JP3951135B2 - Emulsion composition for building material and building material - Google Patents

Description

The present invention relates to an emulsion composition for building materials, which contains a graft copolymer emulsion obtained by emulsion graft copolymerizing a (meth) acrylic monomer or a mixed monomer component mainly composed of an organopolysiloxane. In particular, an emulsion composition for building materials that is rich in adhesiveness, forms a film excellent in elasticity, flexibility, weather resistance, water resistance, water repellency, and heat resistance, and retains its performance over a long period of time , and The present invention relates to a building material obtained by coating and curing the composition .

  In recent years, from the viewpoint of ensuring environmental pollution and a safe working environment, in the field of paints or coating agents, it is required to change the dispersion medium from an organic solvent to an aqueous system. Based on this requirement, emulsions obtained by emulsion polymerization of radical-polymerizable vinyl monomers typified by acrylic resins form excellent films and are widely used as basic materials for paints and coating agents. Have the disadvantage that the properties, water resistance and weather resistance are insufficient.

  Therefore, various attempts have been made to improve these drawbacks. For example, a method of emulsion-polymerizing a vinyl polymerizable functional group-containing alkoxysilane together with a radical polymerizable vinyl monomer to prepare an emulsion (JP-A-69-1463, JP-A-8-27347 (Patent Documents 1 and 2)) Has been proposed. Further, an alkoxysilane compound or a partially hydrolyzed / condensed product thereof is emulsified with various surfactants to form an aqueous emulsion (Japanese Patent Laid-Open Nos. 58-213046, 62-197369, and Japanese Patent Laid-Open No. 3). -115485 (patent documents 3 to 5)) and a system (JP-A-6-344665 (patent document 6)) in which an emulsion obtained by emulsion polymerization of a polymerizable vinyl monomer is further proposed.

  However, in the case of the former, vinyl-polymerizable functional group-containing alkoxysilane is emulsion-polymerized together with radical-polymerizable vinyl monomer, and alkoxy group hydrolysis is also suppressed and preserved, but the coating contains a large amount of silicone resin components. Therefore, it is difficult to improve characteristics such as weather resistance, and it is not a satisfactory level including adhesion when considering exterior use. In the latter case, the active alkoxy group is easily hydrolyzed over time, so that alcohol as an organic solvent is by-produced in the system, and in addition, the degree of polymerization changes with time. The film characteristics shown cannot be obtained.

  As described above, satisfactory film performance cannot be obtained by each conventionally known method, and a film having excellent adhesion, elasticity, flexibility, weather resistance, water resistance, water repellency, and heat resistance is formed. Development of an emulsion composition for building materials that maintains its performance for a long period of time has been desired.

JP 61-9463 A JP-A-8-27347 JP 58-213046 A Japanese Patent Laid-Open No. 62-197369 Japanese Patent Laid-Open No. 3-115485 JP-A-6-344665

The present invention has been made in order to improve the above-described circumstances, and forms a film having excellent adhesion, excellent elasticity, flexibility, weather resistance, water resistance, water repellency, and heat resistance over a long period of time. An object of the present invention is to provide a building material emulsion composition that retains its performance, and a building material obtained by coating and curing the composition .

  As a result of intensive studies to solve the above problems, the present inventors have found that an organopolysiloxane having an organic group containing a radical reactive group and / or an SH group and an organic group containing a primary amino group. Obtained by emulsion graft polymerization of the monomer or mixed monomer to the organopolysiloxane using a mixture of an emulsion and an acrylic and / or methacrylic monomer or a mixed monomer mainly composed thereof. When the composition based on the obtained graft copolymer emulsion is used as a building material, it forms a film with high adhesion and imparts elasticity, flexibility, weather resistance, water resistance, water repellency, and heat resistance. Furthermore, it has been found that these performances can be maintained over a long period of time, and that the conventional problems described above can be solved by using this emulsion composition. Leading to the completion of a bright.

〔式中、Ｒ¹，Ｒ²，Ｒ³，Ｒ⁴はそれぞれ炭素数１〜２０の１価の炭化水素基又は１価のハロゲン化炭化水素基であり、Ｙはラジカル反応性基又はＳＨ基を含む有機基であり、Ｚは第一級アミノ基を含む有機基であり、Ｘは水素原子、１価の低級アルキル基又は式Ｒ¹Ｒ²Ｒ⁵Ｓｉで示される基（Ｒ⁵はＲ¹，Ｙ又はＺであり、Ｒ¹，Ｒ²，Ｙ，Ｚは前記と同じである）であり、ｍは１〜１０，０００の整数、ｋ，ｎは１以上の整数でかつｋ＋ｍ＋ｎが５００〜１２，０００である。〕
で表されるオルガノポリシロキサンの１種又は２種以上：５〜９５質量部
の水中油型エマルジョンに、
（２）下記一般式（ＩＩ）

（式中、Ｒ⁶は水素原子又はメチル基、Ｒ⁷は炭素数１〜１８のアルキル基又はアルコキシ置換アルキル基である。）
で表されるアクリル系単量体及びメタクリル系単量体から選択される１種又は２種以上の単量体を（２）成分全量の７０質量％以上含む単量体又は混合単量体：９５〜５質量部
を添加して前記オルガノポリシロキサンに（２）成分を乳化グラフト共重合させてなるグラフト共重合エマルジョンを主剤とする建材用エマルジョン組成物、及びこの建材用エマルジョン組成物の硬化物を、建材基材上に１０〜８００μｍの厚さで形成させた建材物を提供する。 Therefore, the present invention
(1) The following general formula (I)

[Wherein R ¹ , R ² , R ³ and R ⁴ are each a monovalent hydrocarbon group or monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and Y is a radical reactive group or SH group. Z is an organic group containing a primary amino group, X is a hydrogen atom, a monovalent lower alkyl group or a group represented by the formula R ¹ R ² R ⁵ Si (R ⁵ is R ¹ , Y or Z, and R ¹ , R ² , Y, and Z are the same as above, m is an integer of 1 to 10,000, k and n are integers of 1 or more , and k + m + n is 500. ~ 12,000 . ]
In the oil-in-water emulsion of 5 to 95 parts by mass, one or more of the organopolysiloxanes represented by
(2) The following general formula (II)

(In the formula, R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is an alkyl group having 1 to 18 carbon atoms or an alkoxy-substituted alkyl group.)
A monomer or mixed monomer containing 70% by mass or more of the total amount of component (2) containing one or more monomers selected from acrylic monomers and methacrylic monomers represented by: An emulsion composition for building materials mainly comprising a graft copolymer emulsion obtained by adding 95 to 5 parts by mass and emulsion graft copolymerizing component (2) with the organopolysiloxane , and a cured product of the emulsion composition for building materials Is provided with a thickness of 10 to 800 μm on a building material substrate .

  In this case, it is preferable that the glass transition point of the monomer or mixed monomer polymerized product (2) to be graft-copolymerized with the organopolysiloxane (1) is 0 ° C. or lower.

  Moreover, it is preferable to mix | blend the liquid organopolysiloxane containing the hydrogen atom couple | bonded with at least 3 silicon atom in 1 molecule as a crosslinking agent with the said composition, and the catalyst for crosslinking reactions.

  The emulsion composition for building materials of the present invention has excellent adhesion, forms a film excellent in elasticity, flexibility, weather resistance, water resistance, water repellency, and heat resistance, and maintains its performance over a long period of time. It can be used widely as a basic material for paints and coatings. Furthermore, it is possible to further improve the adhesion, elasticity, flexibility, weather resistance, water resistance, water repellency, and heat resistance by blending a crosslinking agent and a crosslinking reaction catalyst. Due to this characteristic, the building material emulsion composition of the present invention is extremely advantageous in practice.

Hereinafter, the present invention will be described in more detail.
The organopolysiloxane of component (1) used in the building material emulsion composition of the present invention is represented by the following general formula (I).

In the above formula (I), R ¹ , R ² , R ³ and R ⁴ are each an aryl group such as a methyl group, an ethyl group, a propyl group or a butyl group, an aryl group such as a phenyl group, a tolyl group, a xylyl group or a naphthyl group. A monovalent hydrocarbon group having 1 to 20 carbon atoms, particularly 1 to 8 carbon atoms such as a group, or a group in which some or all of hydrogen atoms bonded to carbon atoms of these groups are substituted with a halogen atom, and Y is γ -A radical-reactive group such as acryloxypropyl group, γ-methacryloxypropyl group, γ-mercaptopropyl group, vinyl group, allyl group, or SH group-containing organic group, Z is a γ-aminopropyl group, N-β -(Aminoethyl) an organic group containing a primary amino group such as γ-aminopropyl group, X is a triorganosilyl group represented by R ¹ R ² R ⁵ Si (R ⁵ is R ¹ , Y or Z R ¹ , R ² , Y, Z are the same as above And a hydrogen atom, or a lower alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group. M is an integer of 1 to 10,000, k and n are integers of 1 or more, and preferably 500 ≦ m ≦ 8,000, 1 ≦ k ≦ 3,000, and 1 ≦ n ≦ 500. More preferably, it is an integer in the range of 2,000 ≦ m ≦ 8,000, 500 ≦ k ≦ 2,000, 5 ≦ n ≦ 200 , and k + m + n is 500 to 12,000 .

（式中、ｐは３〜６の整数）
で示される環状オルガノポリシロキサン、下記式 As a raw material of the organopolysiloxane represented by the general formula (I), the following formula

(Wherein p is an integer of 3 to 6)
A cyclic organopolysiloxane represented by the following formula:

（式中、ｑは正の整数）
で示される分子鎖両末端が水酸基で封鎖された液状ジメチルポリシロキサン、下記式

(Where q is a positive integer)
Liquid dimethylpolysiloxane in which both molecular chain ends represented by

（式中、ｒは正の整数）
で例示される分子鎖両末端がアルコキシ基で封鎖された液状ジメチルポリシロキサン、及び下記式

(Where r is a positive integer)
A liquid dimethylpolysiloxane in which both ends of the molecular chain are blocked with alkoxy groups, and the following formula:

（式中、ｓは０又は正の整数）
で示される分子鎖両末端がトリメチルシリル基で封鎖されたジメチルポリシロキサン等が例示される。

(Where s is 0 or a positive integer)
And dimethylpolysiloxane having both ends of the molecular chain blocked with a trimethylsilyl group.

等のシラン類、及びこれらの加水分解生成物として下記式で示されるものが例示される。 Moreover, as a raw material for introducing the radical reactive group and the SH group,

Examples of such silanes and their hydrolysis products include those represented by the following formula.

（式中、ｔは３〜６の整数）

(Wherein t is an integer of 3 to 6)

等のシラン類、及びこれらの加水分解生成物として下記式で示されるものが例示される。

（式中、ｕは３〜６の整数） Furthermore, as a raw material for introducing an organic group containing a primary amino group,

Examples of such silanes and their hydrolysis products include those represented by the following formula.

(Where u is an integer from 3 to 6)

  It should be noted that a trifunctional trialkoxysilane and a hydrolysis product thereof can be used as long as they do not interfere with the object of the present invention.

  The production of the oil-in-water emulsion of the organopolysiloxane represented by the general formula (I) may be carried out according to a known method, and one method is to use a cyclic low molecule such as the above-mentioned octamethylcyclotetrasiloxane as a raw material. Siloxane, dialkoxysilane compound containing radical reactive group or SH group and / or hydrolyzate thereof, dialkoxysilane compound containing organic group containing primary amino group and / or hydrolyzate thereof And polymerized in the presence of a strong alkaline catalyst or strong acidic catalyst to obtain a high molecular weight organopolysiloxane, and then emulsified and dispersed in water in the presence of a suitable emulsifier.

  As another method, the raw material contains, for example, the above-described low-molecular organopolysiloxane, a dialkoxysilane containing a radical reactive group or SH group and / or a hydrolyzate thereof, and a primary amino group. It is obtained by subjecting a dialkoxysilane compound containing an organic group and / or a hydrolyzate thereof to emulsion polymerization in water in the presence of a sulfonic acid surfactant and / or a sulfate ester surfactant. is there.

  In the case of this emulsion polymerization, the same raw materials are used, and after emulsifying and dispersing in water with a cationic surfactant such as alkyltrimethylammonium chloride or alkylbenzylammonium chloride, an appropriate amount of potassium hydroxide, sodium hydroxide, etc. It is also possible to perform polymerization by adding a strong alkaline substance.

  In the above-described method for producing an organopolysiloxane emulsion, potassium hydroxide, sodium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, tetrabutyl are used as a strong alkaline polymerization catalyst for obtaining a high molecular weight organopolysiloxane in advance. Phosphonium hydroxide and the like, and strong acid polymerization catalysts include sulfuric acid, trifluoromethanesulfonic acid and the like, and any of them can be used for subsequent use if neutralization is performed after the completion of polymerization to eliminate the catalytic activity. .

  Surfactants for emulsifying the resulting high molecular weight organopolysiloxane include various nonionic polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, sorbitan fatty acid esters, polyoxy Examples include ethylene sorbitan fatty acid ester, sucrose fatty acid ester, anionic sodium lauryl sulfate, polyoxyethylene dodecyl sulfate sodium, and cationic alkyltrimethylammonium chloride, alkylbenzylammonium chloride, and dialkyldimethylammonium chloride. .

Ｃ₈Ｈ₁₇（ＯＣ₂Ｈ₄）₂ＯＳＯ₃Ｈ，Ｃ₁₀Ｈ₂₁（ＯＣ₂Ｈ₄）ＯＳＯ₃Ｈ、ラウリル硫酸ソーダ、ポリオキシエチレンドデシルフェニル硫酸ソーダ等が例示される。 When an emulsion of an organopolysiloxane is produced by an emulsion polymerization method, the sulfonic acid surfactant and the sulfate ester surfactant described above have both an emulsifier and a polymerization catalyst.

Examples thereof include C ₈ H ₁₇ (OC ₂ H ₄ ) ₂ OSO ₃ H, C ₁₀ H ₂₁ (OC ₂ H ₄ ) OSO ₃ H, sodium lauryl sulfate, polyoxyethylene dodecyl phenyl sodium sulfate, and the like.

  Among these, sulfate ester salts change to the corresponding acid by contacting with a cation exchange resin after the completion of emulsification, and function as a polymerization catalyst. After the completion of the emulsion polymerization, the catalytic activity may be lost by neutralizing the surfactant in the acid form.

  Further, as the cationic emulsifier, the quaternary ammonium salt system as described above is mainly used, and after the emulsion polymerization, the basic surfactant is neutralized to lose the catalytic activity.

  When the molecular weight of the organopolysiloxane represented by the general formula (I) is small, the effect of imparting the elasticity and flexibility of the target film is poor. Therefore, when emulsifying and dispersing an organopolysiloxane obtained by polymerization in advance, it is preferable to keep the organopolysiloxane having a high molecular weight. In the case of emulsion polymerization, the temperature during aging performed after polymerization should be lowered. Since the molecular weight of the organopolysiloxane increases, the aging temperature is desirably 30 ° C. or less, more desirably 15 ° C. or less, and the aging time is desirably 24 to 72 hours, more desirably 48 to 72 hours. Good. In addition, as molecular weight of this organopolysiloxane, in Formula (I), it is preferable that k + m + n is 500-12,000, especially 2,500-11,000.

  Next, the component (2) will be described. This is a polymerizable monomer or a mixed monomer for graft copolymerization with the organopolysiloxane of the component (1), which has the following general formula (II): (1) One or two or more monomers selected from acrylic monomers and methacrylic monomers represented by the formula (2) can be contained in an amount of 70% by mass or more based on the total amount of the component (2). In this case, as the monomer other than the acrylic monomer and the methacrylic monomer of the following general formula (II), the following (b) and (c) components can be mentioned, The following three components (a) to (c) are preferably included.

  Component (a) is a (meth) acrylic monomer represented by the following general formula (II) [wherein the expression (meth) acrylic represents both acrylic and methacrylic, and the same shall apply hereinafter. is there. ].

（式中、Ｒ⁶は水素原子又はメチル基、Ｒ⁷は炭素数１〜１８のアルキル基又はアルコキシ置換アルキル基である。）

(In the formula, R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is an alkyl group having 1 to 18 carbon atoms or an alkoxy-substituted alkyl group.)

In the above formula (II), R ⁷ is an alkyl group having 1 to 18 carbon atoms or an alkoxy-substituted alkyl group, particularly an alkyl group having 1 to 8 carbon atoms or an alkoxy-substituted alkyl group. For example, methyl group, ethyl group, propyl group Examples thereof include alkyl groups such as a group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group and octyl group, and alkoxy-substituted alkyl groups such as methoxyethyl group, ethoxyethyl group and butoxyethyl group.

  Examples of the (meth) acrylic monomer represented by the formula (II) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth). Alkyl (meth) acrylates such as acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and methoxyethyl Examples thereof include alkoxyalkyl (meth) acrylates such as (meth) acrylate and butoxyethyl (meth) acrylate, and these are used alone or in combination of two or more.

  The monomer represented by the general formula (II) is 70% by mass or more of the total amount of the component (2), preferably 70 to 98% by mass, and more preferably 80 to 95% by mass. When the monomer represented by the formula (II) is less than 70% by mass of the total amount of the component (2), the acrylic properties, particularly mechanical strength, ozone resistance, and adhesion performance are insufficient.

  The component (b) is a polyfunctional monomer, and includes (meth) acrylamide, diacetone (meth) acrylamide, N- as ethylenically unsaturated amide, alkylol or alkoxyalkyl-substituted compound of ethylenically unsaturated amide. As an oxirane group-containing ethylenically unsaturated monomer such as methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, hydroxyl group such as glycidyl (meth) acrylate, glycidyl allyl ether, etc. As the ethylenically unsaturated monomer, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. As the carboxyl group-containing ethylenically unsaturated monomer, (meth) acrylic acid, maleic anhydride , Crotonic acid, itacone Etc., as the amino group-containing ethylenically unsaturated monomer, N- dimethylaminoethyl (meth) acrylate, N- diethylaminoethyl (meth) acrylate, as a sulfonic acid group-containing ethylenically unsaturated monomer,

（式中、Ｒ⁸は炭素数１〜１８のアルキル基、Ｒ⁹は水素原子又はメチル基、ＡはＨ，Ｎａ，Ｋ又はＮＨ₄）

(Wherein R ⁸ is an alkyl group having 1 to 18 carbon atoms, R ⁹ is a hydrogen atom or a methyl group, and A is H, Na, K or NH ₄ )

（式中、Ｒ⁹は前記に同じ、ｖは１以上、好ましくは１〜１０の整数） As a phosphoric acid group-containing ethylenically unsaturated monomer,

(Wherein R ⁹ is the same as above, v is 1 or more, preferably an integer of 1 to 10)

（式中、Ｒ⁹は前記に同じ、ｗは２以上、好ましくは１〜２０の整数） As an ethylenically unsaturated monomer containing a polyalkylene oxide group,

(Wherein R ⁹ is the same as above, w is 2 or more, preferably an integer of 1 to 20)

As an ethylenically unsaturated monomer containing a quaternary ammonium base,

As complete esters of polyhydric alcohol and (meth) acrylic acid, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and allyl (meth) acrylate, divinylbenzene, etc. And one of these can be used alone or in combination of two or more.

  These polyfunctional monomers are used for the purpose of imparting adhesion. Increasing the amount used improves adhesion and the like, but conversely, the elasticity and flexibility of the coating are impaired. Therefore, it is preferable that the usage-amount of a polyfunctional monomer is 2-10 mass% in (2) component, More preferably, it is 2-7 mass%, and when it exceeds 10 mass%, it is elastic and flexible. May be significantly impaired, and if it is less than 2% by mass, adhesion may be impaired, and a uniform film may not be formed.

  Component (c) is another ethylenically unsaturated monomer. Examples of these monomers include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate, and vinyl propionate. And vinyl versatate.

  The component (c) can be blended in the component (2) preferably in the range of 0 to 20% by mass, more preferably in the range of 2 to 15% by mass, as required. The component represented by the general formula (II) Adhesiveness and the like that cannot be expressed only by a monomer or a polyfunctional monomer are imparted, but if it exceeds 20% by mass, the acrylic properties may be impaired.

  In the present invention, in order to impart flexibility to the film, from the monomer (2) component or the polymerized product of the mixed monomer, that is, from the component (2) grafted on the straight chain of the component (1) What is necessary is just to soften the polymerized product to be obtained. For this purpose, it is desirable that the glass transition point of the polymerized product of the monomer (2) or the mixed monomer is 0 ° C. or lower, preferably −10 ° C. or lower. Therefore, it is desirable to consider this glass transition point in selecting each of the above monomers. In the present invention, the glass transition point of the polymerized product of the monomer (2) or mixed monomer of the component (2) is the same as that of Bull. Am. Phys. Soc. T. described in Volume 1, p. 123. G. The numerical value calculated | required by calculation by the method of Fox is shown.

  About the ratio of (1) component and (2) component, it is (1) component: (2) component = 5: 95-95: 5 (mass part), 20: 80-80: 20 (mass part) Preferably there is. When the component (1) is less than 5 parts by mass, the tackiness that is a drawback of the (meth) acrylic polymer is produced and the flexibility becomes poor. When the component (1) exceeds 95 parts by mass, the toughness and adhesion of the film Performance and durability are impaired, which is not practical.

  The emulsion graft copolymerization of the component (1) and the component (2) can be performed by a known emulsion polymerization method using a normal radical initiator.

  Examples of the radical initiator used herein include water-soluble types such as persulfates such as potassium persulfate and ammonium persulfate, hydrogen persulfate water, t-butyl hydroperoxide, and HCl salt of azobisamidinopropane, benzoylpersulfate. Examples include oil-soluble types such as oxide, cumene hydroperoxide, dibutyl peroxide, diisopropyl peroxycarbonate, cumyl peroxyneodecanoate, cumyl peroxyoctoate, and azobisisobutyronitrile. If necessary, a redox system using a reducing agent such as acidic sodium sulfite, Rongalite, L-ascorbic acid, saccharides and amines can also be used.

  The emulsifier does not necessarily need to be newly used since the emulsifier is contained in the emulsion of component (1). However, a necessary amount of emulsifier is added to prevent the generation of pseudo-lumps during polymerization and to improve the stability of the emulsion. Can be added. Examples of the emulsifier used herein include anionic emulsifiers such as alkyl or alkyl allyl sulfates or sulfonates and dialkyl sulfosuccinates, cationic emulsifiers such as alkyl trimethyl ammonium chloride and alkyl benzyl ammonium chloride, and polyoxy Nonionic emulsifiers such as ethylene alkylphenyl ether, polyoxyethylene alkyl ether, and polyoxyethylene carboxylic acid ester can be suitably used.

  In the present invention, it is preferable to blend a crosslinking agent and a crosslinking reaction catalyst in the graft copolymer emulsion as the main component. Below, the crosslinking agent and the catalyst for crosslinking reaction to be blended are described.

  As the crosslinking agent component, it is preferable to use a liquid organopolysiloxane having hydrogen atoms bonded to at least three silicon atoms in one molecule, and examples thereof include those represented by the following formula.

（式中、ｘは３以上の整数、好ましくは３〜１００の整数、ｙは正の整数、好ましくは３〜１００の整数）

(Wherein x is an integer of 3 or more, preferably an integer of 3 to 100, y is a positive integer, preferably an integer of 3 to 100)

Copolymerized siloxanes of (CH ₃ ) ₂ HSiO _1/2 units, (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units can also be used, which are small amounts of (CH ₃ ) HSiO units or ( CH ₃ ) ₂ SiO units may be included, and the molar ratio of triorganosiloxy units to SiO ₂ units may be set in the range of 0.5 to 2.0.

  The viscosity of the cross-linking agent is not particularly limited as long as it is liquid, but is preferably 10 to 500 mPa · s, particularly 50 to 250 mPa · s at 25 ° C.

  This crosslinking agent component forms a crosslinked film by reacting with the hydroxyl group or alkoxy group bonded to the silicon atom of the organopolysiloxane (1) component, and further enhances the elasticity and flexibility effects.

  Examples of the catalyst for the crosslinking reaction include dibutyltin and dioctyltin acetates, organic salts such as octylates and laurates, titanates, and the like.

  It is preferable that the compounding quantity of a crosslinking agent is 0-50 mass parts with respect to 100 mass parts of copolymers of said (1) component and (2) component, especially 5-40 mass parts. Similarly, the blending amount of the catalyst for crosslinking reaction is preferably 0 to 50 parts by mass, particularly 2 to 25 parts by mass with respect to 100 parts by mass of the copolymer of the components (1) and (2). Both the cross-linking agent component and the cross-linking reaction catalyst can be blended as an emulsion by emulsifying and dispersing in water using an emulsifier as described above.

  Moreover, the emulsion composition for building materials of this invention can add another additive according to the objective. For example, to obtain a matte coating, silicic acid such as anhydrous silicic acid and hydrous silicic acid, silicate compounds such as aluminum silicate, magnesium silicate, clay and talc, calcium carbonate, barium carbonate, gypsum, talc, alumina white, synthetic A matting agent such as resin powder is added, and then the matting agent is dispersed by a dispersing machine such as a ball mill, a colloid mill, a homomixer, a sand mill, or a disper. A dye or pigment may be added to obtain a colored film.

  When it is necessary to adjust the viscosity of the emulsion composition for building materials, cellulose derivatives such as polyvinyl alcohol, gelatin, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, xanthan gum, sodium polyacrylate, polyacrylamide, etc. Appropriate amount may be added.

  In addition, an antifoaming agent, an antiseptic agent, an antifungal agent and the like can be added as necessary within a range not impairing the object of the present invention.

  The building material emulsion composition of the present invention can be obtained by adding and mixing the above-described components to the graft copolymer emulsion, which is the main agent, as necessary.

  The above-mentioned emulsion composition for building materials can be used by coating various building materials so that the film thickness after curing is 10 to 800 μm, particularly 20 to 500 μm, and curing the coating. In this case, the curing conditions may be a temperature of 100 to 180 ° C., particularly 130 to 160 ° C., for 2 to 30 minutes, particularly 2 to 20 minutes.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, the part and% in an example show a mass part and mass%, respectively.

[Examples 1 to 12, Comparative Examples 1 to 5]
(Preparation of organopolysiloxane emulsion)
1,500 parts of octamethylcyclotetrasiloxane, 3.8 parts of methacryloxypropylmethylsiloxane, 50 parts of γ-aminopropylmethylsiloxane and 1,500 parts of ion-exchanged water are mixed, and 18 parts of sodium lauryl sulfate and dodecylbenzene are mixed therewith. After adding 12 parts of sulfonic acid, the mixture was stirred and emulsified with a homomixer, and then passed through a homogenizer at a pressure of 3,000 bar twice to form a stable emulsion. Next, this was charged into a flask, heated at 70 ° C. for 12 hours, cooled to 15 ° C. and aged for 72 hours, then adjusted to pH 7 with sodium carbonate and blown with nitrogen gas for 4 hours. Then, volatile siloxane was distilled off by steam distillation, and then ion-exchanged water was added to adjust the non-volatile content to 45% to obtain a polysiloxane emulsion (hereinafter abbreviated as E-1).
Moreover, as shown in Table 1, polysiloxane emulsions E-2 to E-7 were obtained in the same manner as E-1, except that the type, amount and aging conditions of siloxane were changed.

(Preparation of copolymer emulsion)
Into a 2 L three-necked flask equipped with a stirrer, condenser, thermometer and nitrogen gas inlet, 333 parts of the emulsion E-1 obtained above (150 parts of siloxane) and 517 parts of ion-exchanged water were charged, and nitrogen gas was added. After adjusting the inside of the vessel to 30 ° C. under an air stream, 1.0 part of t-butyl hydroperoxide, 0.5 part of L-ascorbic acid and 0.002 part of ferrous sulfate heptahydrate were added, and then the vessel was added. While maintaining the internal temperature at 30 ° C., a mixture of 328.6 parts of butyl acrylate, 10.5 parts of acrylic acid, 5.3 parts of methacrylic acid, and 56 parts of a 10% aqueous solution of N-methylolacrylamide were added dropwise over 3 hours. . After completion of the dropwise addition, stirring was continued for 1 hour to complete the reaction. The obtained copolymer emulsion (hereinafter abbreviated as P-1) had a solid content concentration of 39.2%, and the calculated glass transition point of a polymerized product such as an acrylic monomer was −46 ° C. (measurement method) Is based on Bull. Am. Phys. Soc. Vol. In the same manner as above, copolymerization was carried out with the types and amounts of polysiloxane emulsions and acrylic monomers shown in Table 2 to obtain emulsions P-2 to P-14.

《（ ）内の数字はポリシロキサン分を表す》

<< Numbers in parentheses indicate polysiloxane content >>

(Evaluation)
For copolymer emulsions P-1 to P-14, treatment liquids as shown in Table 3 were prepared, and coated on a polished steel plate having a clean surface so that the film thickness after curing was 500 μm. The heating curing condition after coating was 150 ° C./5 minutes.
Using the resulting coated plate, the elasticity, flexibility, gloss durability, water resistance, water contact angle, adhesion, heat resistance, and adhesion of the coating film were evaluated by the following evaluation test methods. . The results are also shown in Table 3.

で示される粘度１５０ｍＰａ・ｓのメチルハイドロジェンポリシロキサン３０部をポリオキシエチレンアルキルフェニルエーテル５部を用いてイオン交換水６５部の中に乳化分散せしめたエマルジョンであり、また、触媒は、ジブチル錫ジラウレート３０部をポリオキシエチレンアルキルエーテル３部を用いてイオン交換水６７部中に乳化分散せしめたエマルジョンである。 In addition, the crosslinking agent in Table 3 has the following formula

Is an emulsion obtained by emulsifying and dispersing 30 parts of methylhydrogenpolysiloxane having a viscosity of 150 mPa · s in 65 parts of ion-exchanged water using 5 parts of polyoxyethylene alkylphenyl ether, and the catalyst is dibutyltin. An emulsion obtained by emulsifying and dispersing 30 parts of dilaurate in 67 parts of ion-exchanged water using 3 parts of polyoxyethylene alkyl ether.

[Evaluation test method]
(Elastic)
Evaluation was made according to the following criteria by touch.
○: Good resilience and torsional recovery.
×: Resilience and torsional restoration poor.

(Flexibility)
Evaluation was made according to the following criteria by touch.
○: Bending recovery is good.
X: Bending recovery failure.

(Glossy persistence)
The following criteria were used for visual evaluation.
○: The gloss of the specimen after outdoor exposure for one year is the same as that of unexposed.
Δ: The gloss of the specimen after outdoor exposure for one year is inferior to that of the unexposed specimen.
X: The test piece after outdoor exposure for one year is not glossy.

(water resistant)
The state of the coating film after being immersed in distilled water at 20 ° C. for 72 hours was visually judged according to the following criteria.
○: No change in coating state.
Δ: There are swelling and whitening in part of the coating film.
X: There are swelling and whitening on the entire surface of the coating film.

(Water contact angle)
Using a contact angle meter CA-D type manufactured by Kyowa Interface Science Co., Ltd., ion-exchanged water was dropped on the coating film, and the contact angle was measured for 30 seconds after the dropping.

(Adhesion)
It measured by the cross-cut test of JIS K-5400, and the evaluation point was attached | subjected by the observation shown below.
100 points: Each of the cuts is thin, and the intersection of the cuts and the first glance of the square are not peeled off.
80 points: There is slight peeling at the intersection of the cuts, and the area of the defect is 10% of the total square area
Less than.
60 points: There is peeling at both sides of the cut and at the intersection, and the area of the defect is not 20% of the total square area
Full.
40 points: The width of peeling due to cuts is wide, and the area of the missing part is less than 40% of the total square area.
20 points: The width of peeling due to cuts is wide, and the area of the missing part is less than 60% of the total square area.
0 point: The peeling area is 60% or more of the total square area.

(Heat-resistant)
The coating film was heat-treated in a dryer at 100 ° C. for 48 hours and visually observed for discoloration, and evaluated according to the following criteria.
○: No thermal discoloration.
Δ: Some thermal discoloration.
X: Thermal discoloration is remarkable.

(Adhesiveness)
For the copolymer emulsion, a treatment solution as shown in Table 3 was prepared and applied to a wooden board piece in an amount of 200 g / m ² . The heating curing condition after coating was 150 ° C./5 minutes. After that, a polyolefin foam skin material is pressure-bonded to a wooden board piece at a pressure of 0.2 MPa for 30 seconds to obtain a test piece, cured for 240 hours in an atmosphere of 20 ° C. × 60% RH, and peel strength (unit: kgf / 25 mm) The measurement of was carried out.

Claims (7)

(1) The following general formula (I)

[Wherein R ¹ , R ² , R ³ and R ⁴ are each a monovalent hydrocarbon group or monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and Y is a radical reactive group or SH group. Z is an organic group containing a primary amino group, X is a hydrogen atom, a monovalent lower alkyl group or a group represented by the formula R ¹ R ² R ⁵ Si (R ⁵ is R ¹ , Y or Z, and R ¹ , R ² , Y, and Z are the same as described above), m is an integer of 1 to 10,000, k and n are integers of 1 or more, and k + m + n is 500. ~ 12,000. ]
In the oil-in-water emulsion of 5 to 95 parts by mass, one or more of the organopolysiloxanes represented by
(2) The following general formula (II)

(In the formula, R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is an alkyl group having 1 to 18 carbon atoms or an alkoxy-substituted alkyl group.)
A monomer or mixed monomer containing 70% by mass or more of the total amount of component (2) containing one or more monomers selected from acrylic monomers and methacrylic monomers represented by: An emulsion composition for building materials comprising a graft copolymer emulsion obtained by adding 95 to 5 parts by mass and emulsion-copolymerizing component (2) with the organopolysiloxane.   (1) In the general formula (1) of the component, m, k, n are integers in the range of 500 ≦ m ≦ 8,000, 1 ≦ k ≦ 3,000, 1 ≦ n ≦ 500, and k + m + n is The emulsion composition for building materials according to claim 1, wherein the composition is 2,500 to 11,000. (2) The component is
(A) The following general formula (II)

(In the formula, R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is an alkyl group having 1 to 18 carbon atoms or an alkoxy-substituted alkyl group.)
One or two or more monomers selected from acrylic monomers and methacrylic monomers represented by 70 to 98% by mass
(B) Ethylenically unsaturated amide, alkylol or alkoxyalkyl substituted compound of ethylenically unsaturated amide, oxirane group, hydroxyl group, carboxyl group, amino group, sulfonic acid group, phosphoric acid group, polyalkylene oxide group or quaternary One or more polyfunctional monofunctional monomers selected from the group consisting of ammonium base-containing ethylenically unsaturated monomer, complete ester of polyhydric alcohol and acrylic acid or methacrylic acid, allyl acrylate, allyl methacrylate and divinylbenzene 2-10% by mass
(C) Ethylenically unsaturated monomers other than the components (a) and (b) 0 to 20% by mass
The emulsion composition for building materials according to claim 1, wherein the emulsion composition is a mixed monomer.   (B) The emulsion composition for building materials according to claim 3, wherein the polyfunctional monomer of component is N-methylolacrylamide or N-butoxymethylacrylamide.   The glass transition point of the monomer or mixed monomer polymerized product (2) to be graft copolymerized with the organopolysiloxane (1) is 0 ° C. or lower. The emulsion composition for building materials according to Item.   Furthermore, the liquid organopolysiloxane containing the hydrogen atom couple | bonded with at least 3 silicon atom in 1 molecule as a crosslinking agent, and the catalyst for bridge | crosslinking reaction are mix | blended in any one of Claim 1 thru | or 5 The emulsion composition for building materials as described.   The building material thing which formed the hardened | cured material of the emulsion composition for building materials of any one of Claims 1-6 on the building material base material with the thickness of 10-800 micrometers.