polymerization. Any of solution polymerization, bulk polymerization, and dispersion polymerization may be employed, and living radical polymerization may also be used. The reaction process may be batch, semi-batch or continuous polymerization. Among these, a high-temperature continuous polymerization method at 150 to 350° C. is preferred.
If the polymerization temperature is 150°C or higher, a scission reaction that starts with a hydrogen abstraction reaction from the polymer chain occurs due to high temperature polymerization, so it is easy to control the molecular weight without containing a large amount of impurities such as initiators and chain transfer agents. can be manufactured to It is preferable not to use chain transfer agents such as mercaptans, since they lead to deterioration in weather resistance. On the other hand, if the temperature is 350° C. or lower, it is preferable because there is no risk of coloration of the polymerization solution or reduction in molecular weight due to a decomposition reaction. By polymerizing in the above temperature range, it is possible to efficiently produce a copolymer having an appropriate molecular weight, a low viscosity, no coloring, and few contaminants. That is, according to the polymerization method, a very small amount of a polymerization initiator may be used, and a high-purity copolymer can be obtained without the need to use a chain transfer agent such as mercaptan or a polymerization solvent. .

In general, when the crosslinkable functional groups are uniformly introduced into the polymer, the curability of the curable composition containing the polymer and physical properties such as weather resistance of the resulting cured product are improved. In this regard, it is preferable to use a stirred tank type reactor because a (meth)acrylic polymer having a relatively narrow composition distribution (distribution of crosslinkable functional groups) and a relatively narrow molecular weight distribution can be obtained. Further, 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, etc. may be followed. For example, after filling a pressurizable reactor with a solvent and setting it to a predetermined temperature under pressure, a monomer mixture consisting of each monomer and, if necessary, a polymerization solvent is fed into the reactor at a constant rate. and withdrawing an amount of the polymerization liquid corresponding to the amount of the monomer mixture supplied. Moreover, a polymerization initiator can be added to the monomer mixture, if necessary. When blended, 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 and the boiling points of the monomer mixture and solvent used, 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. A preferred residence time is 2 to 40 minutes.

Among the polymers that are the component (A) above, the polyoxyalkylene polymer containing a reactive silyl group contains a repeating unit represented by the following general formula (2), and the constituent monomer unit is the above It is not particularly limited as long as it does not contain the monomer represented by general formula (1).
- OR ¹ - (2)
(In the formula, R ¹ is a divalent hydrocarbon group.)
Examples of R ¹ in the general formula (2) are as follows.
(CH ₂ ) _n (n is an integer of 1 to 10)
CH( _CH3 ) _CH2
CH _{( C2H5} ) _CH2
C ( _CH3 ) _2CH2
The above polyoxyalkylene polymer may contain one or a combination of two or more of the above repeating units. Among these, CH(CH ₃ )CH ₂ is preferred from the viewpoint of excellent workability.

As the reactive silyl group contained in the polyoxyalkylene polymer containing a reactive silyl group, the reactive silyl group possessed by the acrylic polymer containing the reactive silyl group can be applied as it is.

The method for producing the polyoxyalkylene polymer is not particularly limited, but for example, a polymerization method using a corresponding epoxy compound or diol as a raw material using an alkali catalyst such as KOH, or a polymerization method using a transition metal compound-porphyrin complex catalyst. method, a polymerization method using a double metal cyanide complex catalyst, a polymerization method using phosphazene, and the like.
Moreover, the polyoxyalkylene polymer may be either a linear polymer or a branched polymer. Moreover, you may use these in combination.

The average number of reactive silyl groups contained in one molecule of the polyoxyalkylene polymer having a reactive silyl group 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 in the range of 1.5 to 3.
The position of the reactive silyl group contained in the polyoxyalkylene polymer is not particularly limited, and can be the side chain and/or terminal of the polymer.
Moreover, the polyoxyalkylene polymer may be either a linear polymer or a branched polymer. Moreover, you may use these in combination.

The number average molecular weight (Mn) of the polyoxyalkylene polymer containing reactive silyl groups is preferably in the range of 3,000 to 60,000, more preferably in the range of 4,000 to 50,000, More preferably, it is in the range of 5,000 to 40,000. When the Mn is within the above range, a cured product having excellent tensile properties can be obtained.

Specific examples of polyoxyalkylene polymers having reactive silyl groups include "MS Polymer S203", "MS Polymer S303", "Silyl SAT200" and "Silyl SAT30" manufactured by Kaneka Corporation, and "Exe" manufactured by Asahi Glass Co., Ltd. Star ES-S2410", "Exester ES-S2420" and "Exester ES-S3430" (all trade names) are exemplified, and these can be used in the present invention.

<(B) component: (meth)acrylic polymer>
Component (B) is a (meth)acrylic acid alkyl ester monomer (b-1) having an alkyl group having 10 or more carbon atoms, and a monomer (b-2) represented by the general formula (1). A polymer obtained by polymerization, when the total amount of constituent monomers of the (meth)acrylic polymer as component (B) is 100 parts by mass, (b-1) 2 to 60 parts by mass, and (b-2) a polymer containing 40 to 98 parts by mass as constituent monomer units. The (meth)acrylic polymer that is the component (B) may be a random polymer or a structurally controlled polymer such as a block polymer or a graft polymer.

In the present invention, the (A) component polymer is combined with the (B) component (meth)acrylic polymer having both hydrophilic groups and hydrophobic groups in a specific ratio to improve the durability of the cured product. Stainability is improved. That is, it is believed that the presence of the hydrophilic group improves the wettability of the cured product with water, and improves the washability with rainwater or the like. On the other hand, due to the presence of hydrophobic groups, the (meth)acrylic polymer having both a hydrophilic group and a hydrophobic group, which is the component (B), is concentrated in the vicinity of the surface of the cured product, thereby improving wettability. be conspicuous.
In addition, since the (meth)acrylic polymer, which is the component (B), has a certain molecular weight or more compared to surfactants and the like, bleeding from the cured product over time is slowed down, so For a period of time, the effect of stain resistance is retained.
It should be noted that these action mechanisms are presumed and do not limit the present invention.

The (meth)acrylic acid alkyl ester monomer (b-1) having an alkyl group having 10 or more carbon atoms, which is a constituent monomer of the (meth)acrylic polymer as the component (B), is specifically is decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, (meth) heptadecyl acrylate, stearyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, heneicosyl (meth) acrylate, behenyl (meth) acrylate, tetracosyl (meth) acrylate, ( meth)hexacosyl acrylate, octacosyl (meth)acrylate, triacontyl (meth)acrylate, dotriacontyl (meth)acrylate, tetratriacontyl (meth)acrylate, hexatriacontyl (meth)acrylate, (meth)acrylate octatriacontyl acrylate, tetracontyl (meth)acrylate, isodecyl (meth)acrylate, isoundecyl (meth)acrylate, isolauryl (meth)acrylate, isotridecyl (meth)acrylate, isotetradecyl (meth)acrylate , isopentadecyl (meth) acrylate, isohexadecyl (meth) acrylate, isoheptadecyl (meth) acrylate, isostearyl (meth) acrylate, isononadecyl (meth) acrylate, isoeicosyl (meth) acrylate, (meth) ) isoheneicosyl acrylate, isobehenyl (meth)acrylate, isotetracosyl (meth)acrylate, isohexacosyl (meth)acrylate, isooctacosyl (meth)acrylate, isotriacontyl (meth)acrylate, isodotria (meth)acrylate Examples include contyl, isotetratriacontyl (meth)acrylate, isohexatriacontyl (meth)acrylate, isooctatriacontyl (meth)acrylate, and isotetracontyl (meth)acrylate. One or more of these can be used.

Among the (meth)acrylic acid alkyl esters having an alkyl group having 10 or more carbon atoms, the alkyl group preferably has 10 to 20 carbon atoms, more preferably 12 to 18 carbon atoms. When the number of carbon atoms in the alkyl group is 10 or more, the component (B) tends to be concentrated on the surface of the cured product, and the free energy of the surface is lowered, thereby improving stain resistance, which is preferable. If the number of carbon atoms in the alkyl group is 20 or less, the (meth)acrylic polymer, which is the component (B), is less likely to crystallize and more likely to migrate within the coating film, thus facilitating concentration on the surface.

The amount of (b-1) used as a constituent monomer of component (B) is 2, when the total constituent monomers of the (meth)acrylic polymer that is component (B) is 100 parts by mass. to 60 parts by mass, preferably 2 to 45 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 3 to 25 parts by mass. When the mass ratio of (b-1) is 2 parts by mass or more, surface concentration proceeds, and when the mass ratio is 60 parts by mass or less, the hydrophilicity of the surface is maintained.

As the monomer (b-2) represented by the general formula (1), which is a constituent monomer of the (meth)acrylic polymer that is the component (B), polyoxyalkylene glycol mono(meth)acrylate and / Or polyoxyalkylene glycol monoalkyl ether mono (meth) acrylate, and one or more of these are used. Polyoxyalkylene glycol mono(meth)acrylates include polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polybutylene glycol mono(meth)acrylate, poly(ethylene glycol-propylene glycol) mono(meth)acrylate. , polyethylene glycol-polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, polyethylene glycol-polytetramethylene glycol mono (meth) acrylate, etc. Specific trade names include Examples include BLEMMA AP series, AEP series, PEP series and PET series manufactured by NOF Corporation. Polyoxyalkylene glycol monoalkyl ether mono(meth)acrylates include polyethylene glycol monoalkyl ether mono(meth)acrylate, polypropylene glycol monoalkyl ether mono(meth)acrylate, and polybutylene glycol monoalkyl ether mono(meth)acrylate. etc. are exemplified.
The alkyl group (R ³ ) of the alkyl ether is methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-pentyl, n-hexyl, n- Examples include butyl group, n-octyl group, 2-ethylhexyl group and the like. Specific product names include Blemmer PME series, AME series, and AEE series manufactured by NOF Corporation. (Poly)oxyethylene glycol monomethyl ether mono(meth)acrylate is preferred from the viewpoint of weather resistance, workability and discoloration resistance.

n representing the average number of repeating oxyalkylene groups in the general formula (1) is 2 to 25, preferably 3 to 20, more preferably 6 to 15, and still more preferably 9 to 12. is. When n is 2 or more, a cleaning effect can be obtained, and when n is 25 or less, durability such as water resistance and weather resistance of the cured product is high.
In addition, it is preferable that R ² representing an oxyalkylene group in the general formula (1) contains ethylene having 2 carbon atoms in order to exhibit good hydrophilicity.

The amount of (b-2) used as a constituent monomer of component (B) is 40 when the total constituent monomers of the (meth)acrylic polymer that is component (B) is 100 parts by mass. to 98 parts by mass, preferably 50 to 95 parts by mass, more preferably 60 to 90 parts by mass. When the mass ratio of (b-2) is 40 parts by mass or more, the wettability of water is high and stain resistance is exhibited. high.

The (meth)acrylic polymer as component (B) may contain other copolymerizable monomers as constituent monomers. Such monomers are not particularly limited as long as they are copolymerizable with (b-1) and (b-2). A monomer etc. can be mentioned.

(Meth)acrylic acid alkyl esters specifically include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and 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 Linear or (Meth)acrylic acid alkyl esters having a branched aliphatic alkyl group or an alicyclic alkyl group are exemplified, and one or more of these may be used. Among these, (meth)acrylic acid alkyl esters having a linear or branched aliphatic alkyl group having 1 to 8 carbon atoms are preferred from the viewpoint of mechanical properties of the cured product.

A compound having a reactive silyl group and a polymerizable vinyl group in the molecule can be used as the vinyl-based monomer having a reactive silyl group. The reactive silyl group is not particularly limited, and includes an alkoxysilyl group, a halogenosilyl group, a silanol group and the like, but an alkoxysilyl group is preferable from the viewpoint of easy control of reactivity. Specific examples of the alkoxysilyl group include trimethoxysilyl group, methyldimethoxysilyl group, dimethylmethoxysilyl group, triethoxysilyl group, methyldiethoxysilyl group, dimethylethoxysilyl group and the like.
Specific examples of vinyl-based monomers having a reactive silyl group include vinylsilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, and vinyldimethylmethoxysilane; trimethoxysilyl (meth)acrylate; Silyl group-containing (meth)acrylic acid esters such as propyl, triethoxysilylpropyl (meth)acrylate, dimethylmethoxysilylpropyl (meth)acrylate and methyldimethoxysilylpropyl (meth)acrylate; trimethoxysilylpropyl vinyl ether, etc. silyl group-containing vinyl ethers; silyl group-containing vinyl esters such as vinyl trimethoxysilylundecanoate; one or more of these can be used.

In addition to (meth)acrylic acid alkyl esters and/or vinyl monomers having a reactive silyl group, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acrylic acid functional group-containing monomers such as 4-hydroxybutyl, glycidyl (meth)acrylate, and 2-aminoethyl (meth)acrylate;
(meth)acrylic acid aromatic esters such as phenyl (meth)acrylate, toluyl (meth)acrylate, and benzyl (meth)acrylate;
Alkoxyalkyl (meth)acrylates such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and 3-methoxypropyl (meth)acrylate;
(Meth)trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutyl (meth)acrylate Ethyl, 2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl (meth)acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate , Fluorine-containing (meth)acrylic acid 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, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof;
maleic anhydride; unsaturated dicarboxylic acids such as maleic acid and fumaric acid, and their mono- 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 and vinyl cinnamate;
alkenes such as ethylene, propylene, vinyl chloride, vinylidene chloride, allyl chloride and allyl alcohol; conjugated dienes such as butadiene and isoprene;
etc., but not limited to these. Also, one or more of these can be used.

Further, when a (meth)acrylic ester monomer having a reactive silyl group is used as a copolymerizable monomer, the entire constituent monomers of the (meth)acrylic polymer, which is the component (B), Based on 100 parts by mass, it is preferably 0.1 to 14 parts by mass, more preferably 0.5 to 7 parts by mass, and still more preferably 1.0 to 3.5 parts by mass. When the amount of the monomer having a silyl group is 0.1 parts by mass or more, the (meth)acrylic polymer, which is the component (B), is difficult to escape from the cured product during exposure, and the stain resistance is maintained for a long period of time. It is advantageous from the viewpoint of On the other hand, if the amount of the monomer having a silyl group is 14 parts by mass or less, the (meth)acrylic polymer, which is the component (B), reacts and is fixed in the cured product during the curing process before the surface concentrates. It is less likely to be turned into a tarnish, and the surface concentration proceeds, and the stain resistance is exhibited.

The weight average molecular weight of the (meth)acrylic polymer as component (B) is preferably in the range of 2,000 to 25,000. By setting it to 2,000 or more, good weather resistance is exhibited, and since it is retained in the cured product for a long period of time, the effect of stain resistance is maintained. On the other hand, by setting the molecular weight to 25,000 or less, the component (B) moves easily in the cured product and tends to concentrate on the surface. It is more preferably in the range of 2,500 to 10,000, still more preferably in the range of 3,000 to 7,000.

The viscosity of the (meth)acrylic polymer as component (B) at 25° C. is preferably in the range of 100 to 25,000 mPa s, more preferably in the range of 100 to 10,000 mPa s, and further It is preferably in the range of 200 to 5,000 mPa·s. A viscosity of 100 mPa·s or more is preferable because dripping when applied to a vertical surface is suppressed, and a viscosity of 25,000 mPa·s or less improves the workability of the curable composition.

The method for producing the (meth)acrylic polymer as component (B) is the production method described for the case where the polymer as component (A) is a (meth)acrylic polymer containing a reactive silyl group. can be applied.

<Curable composition>
As described above, the curable composition of the present invention comprises the polymer as component (A) and the (meth)acrylic polymer as component (B) as essential components.

The amount of component (B) used is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, still more preferably 2 to 10 parts by weight, when the amount of component (A) used is 100 parts by mass. weight part. When the amount of component (B) used is 1 part by mass or more, the stain resistance is high, and when it is 30 parts by mass or less, the weather resistance is high.

In the curable composition of the present invention, the (meth)acrylic polymer as component (B) mainly functions as a plasticizer, but it is preferable to use a plasticizer other than component (B) in combination. By using a plasticizer other than the component (B) together, weather resistance, water resistance, etc. may be improved.

Plasticizers other than the component (B) that can be blended in the curable composition of the present invention include phthalates having a molecular weight of 100 to 600, epoxy group-containing compounds having a molecular weight of 100 to 600, and weight average molecular weights of 1. 000 to 15,000 and does not contain a reactive silyl group, and does not contain a monomer represented by the general formula (1) as a constituent monomer unit and is a reactive silyl (Meth)acrylic polymers containing no group and having a weight average molecular weight of 1,000 to 6,000. Two or more of these may be used in combination.

Specific examples of phthalates having a molecular weight of 100 to 600 include di-octyl phthalate, di-2-ethylhexyl phthalate, isopropyl phthalate and di-dodecyl phthalate. Examples of epoxy group-containing compounds having a molecular weight of 100 to 600 include epoxy group-containing compounds such as epoxidized di-2-ethylhexyl hexahydrophthalate.
Specific examples of polyalkylene glycols having a weight average molecular weight of 1,000 to 15,000 and containing no reactive silyl group include "Preminol 4010", "Preminol 5005" and "Preminol 3010" manufactured by Asahi Glass Co., Ltd. ”, “Unior D4000” and “Unior TG4000” manufactured by NOF Corporation.
A (meth)acrylic polymer having a weight average molecular weight of 1,000 to 6,000, which does not contain a monomer represented by the general formula (1) as a constituent monomer unit and does not contain a reactive silyl group The coalescence may be obtained by continuous radical polymerization of monomers containing acrylic acid ester as a main component at a polymerization temperature of 150 to 350°C. Specific examples of such compounds include "ARUFON UP1000", "ARUFON UP1010", "ARUFON UP1020", "ARUFON UP1080", "ARUFON UP1110", "ARUFON UP1120", "ARUFON UH2032" and "ARUFON" manufactured by Toagosei Co., Ltd. UH2041", "ARUFON UH2130" (the above are trade names. "ARUFON" is a registered trademark of Toagosei Co., Ltd.), and the like.

The amount of plasticizer used is preferably in the range of 0 to 100 parts by mass, and may be in the range of 0 to 80 parts by mass, when the total amount of components (A) and (B) is 100 parts by mass. , may be in the range of 0 to 50 parts by mass.

The curable composition of the present invention can contain components other than components (A) and (B) as long as the effects achieved by the present invention are not impaired. Such components include, in addition to the plasticizer, fillers, anti-aging agents, curing accelerators, anti-tack agents, adhesion-imparting agents, and the like.

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

Antiaging agents include UV absorbers such as benzophenone compounds, benzotriazole compounds and anilide oxalate compounds, light stabilizers such as hindered amine compounds, antioxidants such as hindered phenols, heat stabilizers, or An anti-aging agent which is a mixture of these can be used.
Examples of the ultraviolet absorber include BASF's trade names "TINUVIN 571", "TINUVIN 1130" and "TINUVIN 327". Examples of the light stabilizer include "TINUVIN 292", "TINUVIN 144" and "TINUVIN 123" manufactured by the same company, and "SANOL 770" manufactured by Sankyo. Examples of heat stabilizers include trade names "Irganox 1135", "Irganox 1520" and "Irganox 1330" manufactured by BASF. A mixture of UV absorbers/light stabilizers/heat stabilizers under the trade name "TINUVIN B75" manufactured by BASF may also 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, and dioctyltin dilaurate. Specifically, the product names manufactured by Nitto Kasei Co., Ltd. “Neostan U-28”, “Neostan U-100”, “Neostan U-200”, “Neostan U-220H”, “Neostan U-303”, “SCAT- 24” and the like are exemplified.
Examples of titanium-based catalysts include tetraisopropyl titanate, tetra-n-butyl titanate, titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethyl acetylacetonate, dibutoxytitanium diacetylacetonate, diisopropoxytitanium diacetylacetonate, titanium octylene glycolate, titanium lactate and the like.
Examples of tertiary amines include triethylamine, tributylamine, triethylenediamine, hexamethylenetetramine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), diazabicyclononene (DBN), N- Examples include methylmorpholine, N-ethylmorpholine and the like.

The amount of curing accelerator to be used is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 2 parts by mass, per 100 parts by mass of components (A) and (B).

Examples of anti-tack agents include acrylic oligomers manufactured by Toagosei under the trade names of "Aronix M8030", "M8100" and "M309", or mixtures with photopolymerization initiators, saturated fatty acid oils such as tung oil and linseed oil, 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 Chemistry Co., Ltd. are exemplified.

Examples of adhesion-imparting agents 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 added.

The curable composition of the present invention can be prepared as a one-component type in which all of the ingredients are premixed, stored in a sealed container, and cured by absorbing moisture in the air after application. In addition, it is also possible to prepare a two-component type in which components such as a curing catalyst, a filler, a plasticizer, and water are separately blended as a curing agent, and the blending materials and the polymerization composition are mixed before use. A one-component type is more preferable because it is easy to handle and there are few mixing errors during application.

EXAMPLES The present invention will be specifically described below based on examples. It should be noted that the present invention is not limited by these examples. In the following, "parts" and "%" mean parts by weight and % by weight unless otherwise specified.
Methods for analyzing the polymers obtained in Synthesis Examples and methods for evaluating cured products obtained from the curable compositions of Examples and Comparative Examples are described below.

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

<Viscosity of (meth)acrylic polymer>
Using an E-type viscometer (TVE-20H type viscometer manufactured by Toki Sangyo Co., Ltd.), the measurement was performed at a temperature of 25°C ± 0.5°C. When the viscosity of the (meth)acrylic polymer is less than 10,000 mPas, the rotor is No. No. 1 is used and No. 1 is used when it is 10,000 mPas or more. 7 was used.

<Average number of reactive silyl groups contained in (meth)acrylic polymer>
The number (average number) f (Si) of alkoxysilyl groups that are reactive silyl groups is calculated by the following formula from the mass parts of the monomer having a reactive silyl group when the total number of constituent monomers is 100 parts by mass. calculated using
f(Si) = {mass parts of silyl group monomer/(molecular weight of silyl group monomer x 100/Mn)}

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

<Water resistance test>
Each curable composition was applied to a Teflon (registered trademark) sheet to a thickness of 2 mm and cured for 1 week at 23° C. and 50% RH to prepare a cured sheet. The obtained cured product was immersed in water at 23° C. for one week. The cured product was taken out and left at rest for 1 day under conditions of 23° C. and 50% RH, and then subjected to the tensile test described above, and the retention rate of breaking strength and breaking elongation was obtained from the following equations.
Breaking strength retention (%) = (breaking strength after immersion) / (breaking strength after standard curing) x 100
Breaking strength after standard curing = Breaking strength in the tensile test shown in Table 2 Retention rate of breaking elongation (%) = (breaking elongation after immersion) / (breaking elongation after standard curing) x 100
Elongation at break after standard curing = Elongation at break in the tensile test shown in Table 2

<Stain resistance test>
Each curable composition was applied to a slate plate to a thickness of 3 mm and cured for 1 week under conditions of 23° C. and 50% RH to prepare a cured sheet. The resulting cured product was passed through a 200-mesh wire mesh and contaminated powder (8 types of test dust (manufactured by Japan Powder Technology Association) 9 g, Shinoka (manufactured by Holbein Kogyo Co., Ltd.) 27 g, 3 types of test dust (Japan Powder Industry Technology A mixture of 2 g (manufactured by Japan Association) was sprinkled on the surface, left to stand for 5 minutes, and the powder was removed (air blow, water washing). After that, the yellowness index (YI) was determined by the following formula from the values measured using a spectrocolorimeter SE-2000 manufactured by Nippon Denshoku Co., Ltd. Stain resistance was evaluated based on the degree of yellowing (ΔYI), which is the difference from the YI (=YI0) immediately after curing. This is shown in Tables 3 and 4 as ΔYI of the first contamination test.
YI=100(1.28X−1.06Z)/Y
In the formula, Y represents the reflectance measured with a spectral colorimeter. X and Z represent values obtained by substituting reflectance Y and coordinate values x and y measured with a spectral colorimeter into the following equations.
X = (Y/y) x x
Z = (Y/y) x (1-xy)
After measuring the YI of the contamination test, leave the cured product at 70 ° C. for 3 hours, then at 23 ° C. for 1 hour, sprinkle the staining powder in the same manner as above, and measure the next YI as one cycle. , repeated for a total of 4 cycles. Tables 3 and 4 show the difference between the YI obtained after the 5th cycle test including the 1st staining test and the YI immediately after curing (=YI0) as ΔYI for the 5th staining test.

<Weather resistance test>
Each curable composition was applied to a Teflon (registered trademark) sheet to a thickness of 2 mm, and cured for 1 week at 23° C. and 50% RH to prepare a cured sheet. The obtained cured product was placed in a metering weather meter ("DAIPLA METAL WEATHER KU-R5NCI-A" manufactured by Daipla Wintes Co.) to conduct an accelerated weather resistance test. The test was carried out under the conditions of irradiation at 63° C., 70% RH, and illuminance of 80 mW/cm ² and showering for 2 minutes once every 2 hours. The time at which cracks began to appear in the appearance was recorded.

<<(A) component: production of polymer>>
Synthesis Example 1 (production of polymer A-2)
The temperature of a 1000 mL pressurized stirred tank reactor equipped with an oil jacket was maintained at 180°C. Next, while keeping the pressure of the reactor constant, 3-methacryloxypropylmethyldimethoxysilane (manufactured by Dow Corning Toray Co., Ltd., trade name "Z6033", hereinafter referred to as "DMS") was added as a monomer at 2.8. part, n-butyl acrylate (hereinafter referred to as "BA") 60.2 parts, 2-ethylhexyl acrylate (hereinafter referred to as "HA") 20 parts, n-tetradodecyl acrylate (hereinafter referred to as "TDA ”), 10 parts of methyl methacrylate (hereinafter referred to as “MMA”), 10 parts of isopropyl alcohol (hereinafter referred to as “IPA”) as a solvent, methyl ethyl ketone (hereinafter referred to as “MEK”) 5 parts of methyl orthoacetate (hereinafter referred to as "MOA"), 5 parts of di-t-hexyl peroxide (manufactured by NOF, trade name "Perhexyl D", hereinafter referred to as "DTHP") as a polymerization initiator A monomer mixture consisting of 0.1 part of is continuously supplied from the raw material tank to the reactor at a constant supply rate (48 g / min, residence time: 12 minutes), equivalent to the supply amount of the monomer mixture The reaction solution was continuously withdrawn from the outlet. Immediately after the start of the reaction, the reaction temperature was once lowered and then increased due to the heat of polymerization.
The point at which the temperature stabilized from the start of the supply of the monomer mixture was the starting point for collecting the reaction solution, and the reaction was continued for 25 minutes. 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 polymer A-2. A-2 had a weight average molecular weight of 18,900, a number average molecular weight of 4,900, a viscosity of 39,000 mPas, and a silyl group number of 0.59 per molecule.

<<Component (B): Production of (meth)acrylic polymer>>
Synthesis Examples 2-20, Comparative Synthesis Examples 1-2
As shown in Tables 1 and 2, polymerization was carried out in the same manner as in Synthesis Example 1, except that the type and amount of the monomer, solvent, polymerization initiator, and the temperature in the reactor were changed. (Meth)acrylic polymers B-1 to B-19, and polymers B-20 and B-21 as comparative synthesis examples. Tables 1 and 2 show the properties of each polymer.

The details of the compounds shown in Tables 1 and 2 are as follows.
PME-200: Blemmer PME-200 (manufactured by NOF Corporation, methoxy polyethylene glycol methacrylate, polyethylene glycol chain repetition number n = about 4)
PME-400: Blemmer PME-400 (manufactured by NOF Corporation, methoxy polyethylene glycol methacrylate, polyethylene glycol chain repetition number n = about 9)
PME-1000: Blemmer PME-1000 (manufactured by NOF Corporation, methoxy polyethylene glycol methacrylate, polyethylene glycol chain repetition number n = about 23)
DTBP: Perbutyl D (manufactured by NOF Corporation, di-t-butyl peroxide)
TDA: tetradecyl acrylate SA: stearyl acrylate LA: lauryl acrylate DMS: 3-methacryloxypropylmethyldimethoxysilane TMS: 3-methacryloxypropyltrimethoxysilane

<<Preparation and evaluation of curable composition>>
Examples 1-27, Comparative Examples 1-6
The polymer (A-2) obtained in Synthesis Example 1, the (meth)acrylic polymer (B component), and commercially available raw materials were blended in the proportions shown in Tables 3 and 4, and the mixture was blended using a planetary mixer. , a temperature of 60° C. and 10 Torr for 1 hour to obtain a curable composition. A tensile test, a water resistance test, a stain resistance test, and a weather resistance test were performed on the cured product obtained from each composition, and the results are shown in Tables 3 and 4.

Details of the compounds shown in Tables 3 and 4 are as follows.
A-1: Exester ES-S2420 (manufactured by Asahi Glass Co., Ltd., modified silicone)
UP-1110: ARUFON UP-1110 (manufactured by Toagosei Co., Ltd., (meth) acrylic polymer)
CCR: Light calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name “Shiraenka CCR”)
Super SS: Heavy calcium carbonate (manufactured by 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 (manufactured by Nitto Kasei Co., Ltd.)
SH6020: 3-(2-aminoethyl)aminopropyltrimethoxysilane (manufactured by Dow Corning Toray)
SZ6030: Vinyltrimethoxysilane (manufactured by Dow Corning Toray)

Examples 1-27 are evaluations of the curable compositions of the present invention. The yellowing index (ΔYI) in the first stain resistance test shown in Tables 3 and 4 indicates the degree of initial stain resistance. All the examples showed that the cured products obtained from the curable compositions of the present invention had high initial stain resistance. In addition, the yellowing index (ΔYI) in the fifth stain resistance test shown in Tables 3 and 4 indicates that the stain resistance is maintained at a high level over a long period of time by repeating a total of five cycles of the stain resistance test. , and the effect was satisfactory in any of the examples.
On the other hand, Comparative Examples 1 and 2 are the results of using a composition that does not contain the component (B) ((meth)acrylic polymer), which is an essential component of the curable composition of the present invention. Both had insufficient stain resistance.
Comparative Examples 3 and 5 were obtained from compositions blended with (meth)acrylic polymers containing only 36% by mass of monomer units (b-2) having a polyoxyalkylene group. These are the evaluation results for the cured products obtained by the above tests, and although the initial stain resistance was high, the long-term stain resistance was inadequate. On the other hand, according to the results of Example 6, the curable composition of the present invention using a (meth)acrylic polymer containing 43% by mass of the monomer (b-2) having a polyoxyalkylene group as a monomer unit It was shown that the cured product obtained from the product has high initial and long-term stain resistance.
In Comparative Examples 4 and 6, a (meth)acrylic polymer containing no (meth)acrylic acid alkyl ester monomer (b-1) having an alkyl group having 10 or more carbon atoms as a monomer unit. These are the evaluation results of the cured products obtained from the blended compositions. Although the initial stain resistance was high, the long-term stain resistance was insufficient.

In the tensile test, water resistance test, and weather resistance test, the workability (ease of application) when each curable composition was applied to a Teflon (registered trademark) sheet with a thickness of 2 mm was as shown in Examples 1 to 27. All were good. Further, in the stain resistance test, the workability (ease of application) when each curable composition was applied to a slate plate with a thickness of 3 mm was good in all of Examples 1 to 27. In addition, the results obtained in the tensile test, water resistance test, and weather resistance test show that the curable composition of the present invention can be suitably used as a curable composition for sealing materials and the like in all of Examples 1 to 27. It showed what we could do. Although the cured product obtained from the curable composition of the present invention contained a methacrylic polymer having a high concentration of polyoxyethylene chains, it had high water resistance and weather resistance. The curable composition of Example 3 used a (meth)acrylic polymer containing only 5% by mass of structural units derived from a (meth)acrylic acid alkyl ester having an alkyl group having 10 or more carbon atoms. In some cases, the stain resistance of the cured product was high.
From these results, in order for the cured product to exhibit good water resistance and weather resistance, as well as high stain resistance and its longevity, the (meth)acrylic polymer as the component (B) must have a hydrophobic group and It is understood that it is important to have hydrophilic groups in the specific proportions indicated in the present invention.

The curable composition of the present invention cures at room temperature with moisture in the air or the like, and a cured product having stain resistance superior to that of conventional compositions can be obtained, and the effect is sustained. In addition, the cured product has high water resistance and weather resistance. Furthermore, the curable composition of the present invention has an appropriate viscosity and is therefore excellent in workability. Therefore, it is suitable as a curable composition for sealants and the like in the construction field.

Claims (8)

A curable composition (excluding an aqueous emulsion) containing the following (A) and (B) , wherein the (A) polymer is added to 100 parts by mass of the (B) (meth)acrylic 1 polymer
A curable composition containing ~30 parts by mass .
(A) a polymer having a reactive silyl group (excluding a polymer containing 40 to 98% by mass of a monomer represented by the following general formula (1) as a constituent monomer unit);

(R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 2 to 4 carbon atoms, R ³ is a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, n is 2 to 25 represents an integer of
(B) 2 to 60% by mass of units derived from a (meth)acrylic acid alkyl ester having an alkyl group having 10 or more carbon atoms as constituent monomer units, and a monomer represented by the general formula (1) A (meth)acrylic polymer containing 40 to 98% by mass of units derived from. 2. The curable composition according to claim 1, wherein the polymer (A) comprises a polyoxyalkylene polymer having a reactive silyl group. 3. The curable composition according to claim 1, wherein the polymer (A) comprises a (meth)acrylic polymer having a reactive silyl group. The curing according to any one of claims 1 to 3, wherein the (B) (meth)acrylic polymer comprises a (meth)acrylic acid ester monomer having a reactive silyl group as a constituent monomer unit. sex composition. Any one of claims 1 to 4, wherein the (B) (meth)acrylic polymer contains, as a constituent monomer unit, a monomer in which n in the general formula (1) is an integer of 9 to 12. The curable composition according to . The curable composition according to any one of claims 1 to 5 , further comprising a plasticizer. The plasticizer has a weight average molecular weight of 1,000 to 6,000 (meta 7.) The curable composition according to claim 6 , which is an acrylic polymer. A sealant composition comprising the curable composition according to any one of claims 1 to 7 .