JP2006273919A - High durability emulsion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous emulsion of a silicone-modified acrylate polymer whose resin composition has excellent weather resistance, soil resistance, water resistance and crack resistance. <P>SOLUTION: The emulsion is a silicone-containing polymer emulsion which is obtained by subjecting [A] a silicone modifying agent, [B] an ethylenic unsaturated monomer having at least one kind of carboxylic group and at least [C] another kind of ethylenic unsaturated monomer to emulsion polymerization. Silicone modifying agent [A] is selected from the group consisting of silanes having a silicone structure such as phenyltrimethoxysilane, diphenyltrimethoxysilane, methyltrimethoxysilane, dimethyltrimethoxysilane, octamethylcyclotetrasiloxane and &gamma;-acryloxypropyltrimethoxysilane. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention is excellent in storage stability, capable of forming a coating film excellent in stain resistance, flexibility, water resistance, weather resistance, durability, pigment dispersibility, gloss retention, adhesion, and rust prevention. The present invention relates to a silicone-containing polymer emulsion. Specifically, it is useful as a finishing material for paints, building materials, surface treatments or finishing materials, adhesives, paper processing agents, woven fabrics, and non-woven fabrics, and in particular, concrete, cement mortar, slate plates, calcium plates, plaster. Main materials and tops for multi-layer finishing coating materials as paints or building finishing materials for various substrates such as boards, extruded plates, inorganic building materials such as expandable concrete, building materials based on woven or non-woven fabric, and metal building materials The present invention relates to a silicone-containing polymer emulsion useful as a metal paint, a wood part paint, and a tile paint as a synthetic resin emulsion paint such as a coat, a thin finish paint, a thick finish paint, a stone finish finish, and a gloss paint.

  Water-based emulsions obtained by emulsion polymerization are often used as resins for water-based paints because the film formed by drying at room temperature or under heating exhibits relatively good durability, but have been exposed outdoors for a long time. In some cases, the film is contaminated by adhesion of dust, smoke, sand, etc., and further has weather resistance, that is, deterioration due to deterioration of color, discoloration, blistering, and cracking due to light, heat, rain, etc. Therefore, the beautiful appearance immediately after the paint is applied becomes a very dirty film due to contamination over time. In addition, it has the disadvantage that it cannot maintain its aesthetics immediately after painting due to a decrease in water resistance, such as whitening or weakening due to rain or condensation.

Patent Document 1 discloses an emulsion in which silicone is combined and has an effect of improving weather resistance, but its film is inferior in flexibility, and even in an example using phenyltrimethoxysilane, long-term weather resistance is cracked. There was a problem of alteration.
In Patent Document 2, in a silicone-complexed emulsion, a silane represented by formula (2) of the present invention and a cyclic silane of the present invention or a silane represented by formula (3) are used in combination in the silicone part. In fact, the weather resistance was improved and the flexibility of the coating was improved. However, long-term weather resistance has problems of deterioration such as cracks.

In Patent Document 3, there is a method in which in a silicone complexed emulsion, a cyclic silane, a silane represented by the formula (2) of the present invention, and diphenyldimethoxysilane which is the silane (1) of the present invention are used in combination with the silicone part. It is disclosed. In this document, since the ethylenically unsaturated monomer is emulsion-polymerized after the production of the silicone dispersion, the compatibility of the polymer comprising the silicone and the ethylenically unsaturated monomer is not sufficient, The weather resistance was not sufficient.
Patent Document 4 discloses a method in which in a silicone complexed emulsion, a silane represented by formula (2) of the present invention and diphenyldimethoxysilane of the present invention silane (1) are used in combination on the silicone part. However, the film is inferior in toughness, and there has been a problem of deterioration such as cracks in long-term weather resistance.

Japanese Patent No. 3108152 Japanese Patent No. 3159234 JP 2000-319579 A JP 2004-149668 A

  The object of the present invention is to provide a highly durable emulsion capable of forming a coating film excellent in weather resistance and crack resistance.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, the first of the present invention is a silicone modifier [A], an ethylenically unsaturated monomer [B] having at least one carboxyl group, and at least one other ethylenically unsaturated monomer. A silicone-containing polymer emulsion comprising [C], wherein the silicone modifier [A] is represented by the following formula (1):
R ¹ _n —Si—R ³ _{4- (n + m)}
| (1)
R ² _m
((N.m) is a set of (1.0) or (1.1), and when n = 1 and m = 0, R ¹ is a phenyl group or a cyclohexyl group, and each R ³ is Each independently represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group, or when n = 1 and m = 1, R ¹ is a phenyl group or a cyclohexyl group, and R ² is A hydrogen atom, an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an alkyl acrylate group having 1 to 10 carbon atoms, or a 1 to 1 carbon atom Group consisting of silane (1) having a silicone structure represented by 10 alkyl methacrylate groups, and each R ³ is independently an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group. At least one kind selected from And the following formula (2):
CH ₃ —Si— (R ⁴ ) ₃ (2)
(Wherein each R ⁴ is independently an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group) and includes at least one selected from the group consisting of silanes (2) having a silicone structure The following formula (3):
(CH ₃ ) ₂ —Si— (R ⁵ ) ₂ (3)
(Wherein each R ⁵ is independently an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group) and / or at least one selected from the group consisting of silanes (3) having a silicone structure Or it is a silicone containing polymer emulsion characterized by including cyclic silane.

The second of the invention is a silicone modifier [A], an ethylenically unsaturated monomer [B] having at least one carboxyl group, and at least one other ethylenically unsaturated monomer [C]. Is a silicone-containing polymer emulsion according to the first aspect of the invention, which is obtained by emulsion polymerization.
According to a third aspect of the invention, the ethylenically unsaturated monomer having a carboxyl group is added to the total weight of the ethylenically unsaturated monomer having a carboxyl group [B] and the other ethylenically unsaturated monomer [C]. The monomer [B] and other ethylenically unsaturated monomers [C] were used in an amount of 90 to 99.5 wt% and 0.5 to 10 wt%, respectively, and the silicone modifier [A] was used as follows: Formula 1/5 ≦ {monomer [B] + monomer [C]} / monomer [A] ≦ 99.5 / 0.5
The silicone-containing polymer emulsion according to the first or second aspect of the invention, which is obtained using an amount satisfying the relationship represented by

In a fourth aspect of the invention, the silicone modifier [A] is at least one selected from the group consisting of silane (2) having a silicone structure represented by the formula (2), the cyclic silane and the formula (3 From the group consisting of silane (2) having a silicone structure represented by the formula (2), with respect to at least one total weight selected from the group consisting of silane (3) having a silicone structure represented by The molar ratio of at least one selected from the group consisting of the cyclic silane and the silane (3) having a silicone structure represented by the formula (3) to at least one selected is at least 1/100, and At least one selected from the group consisting of silane (1) having a silicone structure represented by formula (1) is represented by the following formula 1/100 ≦ silane (1) / {silane (2) + silane ( 3)} ≦ 10/1
The silicone-containing polymer emulsion according to any one of the first to third aspects of the invention, which is used in a molar ratio satisfying the relationship represented by:

  According to a fifth aspect of the invention, the silicone modifier [A] comprises the same or different (A-1) and (A-2), and the ethylenically unsaturated monomer [B] having the carboxyl group is The same or different (B-1) and (B-2), and the other ethylenically unsaturated monomer [C] is the same or different (C-1) and (C-2). The emulsion polymerization is performed in the order of step (1) and step (2). In step (1), the silicone modifier (A-1) and at least one ethylenically unsaturated group having the carboxyl group are used. A monomer (B-1) and at least one other ethylenically unsaturated monomer (C-1) are simultaneously emulsion polymerized to obtain a seed emulsion containing silicone, in step (2) Is the silicone modifier (A-2) and at least one carboxyl group An invention comprising: an ethylenically unsaturated monomer (B-2) having an emulsion polymerized from at least one other ethylenically unsaturated monomer (C-2) The silicone-containing polymer emulsion according to any one of the first to fourth.

  A sixth aspect of the invention is that at least one ethylenically unsaturated monomer [B] is 5% by weight or more of acrylic acid or methacrylic acid based on the weight of the other ethylenically unsaturated monomer [B]. The silicone-containing polymer emulsion according to the first to fifth aspects of the invention, comprising a cycloalkyl ester having 5 to 12 carbon atoms.

  The emulsion of the present invention contains at least one selected from silane (1) as a silicone modifier, thereby forming a coating film having excellent weather resistance and crack resistance as compared with conventional silicone-containing polymer emulsions. it can.

Hereinafter, the present invention will be described in detail.
Silicone modifier [A]
In the present invention, it is essential to use the silicone modifier [A] in order to impart high weather resistance and high durability. The silicone modifier [A] is represented by the following formula (1):
R ¹ _n —Si—R ³ _{4- (n + m)}
| (1)
R ² _m
((N.m) is a set of (1.0) or (1.1), and when n = 1 and m = 0, R ¹ is a phenyl group or a cyclohexyl group, and each R ³ is Each independently represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group, or when n = 1 and m = 1, R ¹ is a phenyl group or a cyclohexyl group, and R ² is A hydrogen atom, an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an alkyl acrylate group having 1 to 10 carbon atoms, or a 1 to 1 carbon atom Group consisting of silane (1) having a silicone structure represented by 10 alkyl methacrylate groups, and each R ³ is independently an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group. At least one kind selected from including. Preferable specific examples of silane (1) include phenyltrimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, cyclohexyltrimethoxysilane, dicyclohexyldimethoxysilane, and cyclohexyltriethoxysilane. , Dicyclohexyldiethoxysilane and the like, and may contain two or more of these.

The silicone modifier [A] contains at least one selected from the group consisting of silane (1) having a silicone structure of the above formula (1), and has the formula (2):
CH ₃ —Si— (R ⁴ ) ₃ (2)
(Wherein each R ⁴ is independently an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group) and includes at least one selected from the group consisting of silanes (2) having a silicone structure. It is preferable for imparting a crosslinking density of the silicone structure. Preferable specific examples of silane (2) include methyltrimethoxysilane, methyltriethoxysilane and the like, and may contain two or more of these.

The silicone modifier [A] contains at least one selected from the group consisting of silane (1) having a silicone structure of the above formula (1), and has the following formula (3):
(CH ₃ ) ₂ —Si— (R ⁵ ) ₂ (3)
(Wherein each R ⁵ is independently an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group) and at least one selected from the group consisting of silanes (3) having a silicone structure] It is preferable that cyclic silane is included. This is because the use of the silane (3) and / or cyclic silane lowers the crosslinking density of the silicone polymer formed by the silicone modifier [A] and prevents the polymer structure from becoming complicated. This is because flexibility can be imparted to the coating film provided from the highly durable emulsion. Preferable specific examples of the silane (3) include dimethyldimethoxysilane and dimethyldiethoxysilane. Further, as the cyclic silane, octamethylcyclotetrasiloxane, octaphenylcyclosiloxane, hexamethylcyclotrisiloxane, decamethylcyclopentasiloxane, tetramethyltetravinylcyclotetrasiloxane, and the like can be used, including two or more of these. You may go out.

  The silicone modifier [A] is added to at least one compound selected from the silane (1) described above, in addition to a compound selected from the silane (2) and / or the silane (3), isobutyltrimethoxysilane, Vinylethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, etc. Can be included.

In the present invention, by using the silicone modifier [A], it is possible to improve the gloss retention of a film obtained from a highly durable emulsion in a long-term exposure such as outdoors, and to obtain a film exhibiting high weather resistance for the first time. . The presence of the above-mentioned silane condensate can be known by ²⁹ SiNMR ( ²⁹ Si nuclear magnetic resonance spectrum) or ¹ HNMR (proton nuclear magnetic resonance spectrum). For example, the condensate of silane (2) can be identified by 29SiNMR chemical shift showing a peak at -40 to -80PPM. The condensate of silane (3) or cyclic silane can be identified by the 29Si NMR chemical shift showing a peak at -16 to -26 PPM.

Ethylenically unsaturated monomer having a carboxyl group [B]
In the present invention, the ethylenically unsaturated monomer [B] having at least one carboxyl group includes (meth) acrylic acid ester (in the present application, acrylic acid and methacrylic acid are combined and expressed as (meth) acrylic acid. It is necessary to include a (meth) acrylate monomer represented by Specific examples of (meth) acrylic acid esters include (meth) acrylic acid alkyl esters having 1 to 18 carbon atoms in the alkyl moiety, and (poly) oxyethylene mono (meth) having 1 to 100 ethylene oxide groups. Acrylate, (poly) oxypropylene mono (meth) acrylate, (meth) acrylic acid hydroxyalkyl ester having 1 to 18 carbon atoms in the alkyl portion, and (poly) oxyethylene di (1) having 1 to 100 ethylene oxide groups And (meth) acrylate. Specific examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) acrylic acid t-. Examples include butyl, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, and (meth) acrylic acid cycloalkyl ester. Specific examples of (poly) oxyethylene mono (meth) acrylate include ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, diethylene glycol methoxy (meth) acrylate, (meta ) Tetraethylene glycol acrylate, tetraethylene glycol methoxy (meth) acrylate, and the like. Specific examples of (poly) oxypropylene mono (meth) acrylate include propylene glycol (meth) acrylate, propylene glycol methoxy (meth) acrylate, dipropylene glycol (meth) acrylate, dipropylene methoxy (meth) acrylate Examples include glycol, tetrapropylene glycol (meth) acrylate, and tetrapropylene glycol methoxy (meth) acrylate. Specific examples of the (meth) acrylic acid hydroxyalkyl ester include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Specific examples of (poly) oxyethylene di (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and di (meth) acryl. Examples include acid tetraethylene glycol. Specific examples other than the above include glycidyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, and the like. The (meth) acrylate monomer is preferably 80 to 100% by mass, more preferably 90% to 100% by mass with respect to the mass of the ethylenically unsaturated monomer [B] having at least one kind of carboxyl group. % Is preferably used.

  Furthermore, in the present invention, a monomer that can be used in combination with the (meth) acrylate monomer as an ethylenically unsaturated monomer [B] having at least one carboxyl group includes a radically polymerizable carboxylic acid monomer. Examples include at least one comonomer that is copolymerizable with the (meth) acrylate monomer and is selected from a monomer. Specific examples of the radical polymerizable carboxylic acid monomer include acrylic acid, methacrylic acid, itaconic acid and its monoester, fumaric acid and its monoester, and maleic acid and its monoester. It is particularly preferable to include at least one selected from the group. This is because these radical polymerizable carboxylic acid monomers also act as a catalyst for promoting the hydrolysis reaction and condensation reaction of the silicone modifier [A].

In the present invention, it is preferable to include a (meth) acrylate monomer having a cycloalkyl group as the ethylenically unsaturated monomer [B] having at least one kind of carboxyl group, since the durability is particularly excellent. A part of hydrogen atoms of the cycloalkyl group may be substituted with an alkyl group having 1 to 6 carbon atoms, a hydroxyl group or an epoxy group. 5% by mass or more, more preferably 5% by mass or more and 99% by mass or less, more preferably 5% by mass or more and 80% by mass or less, of the ethylenically unsaturated monomer [B] having at least one kind of carboxyl group, A (meth) acrylate monomer having an alkyl group or a mixture thereof is preferable. The (meth) acrylate monomer having a cycloalkyl group or a mixture thereof is excellent in durability when it is 5% by mass or more of the ethylenically unsaturated monomer [B] having at least one carboxyl group, and 80% by mass. %, The film formability is good. Examples of the (meth) acrylate monomer having a cycloalkyl group include (meth) acrylic acid cycloalkyl ester. As the (meth) acrylic acid cycloalkyl ester, an ester of a cycloalkyl group having 5 to 12 carbon atoms is preferable, and the cycloalkyl ester is an alkyl group in which a part of hydrogen atoms of the cycloalkyl group has 1 to 6 carbon atoms, It may be substituted with a hydroxyl group or an epoxy group. Examples of the (meth) acrylate monomer having a cycloalkyl group include a compound represented by the following formula (4).

（式中、Ｒ¹ は水素原子またはメチル基であり、Ｒ²はシクロペンチル基、シクロヘキシル基又はシクロドデシル基であり、これらシクロアルキル基は、炭素数１〜６のアルキル基、水酸基またはエポキシ基を置換基として有してもよい。）その具体例としては、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸２−ヒドロキシシクロヘキシル、（メタ）アクリル酸メチルシクロヘキシル、（メタ）アクリル酸２，３シクロヘキセンオキサイドなどを挙げることができる。

(Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a cyclopentyl group, a cyclohexyl group or a cyclododecyl group, and these cycloalkyl groups are alkyl groups, hydroxyl groups or epoxy groups having 1 to 6 carbon atoms. Specific examples thereof include cyclohexyl (meth) acrylate, 2-hydroxycyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, and 2,3-cyclohexene (meth) acrylate. An oxide etc. can be mentioned.

Other ethylenically unsaturated monomers [C]
The other ethylenically unsaturated monomer [C] in the present invention includes at least one copolymerizable with a (meth) acrylate monomer selected from an acrylamide monomer, a methacrylamide monomer, and a vinyl monomer. Specified comonomers. Examples of acrylamide monomers or methacrylamide monomers include (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and vinyl monomers. Examples thereof include vinyl acetate, vinyl propionate, vinyl versatate, vinyl pyrrolidone, methyl vinyl ketone, and examples of vinyl cyanide monomers include acrylonitrile and methacrylonitrile.
Further, as the ethylenically unsaturated monomer [C], monomers that can be used by mixing with (meth) acrylate monomers include aromatic monomers such as vinyltoluene, styrene, α-methylstyrene, and vinyl chloride. And vinyl halides such as vinylidene chloride, butadiene, and ethylene.

Emulsifier [D]
In the present invention, the emulsifier [D] used for emulsion polymerization is at least one of an ethylenically unsaturated monomer having a sulfonic acid group or a sulfonate group and an ethylenically unsaturated monomer having a sulfate group. In order to achieve a high level of water resistance, it is preferable. The ethylenically unsaturated monomer having a sulfonic acid group or a sulfonate group mentioned here has a radically polymerizable double bond and is a free sulfonic acid group, or an ammonium salt or an alkali metal salt thereof. A compound having (ammonium sulfonate group or alkali metal sulfonate group) is preferable. For example, an alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 2 to 4 carbon atoms, a polycarbon having 2 to 4 carbon atoms, which is partially substituted with a group that is an ammonium salt, sodium salt or potassium salt of a sulfonic acid group. It is a compound having a substituent selected from the group consisting of an alkyl ether group, an aryl group having 6 or 10 carbon atoms and a succinic acid group, or bonded to a group which is an ammonium salt, sodium salt or potassium salt of a sulfonic acid group. Preferred are vinyl sulfonate compounds having a vinyl group.

Specific examples of the succinic acid compound partially substituted with a group which is an ammonium salt, sodium salt or potassium salt of a sulfonic acid group in the present invention include allylsulfosuccinate, for example, the following formulas (5), (6), (7), the compound represented by (8) is mentioned.

（式中、Ｒ¹は水素またはメチル基、Ｒ²は炭素数１〜２０のアルキル基、炭素数１〜２０のアルケニル基、炭素数５〜１２のシクロアルキル基、炭素数６〜１９のアラルキル基等の炭化水素基、又はその一部が水酸基、カルボン酸基等で置換されたもの、もしくはポリオキシエチレンアルキルエーテル基（アルキル部分の炭素数が０〜２０、およびアルキレ
ン部分の炭素が２〜４）、ポリオキシアルキレンアルキルフェニルエーテル基（アルキル部分の炭素数が０〜２０、およびアルキレン部分の炭素数が２〜４）等のアルキレンオキサイド 化合物を含む有機基であり、Ａは炭素数２〜４個のアルキレン基または一部が置換されたアルキレン基であり、 ｎは０〜２００の整数であり、Ｍはアンモニウム、ナトリウムまたはカリウムである。）
上記式（５）及び（６）を含むものとして、例えば、エレミノールＪＳ−２、ＪＳ−５（製品名、三洋化成（株）製）があり、上記式（７）及び（８）を含むものとして、例えば、ラテムルＳ−１２０、Ｓ−１８０Ａ、Ｓ−１８０（製品名、花王（株）製）がある。

Wherein R ¹ is hydrogen or a methyl group, R ² is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an aralkyl having 6 to 19 carbon atoms. A hydrocarbon group such as a group, or a group in which a part thereof is substituted with a hydroxyl group, a carboxylic acid group, or the like, or a polyoxyethylene alkyl ether group (wherein the alkyl moiety has 0 to 20 carbon atoms and the alkylene moiety has 2 to 2 carbon atoms) 4), an organic group containing an alkylene oxide compound such as a polyoxyalkylene alkylphenyl ether group (wherein the alkyl moiety has 0 to 20 carbon atoms and the alkylene moiety has 2 to 4 carbon atoms), and A is 2 to 2 carbon atoms. 4 alkylene groups or a partially substituted alkylene group, n is an integer from 0 to 200, and M is ammonium, sodium or potassium.
Examples of those containing the above formulas (5) and (6) include Eleminol JS-2 and JS-5 (product names, manufactured by Sanyo Chemical Co., Ltd.), and those containing the above formulas (7) and (8). As, for example, there are Latemuru S-120, S-180A, S-180 (product name, manufactured by Kao Corporation).

（式中、Ｒ¹ は炭素数６〜１８のアルキル 基、アルケニル基またはアラルキル基であり、Ｒ^２は炭素数６〜１８のアルキル基、アルケニル基またはアラルキル基、Ｒ³は水素またはプロペニル基、Ａは炭素数２〜４のアルキレン基、ｎは１〜２００の整数、Ｍはアンモニウム、ナトリウム、カリウムもしくはアルカノールアミン残基である。） In addition, as an example of a compound having a C2-C4 alkyl ether group or a C2-C4 polyalkyl ether group partially substituted with a group which is an ammonium salt, sodium salt or potassium salt of a sulfonic acid group And compounds represented by the following formulas (9) to (11).

Wherein R ¹ is an alkyl group having 6 to 18 carbon atoms, an alkenyl group or an aralkyl group, R ² is an alkyl group having 6 to 18 carbon atoms, an alkenyl group or an aralkyl group, R ³ is hydrogen or a propenyl group, A is an alkylene group having 2 to 4 carbon atoms, n is an integer of 1 to 200, and M is an ammonium, sodium, potassium, or alkanolamine residue.)

（式中、Ｒ¹は水素またはメチル基、Ｒ^２は炭素数８〜２４のアルキル基またはアルキルフェニル基、アシル基、Ａは炭素数２〜４のアルキレン基、ｎは０〜５０の整数、ｍは０〜２０の整数、Ｍはアンモニウム、ナトリウム、カリウムもしくはアルカノールアミン残基である。）

Wherein R ¹ is hydrogen or a methyl group, R ² is an alkyl group or alkylphenyl group having 8 to 24 carbon atoms, an acyl group, A is an alkylene group having 2 to 4 carbon atoms, n is an integer of 0 to 50, m is an integer of 0 to 20, M is an ammonium, sodium, potassium or alkanolamine residue.)

（式中、Ｒ¹は炭素数８〜３０のアルキル基、Ｒ^２は水素またはメチル基、Ａは炭素数２〜４のアルキレン基、もしくは置換アルキレン基、ｎは０または、１〜２００の整数であり、Ｍはアンモニウム、ナトリウム、カリウムもしくはアルカノールアミン残基である。）

Wherein R ¹ is an alkyl group having 8 to 30 carbon atoms, R ² is hydrogen or a methyl group, A is an alkylene group having 2 to 4 carbon atoms, or a substituted alkylene group, n is 0 or an integer having 1 to 200 And M is an ammonium, sodium, potassium or alkanolamine residue.)

  Examples of the alkylphenol ether compounds represented by the above formula (9) include Aqualon HS-10 (product name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). Examples of the compounds represented by the above formula (10) include Examples of compounds represented by ADEKA rear soap SE-1025A, SR-10N, SR-20N (product names, manufactured by Asahi Denka Kogyo Co., Ltd.) and the above formula (11) include Aqualon KH-10 and KH-05. .

Other specific examples of the compound having an aryl group partially substituted with a sulfonate group include p-styrenesulfonic acid ammonium salt, sodium salt and potassium salt. Specific examples of the compound having an alkyl group partially substituted with a sulfonate group include ammonium salt, sodium salt and potassium salt of methylpropanesulfonic acid acrylamide, ammonium salt of acrylic acid sulfoalkyl ester, sodium salt and potassium salt, Ammonium salts, sodium salts and potassium salts of acrylic acid sulfoalkylesters can be mentioned. Specific examples of the compound having a sulfonate group other than the above include vinyl sulfonate compounds having a vinyl group to which a group which is an ammonium salt, sodium salt or potassium salt of a sulfonic acid group is bonded. The ethylenically unsaturated monomer having a sulfate ester group refers to a compound having a radical polymerizable double bond and a sulfate ester group or a group that is an ammonium salt or an alkali metal salt thereof. Among these, a C1-C20 alkyl group, a C2-C4 alkyl ether group, a C2-C2 partly substituted by the group which is an ammonium salt of a sulfate ester group, sodium salt, or potassium salt. A compound having a group selected from the group consisting of 4 polyalkyl ether groups and aryl groups having 6 or 10 carbon atoms is preferred. Examples of the compound having a C2-C4 alkyl ether group or a C2-C4 polyalkyl ether group partially substituted with an ammonium salt, sodium salt or potassium salt of a sulfate ester group include: There are compounds represented by the above formulas (9) and (10) having an alkyl ether group partially substituted with a sulfonate group.

  These ethylenically unsaturated monomers used as the emulsifier [D] exist in the emulsion as a copolymer obtained by radical polymerization on the emulsion particles, adsorb to the emulsion particles as unreacted materials, or in the emulsion aqueous phase. Or adsorbed to emulsion particles as a copolymer with water-soluble monomers or as a copolymer of ethylenically unsaturated monomers used as an emulsifier, or present in the emulsion aqueous phase . In particular, the water resistance of the film obtained from the emulsion can be enhanced by increasing the ratio of the emulsion particles in the state of radically polymerized copolymer.

The ethylenically unsaturated monomer used as the emulsifier can identify each substance by pyrolysis gas chromatogram mass spectrometry (Py-GC-MS) of a film obtained from the emulsion. As another method, the aqueous phase component of the emulsion can be separated and then identified by fast atom bombardment mass spectrometry (FAB mass spectrum).
In the present invention, the emulsifier [D] is 0.05 mass relative to the total mass of the ethylenically unsaturated monomer [B] having at least one carboxyl group and the ethylenically unsaturated monomer [C]. % To 10% by mass, preferably 0.1% to 5% by mass.

  In the present invention, in addition to the emulsifier [D] containing an ethylenically unsaturated monomer having a sulfonic acid group, a sulfonate group, or a sulfate ester group, a normal surfactant may be used in combination. For example, anionic surfactants such as fatty acid soaps, alkyl sulfonates, alkyl sulfosuccinates, polyoxyethylene alkyl sulfates, polyoxyethylene alkyl aryl sulfates, polyoxyethylene alkyl aryl ethers, polyoxyethylene sorbitan fatty acid esters , Non-reactive nonionic surfactants such as oxyethyleneoxypropylene block copolymers, α- [1] such as ADEKA rear soap NE-20, NE-30, NE-40 (product name, manufactured by Asahi Denka Kogyo Co., Ltd.) -[(Allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxypolyoxyethylene, or Aqualon RN-10, RN-20, RN-30, RN-50 (product name, Daiichi Kogyo Seiyaku ( Polyoxyethylene alkyl prope It said reactive nonionic surfactants such as phenyl ether, such as ethylenically unsaturated monomers copolymerizable with nonionic surfactants can be used in combination.

  The amount of the surfactant used is an anionic type with respect to the total mass of the ethylenically unsaturated monomer [B] having at least one carboxyl group and the ethylenically unsaturated monomer [C]. The surfactant is preferably 0.5% by mass or less, more preferably 0.25% by mass or less, and the non-reactive nonionic surfactant and the reactive nonionic surfactant are 2.0% by mass. Hereinafter, it is preferably 1.0% by mass or less. When used in this range, a film with good water resistance is formed.

An emulsion of the present invention comprises a pre-emulsion comprising an ethylenically unsaturated monomer [B] having at least one carboxyl group, an ethylenically unsaturated monomer [C] and an emulsifier [D], and a silicone modifier After mixing with [A], a highly durable emulsion can be obtained by polymerization in an aqueous medium.
Examples of the polymerization method include emulsion polymerization, suspension polymerization, bulk polymerization, and miniemulsion polymerization. As a method for stably producing an emulsion having an average particle size of about 10 nm to 1 μm and excellent dispersion stability, emulsification is possible. Polymerization is preferred.

  The emulsion of the present invention is, for example, emulsion polymerization, that is, emulsion polymerization by radical polymerization of a radical polymerizable monomer and emulsion polymerization by hydrolysis / condensation reaction of the silicone modifier [A] compound are simultaneously performed in an aqueous medium. Is obtained. The aqueous medium referred to here is one that is introduced into the reaction system, and water is mainly used, but a water-soluble solvent such as a lower alcohol having 1 to 3 carbon atoms or acetone is added to water. Including things. The amount of the solvent other than water added at this time is preferably 20% by mass or less in the emulsion. Here, the amount of the solvent soluble in water is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably water alone. When this amount is exceeded, the emulsified state of the pre-emulsified liquid is destroyed and the polymerization stability becomes poor.

In the present invention, the pH of the pre-emulsion comprising the ethylenically unsaturated monomer [B] having at least one carboxyl group, the ethylenically unsaturated monomer [C] and the emulsifier [D] is limited. However, by carrying out the polymerization at pH 4.0 or lower, the silicone modifier [A]
It is preferable that the condensation reaction of the reaction takes place rapidly and the condensation reaction proceeds after emulsion polymerization, so that the storage stability as a product is good and the pH of the reaction system is preferably 4.0 or less, more preferably pH 1. It is carried out at 5 or more and 3.0 or less.
In the present invention, the pre-emulsified liquid comprising an ethylenically unsaturated monomer [B] having at least one carboxyl group, an ethylenically unsaturated monomer [C] and an emulsifier [D] comprises an acid catalyst, a radical Make an emulsion near neutrality without containing acidic components such as polymerizable carboxylic acid monomer and persulfate for radical initiator, and use acid catalyst, radical polymerizable carboxylic acid monomer and radical initiator Acidic components such as sulfate can be introduced into the reaction system in advance, or can be sequentially introduced into the reaction system from a position different from the emulsion introduction system.

  In the present invention, it is preferable to include an ultraviolet absorber and / or a light stabilizer in the emulsion in order to impart high weather resistance. As a method for adding the ultraviolet absorber and / or the light stabilizer to the emulsion, It is preferable to make it exist at the time of emulsion polymerization. When UV absorbers and / or light stabilizers are added after being mixed with film-forming aids, etc., they are inferior in dispersibility and are concentrated at the particle interface of the resulting coating film. Long-term durability is not improved. The ultraviolet absorber and / or the light stabilizer is 0.1% relative to the total mass of the ethylenically unsaturated monomer [B] having at least one carboxyl group and the ethylenically unsaturated monomer [C]. It is preferable to use 5% by mass to 5% by mass. Also, use a radical polymerizable compound having a radical polymerizable double bond in the molecule as an ultraviolet absorber, and a radical polymerizable compound having a radical polymerizable double bond in the molecule as a light stabilizer. You can also. Further, it is preferable to use an ultraviolet absorber and a light stabilizer in combination because the film is particularly excellent in weather resistance when the film is formed using the highly durable emulsion.

In the present invention, it is preferable to use at least one selected from benzophenone, benzotriazole, and triazine as the ultraviolet absorber, and at least one selected from hindered amines as the light stabilizer. Combined with a highly durable silicone-modified high-durability emulsion and a high UV-absorbing ability, benzophenone-based, benzotriazole-based, triazine-based UV absorbers and hindered amine-based light stabilizers show excellent durability due to a synergistic effect. . Specific examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and 2-hydroxy-4- n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2 ′ -Dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy- 4-methoxy-2'-carboxy Benzophenone, and the like 2-hydroxy-4-stearyloxy benzophenone. Specific examples of radical polymerizable benzophenone-based UV absorbers include 2-hydroxy-4-acryloxybenzophenone, 2-hydroxy-4-methacryloxybenzophenone, 2-hydroxy-5-acryloxybenzophenone, 2-hydroxy-5. -Methacryloxybenzophenone, 2-hydroxy-4- (acryloxy-ethoxy) benzophenone, 2-hydroxy-4- (methacryloxy-ethoxy) benzophenone, 2-hydroxy-4- (methacryloxy-diethoxy) benzophenone, 2-hydroxy-4- (Acryloxy-triethoxy) benzophenone. Specific examples of benzotriazole-based UV absorbers that can be used in the present invention include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-5′-tert-butylphenyl). ) Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2- Hydroxy-3,5-di-tert-octylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α′-dimethylbenzyl) phenyl] benzotriazole), methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate Condensate with reethylene glycol (molecular weight 300) (manufactured by Ciba Geigy Japan, product name: TINUVIN 1130), isooctyl-3- [3- (2H-benzotriazol-2-yl) -5-tert-butyl-4- Hydroxyphenyl] propionate (manufactured by Ciba Geigy Japan, product name: TINUVIN 384), 2- (3-dodecyl-5-methyl-2-hydroxyphenyl) benzotriazole (manufactured by Ciba Geigy Japan, product name: TINUVIN 571) ), 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) ) Benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotri Sol, 2- [2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole, 2,2-methylenebis [ 4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2H-benzotriazol-2-yl) -4,6-bis ( 1-methyl-1-phenylethyl) phenol (manufactured by Nippon Ciba-Geigy Co., Ltd., product name: TINUVIN 900). Specific examples of radically polymerizable benzotriazole-based UV absorbers include 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd., product name: RUVA- 93), 2- (2′-hydroxy-5′-methacryloxyethyl-3-tert-butylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5′-methacrylyloxypropyl-3-tert- Butylphenyl) -5-chloro-2H-benzotriazole, 3-methacryloyl-2-hydroxypropyl-3- [3 ′-(2 ″ -benzotriazolyl) -4-hydroxy-5-tert-butyl] phenylpropi Honate (Nippon Ciba-Geigy Co., Ltd., product name: CGL-104).

  Specific examples of triazine-based ultraviolet absorbers that can be used in the present invention include TINUVIN400 (product name, manufactured by Nippon Ciba-Geigy Co., Ltd.). As the hindered amine light stabilizer that can be used in the present invention, those having a low basicity are preferable, and specifically, those having a base constant (pKb) of 8 or more are preferable. Specifically, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-butylmalonate, 1- [2- [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propynyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propynyloxy] -2,2,6,6-tetramethylpiperidine, A mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidyl-sebacate (Nippon Ciba Geigy ( Co., Ltd., product name: TINUVIN 292), bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, TINUVIN 123 (product name, manufactured by Ciba Geigy Japan, Inc.), and the like. Specific examples of the radical polymerizable hindered amine light stabilizer include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl acrylate, 2, 2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2,6,6-pentamethyl-4-iminopiperidyl methacrylate, 2, 2,6,6, -tetramethyl-4-iminopiperidyl methacrylate, 4-cyano-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4-cyano-1,2,2,6,6- Examples include pentamethyl-4-piperidyl methacrylate.

  In the emulsion polymerization of the present invention, as a radical polymerization catalyst, it can be radically decomposed by heat or a reducing substance to cause addition polymerization of an ethylenically unsaturated monomer, water-soluble or oil-soluble persulfate, Peroxides, azobis compounds and the like can be used advantageously. Examples include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2,2-azobis. (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile) and the like, but as a catalyst for promoting the hydrolysis reaction and condensation reaction of the silicone modifier [A] It is preferable to use potassium persulfate, sodium persulfate, and ammonium persulfate, which are also effective. The amount of the radical polymerization catalyst is usually 0.05% by mass relative to the total mass of the ethylenically unsaturated monomer [B] having at least one carboxyl group and the ethylenically unsaturated monomer [C]. ˜1% by weight can be used.

  Usually, the polymerization reaction is preferably carried out under normal pressure and at a polymerization temperature of 65 to 90 ° C., but can also be carried out under high pressure in accordance with characteristics such as vapor pressure at the polymerization temperature of the monomer. The polymerization time includes introduction time and aging time after introduction. The introduction time is usually several minutes when various raw materials are simultaneously introduced into the reaction system, and when sequentially introducing various raw materials into the reaction system, the heat is gradually introduced into the reaction system in a range where heat generated by polymerization can be removed. Although it depends on the polymer concentration in the finally obtained emulsion, it is usually 10 minutes or longer. The aging time after the introduction is preferably at least 10 minutes or more. Below this polymerization time, each raw material may remain as it is, or the silicone modifier [A] may remain as a hydrolyzate without being condensed. When acceleration of the polymerization rate and polymerization at a low temperature of 70 ° C. or lower are desired, for example, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, or longalite may be used in combination with the radical polymerization catalyst. It is advantageous. Furthermore, a chain transfer agent such as dodecyl mercaptan can be optionally added to adjust the molecular weight.

In the silicone modification in the present invention, after completion of emulsion polymerization, as a curing catalyst during film formation, for example, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, tin octylate, tin laurate, iron octylate, lead octylate, An amine compound such as a metal salt of an organic acid such as tetrabutyl titanate, n-hexylamine, or 1,8-diazabicyclo [5,4,0] -7-undecene may be added to the highly durable emulsion of the present invention. it can.
When these curing catalysts are not water-soluble, they are preferably emulsified with a surfactant and water when used. In order to maintain long-term dispersion stability of the emulsion, the highly durable emulsion of the present invention can be adjusted to a pH range of 5 to 10 using amines such as ammonia, sodium hydroxide, potassium hydroxide, and dimethylaminoethanol. preferable.

The highly durable emulsion produced by the present invention has a pH of 9 to 12 for evaporating and removing volatile substances, water, alcohol, etc. of the unreacted monomer after the completion of the emulsion polymerization, and a pH of 7 after the completion of the concentration step. It is preferable to perform the concentration step as described above.
The highly durable emulsion produced by the present invention preferably has an average particle size of the dispersoid of 10 to 1000 nm. The mass ratio of the dispersoid (solid content) in the obtained emulsion to the aqueous medium as the dispersion medium is 70/30 or less, preferably 30/70 or more and 65/35 or less.

The highly durable emulsion of the present invention is useful as a finishing material for paints, building materials, or as finishing materials for adhesives, paper processing agents, woven fabrics, and non-woven fabrics. In concrete, concrete, cement mortar, slate plate, calcium plate,
Main materials for multi-layer finish coating materials, such as inorganic building materials such as gypsum board, extrusion molding board, foamable concrete, building materials based on woven or non-woven fabrics, and various base materials such as metal building materials It is useful as a top coat, a thin finish coating material, a thick finish coating material, a stone finish finish material, a synthetic resin emulsion paint such as a gloss paint, a metal paint, a wood paint, and a tile paint.
In the highly durable emulsion of the present invention, components that are usually added and blended with water-based paints, etc., for example, film forming aids, thickeners, antifoaming agents, pigments, dispersants, dyes, preservatives, etc. are optionally blended. be able to.

  One preferred embodiment for providing the highly durable emulsion of the present invention is that the silicone modifier [A] comprises the same or different [A1] and [A2] and has at least one carboxyl group. The unsaturated monomer [B] comprises a (meth) acrylic acid ester monomer and is the same or different from each other [B1] and [B2], and other ethylenically unsaturated monomers [C] Are the same or different [C1] and [C2], and the emulsifier [D] is an ethylenically unsaturated monomer having a sulfonic acid group or a sulfonate group, an ethylenically unsaturated monomer having a sulfate group And emulsifiers [D1] and [D2] that are the same or different from each other and selected from the group consisting of mixtures thereof, and the emulsion polymerization is carried out in steps [1] and [2]. In step [1], an ethylenically unsaturated monomer [B1] having at least one carboxyl group, another ethylenically unsaturated monomer [C1], an emulsifier [D1], and Accordingly, an emulsion comprising an aqueous medium and a silicone modifier [A1] are mixed and subjected to emulsion polymerization in an aqueous medium to obtain step [1] emulsion. In step [2], at least 1 An emulsion comprising an ethylenically unsaturated monomer [B2] having a carboxyl group of the species, another ethylenically unsaturated monomer [C2] and an emulsifier [D2], and, if necessary, an aqueous medium; While mixing with the silicone modifier [A2], step [1] is added to the emulsion to effect emulsion polymerization to obtain the final desired emulsion, and the ultraviolet absorber and It is also possible for a light stabilizer to be present during the emulsion polymerization. In the step [1], the ethylenically unsaturated monomer [B1] having at least one carboxyl group contains 2.5% by mass to 20% by mass of a radical polymerizable carboxylic acid monomer, In step [2], the ethylenically unsaturated monomer [B2] having at least one carboxyl group does not contain a radically polymerizable carboxylic acid monomer or contains less than 2.5% by mass. Is preferred.

According to another preferred embodiment for providing the highly durable emulsion of the present invention, the ethylenically unsaturated monomer [B] having at least one carboxyl group is a (meth) acrylic acid ester-based monomer. [B1], [B2] and [B3] which contain the monomer and are the same or different from each other, and other ethylenically unsaturated monomers [C] are the same or different from each other [C1], [C2] And [C3], and the emulsifier [D] is selected from the group consisting of an ethylenically unsaturated monomer having a sulfonic acid group or a sulfonate group, an ethylenically unsaturated monomer having a sulfate ester group, and a mixture thereof. And the same or different emulsifiers [D1], [D2] and [D3], and the emulsion polymerization is carried out in the order of step [1], step [2] and step [3]. In [1], an ethylenically unsaturated monomer [B1] having at least one carboxyl group, another ethylenically unsaturated monomer [C1], an emulsifier [D1], and, if necessary, an aqueous medium Is subjected to emulsion polymerization in an aqueous medium to obtain an emulsion. In step [2], an ethylenically unsaturated monomer having at least one carboxyl group [ B2], another ethylenically unsaturated monomer [C2], an emulsifier [D2] and, if necessary, a pre-emulsion comprising an aqueous medium in the aqueous medium by adding to the step [1] emulsion Step [2] to obtain an emulsion, and in step [3], an ethylenically unsaturated monomer [B3] having at least one carboxyl group and In step [2], an emulsion comprising an ethylenically unsaturated monomer [C3] and an emulsifier [D3] and an aqueous medium as necessary is added to the emulsion. An emulsion is obtained, and if necessary, the silicone is modified during emulsion polymerization while mixing the emulsion and the silicone modifier [A], and an ultraviolet absorber and / or a light stabilizer is present during the emulsion polymerization. A highly durable emulsion is provided. Silicone modification can be performed during emulsion polymerization while mixing the emulsion in step [1], step [2] and / or step [3] with the silicone modifier [A]. In the step [1], the ethylenically unsaturated monomer [B1] having at least one carboxyl group does not contain a radical polymerizable carboxylic acid monomer or contains less than 2.5% by mass. In the above step [2], the ethylenically unsaturated monomer [B2] having at least one carboxyl group is a radical polymerizable carboxylic acid monomer in an amount of 2.5% by mass to 20% by mass. In the above step [3], the ethylenically unsaturated monomer [B3] having at least one carboxyl group does not contain a radical polymerizable carboxylic acid monomer or contains 2.5% by mass. It is preferable that it is less than.

  Preferred embodiments for providing a highly durable emulsion in the present invention include a silicone modifier [A], an ethylenically unsaturated monomer having at least one carboxyl group [B], and other ethylenically unsaturated monomers. The mixture is made by mixing raw materials consisting of the body [C] and supplying them to the reaction site, whereby the condensation and polymerization proceed simultaneously, and the resulting emulsion is an ethylene having a silicone modifier [A] and at least one carboxyl group. It is important that the unsaturated unsaturated monomer [B] and the other ethylenically unsaturated monomer [C] are in a uniform state and the composition is not unevenly distributed. In a particularly preferred embodiment, by introducing silane (1) in which R1 in the formula (1) of the silicone modifier [A] is a phenyl group or a cyclohexyl group, the silicone modifier [A] and at least one carboxyl group are introduced. As the compatibilization of the ethylenically unsaturated monomer [B] and other ethylenically unsaturated monomer [C] proceeds, it becomes possible to obtain emulsion particles made of a more uniform polymer, and more uniform As a result of uniforming the coating film composition formed from the emulsion particles thus formed, a tough coating film can be formed.

  The present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, the part and% in an Example and a comparative example represent a mass part and the mass%, respectively. The evaluation of the polymerization stability and the physical property test of the obtained aqueous silicone-modified acrylate polymer emulsion were carried out using the emulsion according to the following evaluation and test methods.

<Evaluation of polymerization stability>
The aqueous silicone-modified acrylate polymer emulsion obtained after the emulsion polymerization was filtered through a 100-mesh filter cloth, and the residue mass was divided by the solid content mass of the aqueous silicone-modified acrylate polymer emulsion to obtain a residue rate.
(Judgment criteria) ○: Residue rate is less than 100 ppm
Δ: Residue rate is 100 ppm or more
×: A large amount of aggregate is generated

<Evaluation of filterability>
The aqueous silicone-modified acrylate polymer emulsion obtained after the emulsion polymerization was evaluated by the time required to complete the filtration by filtering the coagulated product with a 100 mesh filter cloth.
(Judgment criteria) ○: Filtration time is less than 30 seconds
Δ: Filtration time of 30 seconds or more and less than 60 seconds
X: Filtration time is 60 seconds or more

<Measurement of particle size>
The average particle size of the obtained aqueous silicone-modified acrylate polymer emulsion was measured with a Microtrac particle size distribution meter manufactured by Leeds & Northrup.
<Evaluation of tensile properties>
Using a water-based silicone-modified acrylate polymer emulsion obtained after emulsion polymerization, a clear paint was prepared with the composition shown below, and after coating with a 0.25 mil applicator, a 1 cm wide coating film sample was cut out and 50 ° C. After being prepared by curing for 1 week, a tensile test was performed under the conditions shown below, and the elongation at break and the stress were measured.
Preparation of clear paint formulation Emulsion of each example (solid content conversion) 460 parts Ethylene glycol monobutyl ether 45 parts Ethylene glycol mono 2-ethylhexyl ether 90 parts Tensile test Tester: Tensilon / UTM-III-500
(Toyo Baldwin Co., Ltd.)
Pulling speed: 50mm / min
Test temperature: 20 ° C

<Evaluation of weather resistance>
Using the aqueous silicone-modified acrylate polymer emulsion obtained after emulsion polymerization, an enamel paint is prepared with the following composition, coated on an aluminum plate with a bar coater, and cured at 50 ° C. for 1 week. The coating film was subjected to an irradiation test for 1500 hours under the following test conditions using an i-super UV tester (Iwasaki Electric Co., Ltd.), and the appearance of the coating film (cracks, peeling, etc.) was visually observed. Observed. At the same time, the gloss retention rate was also evaluated.
(Judgment criteria) ○: No change in appearance
×: Cracking and peeling off Adjustment of enamel coating composition Emulsion of each example (solid content 40% conversion) 250 parts Ethylene glycol monobutyl ether 20 parts Ethylene glycol mono 2-ethylhexyl ether 40 parts Titanium oxide 130 parts Thickener 0. Part 1 Eye Super UV Tester Test Conditions Illuminance: 1000 W / m ²
Irradiation: 63 ° C., 50% RH, 8 hours Dark / wet: 30 ° C., 96% RH or more, 4 hours

[Example 1]
Sulfosuccinic acid diester ammonium salt having a double bond copolymerizable with 320 parts of water and ethylenically unsaturated monomer in a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer (product) Name: Ramtel S-180A, manufactured by Kao Corporation), 10 parts of a 20% aqueous solution was added, the temperature was raised to 80 ° C., and 5 minutes after adding 10 parts of a 2% aqueous solution of ammonium persulfate, step (1) As a mixture of 87 parts of methyl methacrylate, 50 parts of cyclohexyl methacrylate and 110 parts of butyl acrylate, 3 parts of methacrylic acid and 30 parts of 20% aqueous solution of Latemul S-180A, 15 parts of 2% aqueous solution of ammonium persulfate and 290 parts of water A liquid was prepared, and the mixed liquid was emulsified with a homomixer to obtain a pre-emulsion liquid. The resulting pre-emulsion was mixed with a silicone modifier [A] comprising 3.3 parts of γ-methacryloxypropyltrimethoxysilane, 136 parts of methyltrimethoxysilane, 136 parts of dimethyldimethoxysilane and 26 parts of phenyltrimethoxysilane. And Y-tube (Molecular Sieves 3A (product name: Wako Pure Chemical Industries, Ltd.) is filled to the point where the outlet of the Y-tube is filled with a 100-mesh wire mesh and the two dripping tanks are mixed together. The emulsified liquid and the silicone modifier [A] were adjusted so as to be gently mixed. ] Was allowed to flow into the reaction vessel from the dropping tank over 1 hour. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and kept for 30 minutes.

  Next, as step (2), 80 parts of water, 65 parts of methyl methacrylate, 20 parts of cyclohexyl methacrylate and 15 parts of butyl acrylate, 5 parts of methacrylic acid, 6 parts of 20% aqueous solution of Latemule S-180A, 2 parts of ammonium persulfate A mixed solution of 5 parts of a% aqueous solution was emulsified with a homomixer, and the obtained pre-emulsified solution was allowed to flow into the reaction vessel from the dropping tank over 1 hour. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After completion of the inflow, the temperature in the reaction vessel was raised to 80 ° C. and kept for 30 minutes.

  Next, as step (3), 63 parts of methyl methacrylate, 30 parts of cyclohexyl methacrylate and 50 parts of butyl acrylate, 2 parts of methacrylic acid, a benzotriazole type ultraviolet absorber (product name: TINUVIN 384, manufactured by Ciba Geigy Japan, Inc.) 5 2.5 parts of a hindered amine light stabilizer (product name TINUVIN123, manufactured by Ciba Geigy Japan) was dissolved, and then 10 parts of a 20% aqueous solution of Latemul S-180A, 8 parts of a 2% aqueous solution of ammonium persulfate, water 230 parts of a mixed liquid mixture was prepared, and the mixed liquid was emulsified with a homomixer. The obtained pre-emulsified liquid was mixed with 1.7 parts of γ-methacryloxypropyltrimethoxysilane, 68 parts of methyltrimethoxysilane, and dimethyldimethoxy. Silicone consisting of 68 parts silane and 13 parts phenyltrimethoxysilane It was flowed over 1 hour from the dropping funnel into the reaction vessel while mixing with a metal mesh of the mixture and Y-tube sexual agent [A]. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and kept for 120 minutes.

After cooling to room temperature, the hydrogen ion concentration was measured and found to be pH 2.7. A 25% aqueous ammonia solution was added to the above mixture to adjust the pH to 10, followed by filtration through a 100 mesh wire mesh. The dry mass of the filtered agglomerate was very small, 20 ppm or less, and the amount of deposits on the inner wall of the reaction vessel and the stirring blade was small. The obtained emulsion had a solid content of 40.2% and an average particle size of 123 nm.
Subsequently, 1 kg of the silicone-modified acrylic emulsion obtained by the emulsion polymerization described above was charged into a SUS separable flask having an internal volume of 2 liters. The latex was heated to 80 ° C. by immersing the flask in a water bath. After adding an appropriate amount of antifoaming agent, the pressure in the flask was reduced to 40 kPa, and concentration was performed until the solid content increased to 45% by mass.
After cooling to room temperature, the hydrogen ion concentration was measured and found to be pH 7.2.
Thereafter, a 25% by mass aqueous ammonia solution was added to adjust the pH to 8.5, followed by filtration through a 100 mesh wire net. The dry weight of the filtered agglomerate was very small at 60 ppm with respect to the total monomer.

[Example 2]
The silicone modifier [A] used in step (1) is 3.3 parts of γ-methacryloxypropyltrimethoxysilane, 136 parts of methyltrimethoxysilane, 136 parts of dimethyldimethoxysilane, 31 parts of phenyltriethoxysilane, and step ( 3) The silicone modifier [A] used in 3) was changed to 1.7 parts of γ-methacryloxypropyltrimethoxysilane, 68 parts of methyltrimethoxysilane, 68 parts of dimethyldimethoxysilane, and 16 parts of phenyltrimethoxysilane. The same treatment as in Example 1 was performed. The dry mass of the filtered agglomerated material was very small at 40 ppm or less with respect to the obtained solid content mass, and the amount of deposits on the inner wall of the reaction vessel and the stirring blade was also slight. The obtained emulsion had a solid content of 42.3% and an average particle size of 146 nm. Thereafter, the same concentration treatment as in Example 1 was performed.

[Example 3]
The silicone modifier [A] used in step (1) is 3.3 parts of γ-methacryloxypropyltrimethoxysilane, 169 parts of methyltrimethoxysilane, 108 parts of dimethyldimethoxysilane, 21 parts of diphenyldimethoxysilane, and step (3 Example 1 except that the silicone modifier [A] used in) is 1.7 parts of γ-methacryloxypropyltrimethoxysilane, 85 parts of methyltrimethoxysilane, 54 parts of dimethyldimethoxysilane, and 10 parts of diphenyldimethoxysilane. The same process was performed. The dry mass of the filtered agglomerate was very small, 20 ppm or less, and the amount of deposits on the inner wall of the reaction vessel and the stirring blade was small. The obtained emulsion had a solid content of 40.5% and an average particle size of 118 nm. Thereafter, the same concentration treatment as in Example 1 was performed.

[Example 4]
The silicone modifier [A] used in step (1) is 3.3 parts of γ-methacryloxypropyltrimethoxysilane, 169 parts of methyltrimethoxysilane, 108 parts of dimethyldimethoxysilane, 23 parts of diphenyldiethoxysilane, and step ( 3) The silicone modifier [A] used in 3) was changed to 1.7 parts of γ-methacryloxypropyltrimethoxysilane, 85 parts of methyltrimethoxysilane, 54 parts of dimethyldimethoxysilane, and 12 parts of diphenyldiethoxysilane. The same treatment as in Example 1 was performed. The dry mass of the filtered agglomerate was very small at 50 ppm or less with respect to the obtained solid content mass, and the deposits on the inner wall of the reaction vessel and the stirring blade were also slight. The resulting emulsion had a solid content of 42.7% and an average particle size of 133 nm. Thereafter, the same concentration treatment as in Example 1 was performed.

[Example 5]
The silicone modifier [A] used in step (1) is 3.3 parts of γ-methacryloxypropyltrimethoxysilane, 136 parts of methyltrimethoxysilane, 136 parts of dimethyldimethoxysilane, 25 parts of cyclohexyltrimethoxysilane, and step ( 3) The silicone modifier [A] used in 3) was changed to 1.7 parts of γ-methacryloxypropyltrimethoxysilane, 68 parts of methyltrimethoxysilane, 68 parts of dimethyldimethoxysilane, and 13 parts of cyclohexyltrimethoxysilane. The same treatment as in Example 1 was performed. The dry mass of the filtered agglomerate was very small at 50 ppm or less with respect to the obtained solid content mass, and the deposits on the inner wall of the reaction vessel and the stirring blade were also slight. The obtained emulsion had a solid content of 44.8% and an average particle size of 156 nm. Thereafter, the same concentration treatment as in Example 1 was performed.

[Example 6]
Sulfosuccinic acid diester ammonium salt having a double bond copolymerizable with 320 parts of water and ethylenically unsaturated monomer in a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer (product) Name: 10 parts of 20% aqueous solution of Ramtel S-180A, manufactured by Kao Corporation), and the temperature was raised to 50 ° C. As step (1), 34 parts of methyl methacrylate, 30 parts of cyclohexyl methacrylate and 83 parts of butyl acrylate, 3 parts of methacrylic acid and 30 parts of 20% aqueous solution of Latemul S-180A, 15 parts of 2% aqueous solution of ammonium persulfate, water 320 parts of a mixed liquid was prepared, and the mixed liquid was emulsified with a homomixer to obtain a pre-emulsified liquid. The resulting pre-emulsified liquid reaction vessel was placed and the temperature was raised to 60 ° C. Next, as a silicone modifier [A], a mixed solution of 3.3 parts of γ-methacryloxypropyltrimethoxysilane, 122 parts of methyltrimethoxysilane, 122 parts of dimethyldimethoxysilane and 23 parts of phenyltrimethoxysilane was put into a reaction vessel. It was allowed to flow from the dropping tank over about 1 minute. After completion of the inflow, the temperature in the reaction vessel was raised to 80 ° C., and 10 parts of a 2% aqueous solution of ammonium persulfate was added and kept for 60 minutes.

Next, as step (2), 181 parts of methyl methacrylate, 70 parts of cyclohexyl methacrylate and 92 parts of butyl acrylate, 7 parts of methacrylic acid, a benzotriazole-based ultraviolet absorber (product name: TINUVIN 384, manufactured by Ciba Geigy Japan) 5 2.5 parts of a hindered amine light stabilizer (product name TINUVIN123, manufactured by Ciba Geigy Japan) was dissolved, and then 10 parts of a 20% aqueous solution of Latemul S-180A, 8 parts of a 2% aqueous solution of ammonium persulfate, water 350 parts of a mixed liquid mixture was prepared, and the mixed liquid was emulsified with a homomixer, and the resulting pre-emulsified liquid was mixed with 1.7 parts of γ-methacryloxypropyltrimethoxysilane, 81 parts of methyltrimethoxysilane, and dimethyldimethoxy. Silico consisting of 81 parts of silane and 15 parts of phenyltrimethoxysilane While mixing with a metal mesh of the mixture and Y-tube denaturing agent [A] were introduced into it over 90 minutes from the dropping tank into the reaction vessel. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and maintained for 90 minutes.

After cooling to room temperature, the hydrogen ion concentration was measured and found to be pH 2.6.
A 25% aqueous ammonia solution was added to the above mixture to adjust the pH to 8, followed by filtration through a 100 mesh wire mesh. The dry mass of the filtered agglomerate was very small, 20 ppm or less, and the amount of deposits on the inner wall of the reaction vessel and the stirring blade was small. The obtained emulsion had a solid content of 40.0% and an average particle size of 103 nm. Thereafter, the same concentration treatment as in Example 1 was performed.

[Example 7]
The silicone modifier [A] used in step (1) is 3.3 parts of γ-methacryloxypropyltrimethoxysilane, 153 parts of methyltrimethoxysilane, 98 parts of dimethyldimethoxysilane, 21 parts of diphenyldimethoxysilane, and step (2 Example 6 with the exception that 1.7 parts of γ-methacryloxypropyltrimethoxysilane, 102 parts of methyltrimethoxysilane, 65 parts of dimethyldimethoxysilane and 13 parts of diphenyldimethoxysilane were used as the silicone modifier [A] used in The same process was performed. The dry mass of the filtered agglomerate was very small, 20 ppm or less, and the amount of deposits on the inner wall of the reaction vessel and the stirring blade was small. The resulting emulsion had a solid content of 39.9% and an average particle size of 99 nm. Thereafter, the same concentration treatment as in Example 1 was performed.

[Comparative Example 1]
Silicone modifier [A] used in step (1) is 3.3 parts of γ-methacryloxypropyltrimethoxysilane, 169 parts of methyltrimethoxysilane, 135 parts of dimethyldimethoxysilane, and silicone modifier used in step (3). The same treatment as in Example 1 was performed except that the agent [A] was 1.7 parts of γ-methacryloxypropyltrimethoxysilane, 85 parts of methyltrimethoxysilane, and 68 parts of dimethyldimethoxysilane. The dry mass of the filtered agglomerate was very small, 20 ppm or less, and the amount of deposits on the inner wall of the reaction vessel and the stirring blade was small. The obtained emulsion had a solid content of 41.6% and an average particle size of 125 nm. Thereafter, the same concentration treatment as in Example 1 was performed.

[Comparative Example 2]
The silicone modifier [A] used in step (1) is 1.7 parts of γ-methacryloxypropyltrimethoxysilane, 203 parts of methyltrimethoxysilane, 108 parts of dimethyldimethoxysilane, and the silicone modifier used in step (3). The same treatment as in Example 1 was performed except that the agent [A] was 1.7 parts of γ-methacryloxypropyltrimethoxysilane, 102 parts of methyltrimethoxysilane, and 54 parts of dimethyldimethoxysilane. The dry mass of the filtered agglomerate was very small, 20 ppm or less, and the amount of deposits on the inner wall of the reaction vessel and the stirring blade was small. The obtained emulsion had a solid content of 41.5% and an average particle size of 121 m. Thereafter, the same concentration treatment as in Example 1 was performed.

Table 1 shows the properties and evaluation results of these emulsions.
As is apparent from Table 1, cracks occurred in the weather resistance promotion test using the eye super UV tester in Comparative Examples 1 and 2, whereas in Examples 1 to 7, cracks did not occur and the gloss retention decreased. There were few. This is because, as the silicone modifier [A] used, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and cyclohexyltrimethoxysilane were used, so that the silicone component was an ethylenically unsaturated monomer. This is thought to be due to being uniformly dispersed in the body polymer.

Claims (6)

A silicone-containing polymer comprising a silicone modifier [A], an ethylenically unsaturated monomer [B] having at least one carboxyl group, and at least one other ethylenically unsaturated monomer [C]. A molecular emulsion, wherein the silicone modifier [A] is represented by the following formula (1):
R ¹ _n —Si—R ³ _{4- (n + m)}
| (1)
R ² _m
((N.m) is a set of (1.0) or (1.1), and when n = 1 and m = 0, R ¹ is a phenyl group or a cyclohexyl group, and each R ³ is Each independently represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group, or when n = 1 and m = 1, R ¹ is a phenyl group or a cyclohexyl group, and R ² is A hydrogen atom, an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an alkyl acrylate group having 1 to 10 carbon atoms, or a 1 to 1 carbon atom Group consisting of silane (1) having a silicone structure represented by 10 alkyl methacrylate groups, and each R ³ is independently an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group. At least one kind selected from And the following formula (2):
CH ₃ —Si— (R ⁴ ) ₃ (2)
(Wherein each R ⁴ is independently an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group) and includes at least one selected from the group consisting of silanes (2) having a silicone structure The following formula (3):
(CH ₃ ) ₂ —Si— (R ⁵ ) ₂ (3)
(Wherein each R ⁵ is independently an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group) and / or at least one selected from the group consisting of silanes (3) having a silicone structure Alternatively, a silicone-containing polymer emulsion comprising a cyclic silane.   The silicone modifier [A], at least one ethylenically unsaturated monomer [B] having a carboxyl group, and at least one other ethylenically unsaturated monomer [C] are subjected to emulsion polymerization. The silicone-containing polymer emulsion according to claim 1, which is obtained as described above. The ethylenically unsaturated monomer [B] having a carboxyl group and the total weight of the ethylenically unsaturated monomer [B] having a carboxyl group and the other ethylenically unsaturated monomer [C] and Other ethylenically unsaturated monomers [C] are used in an amount of 90 to 99.5 wt% and 0.5 to 10 wt%, respectively, and the silicone modifier [A] is represented by the following formula 1/5 ≦ { Monomer [B] + Monomer [C]} / Monomer [A] ≦ 99.5 / 0.5
The silicone-containing polymer emulsion according to claim 1, wherein the silicone-containing polymer emulsion is obtained using an amount satisfying the relationship represented by: The silicone modifier [A] is at least one selected from the group consisting of silane (2) having a silicone structure represented by the above formula (2), the above cyclic silane, and the silicone represented by the formula (3) With respect to at least one selected from the group consisting of silane (2) having a silicone structure represented by the formula (2) with respect to a total weight of at least one selected from the group consisting of silane (3) having a structure The molar ratio of at least one selected from the group consisting of the cyclic silane and the silane (3) having a silicone structure represented by the formula (3) is at least 1/100, and is represented by the formula (1). At least one selected from the group consisting of silane (1) having a silicone structure is represented by the following formula 1/100 ≦ silane (1) / {silane (2) + silane (3)} ≦ 10 / 1
The silicone-containing polymer emulsion according to claim 1, wherein the silicone-containing polymer emulsion is used at a molar ratio satisfying the relationship represented by:   The silicone modifier [A] is the same or different (A-1) and (A-2), and the ethylenically unsaturated monomer [B] having the carboxyl group is the same or different (B -1) and (B-2), and the other ethylenically unsaturated monomers [C] are the same or different (C-1) and (C-2), and the emulsion polymerization is stepped. (1) and step (2) are carried out in this order. In step (1), the silicone modifier (A-1) and at least one ethylenically unsaturated monomer having a carboxyl group (B- 1) and at least one other ethylenically unsaturated monomer (C-1) are simultaneously emulsion polymerized to obtain a seed emulsion containing silicone. In step (2), the silicone modifier ( A-2) and ethylene having at least one carboxyl group It consists of an unsaturated monomer (B-2) and a polymer emulsion-polymerized from at least one other ethylenically unsaturated monomer (C-2). 4. The silicone-containing polymer emulsion according to any one of 4 above.   At least one ethylenically unsaturated monomer [B] is 5% by weight or more of acrylic acid and methacrylic acid having 5 to 12 carbon atoms based on the weight of the ethylenically unsaturated monomer [B]. 6. The silicone-containing polymer emulsion according to claim 1, which contains a cycloalkyl ester.