JP2013221094A - Coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating composition which is excellent in long period stability, good in adhesiveness to substrates, and does not rot without adding a preservative, even when stored for a long period.SOLUTION: A polymer emulsion composition is obtained from an ethylenic unsaturated monomer system (A) and an organic silane compound (B), and includes a cyclic organic silane compound in an amount of 0.02-10 wt.%.

Description

  The present invention relates to a coating composition.

  Emulsion compositions containing water-based polymers 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. (Here, “dry at normal temperature” means the general method of immobilization and fixing using the environment of the place of use as it is, and “dry under heating” means heat from a general heat source or light source, This refers to the general act of immobilizing and fixing a liquid that has been formed into a film by various general methods using methods such as molecular vibration directly or by radiation. However, when exposed to the outdoors or ultraviolet rays for a long time, there are problems of deterioration such as loss of gloss, discoloration, swelling, and cracks due to light, heat, rain, and the like.

  As a method for solving such a problem, for example, a highly weathering coating composition of Patent Document 1 is known.

JP 2008-38113 A

  However, since the composition described in Patent Document 1 generates molds when stored for a long period of time, the composition generally has antibacterial, antifungal and antialgal properties to prevent the growth of harmful microorganisms. Various antibacterial agents, fungicides and anti-algae agents are added. When mold and fungi are generated, there is a problem that not only a load is imposed on a person or environment to handle but also a uniform performance is not exhibited. In addition, when antiseptics such as antibacterial agents, fungicides, and algae preventives are added, there is a problem that uniform coatings cannot be made, so-called repellency and cracks are generated, and depending on the storage state while having such problems Also had the problem that its antiseptic, antibacterial and antifungal properties were deactivated. Further, it is a problem to affect not only the decay but also the long-term stability of the emulsion composition as a raw material and the coating composition itself. Moreover, when there are many cyclic | annular organosilane compounds, it was also a subject that adhesiveness to a base material is bad.

  The present invention provides a coating composition having excellent long-term stability, and further provides a coating composition having an antiseptic effect and good adhesion to a substrate without adding a preservative. Objective.

  As a result of intensive studies to solve the above problems, the present inventor has found that the cyclic organosilane compound has a role of preventing mold, and the cyclic organosilane compound exists in a specific range. Thus, the coating composition itself is a stable composition, has excellent mechanical stability, good adhesion to the base material, and has been found to be free from mold even after long-term storage, leading to the completion of the present invention. Is.

（Ｒ¹は炭素数２以上のアルキル基、炭素数１〜１０のメタクリル酸アルキル基、フェニル基またはシクロヘキシル基を表し、Ｒ^２は水素原子、炭素数２以上の脂肪族炭化水素基を表し、Ｒ^３はそれぞれ、独立して、炭素数１〜８のアルコキシ基、アセトキシ基又は水酸基を表す。ｎは１〜３、ｍは０〜１、ただしｎ＋ｍ≦３である。）
であり、
（ｂ２）は、下記一般式（２）で示される有機シラン化合物：
ＣＨ_３−Ｓｉ−(Ｒ^４)_３ （２）
（Ｒ^４はそれぞれ独立して炭素数１〜８のアルコキシ基、アセトキシ基又は水酸基を表す。）
であり、
（ｂ３）は、下記一般式（３）で示される有機シラン化合物及び環状有機シラン化合物の少なくとも１種：
（ＣＨ_３）_２ −Ｓｉ−（Ｒ^５）_２ （３）
（Ｒ^５はそれぞれ独立して炭素数１〜８のアルコキシ基、アセトキシ基又は水酸基を表す。）
である、［１］又は［２］に記載の重合体エマルジョン組成物。
［４］ 該有機シラン化合物（Ｂ）が（ｂ３）を含み、（ｂ３）の量が、該有機シラン化合物（Ｂ）の重量に対して１０質量％〜７０質量％である、［３］に記載の重合体エマルジョン組成物。
［５］ 有機シラン化合物（Ｂ）が、下記（ｂ１）〜（ｂ３）を含み、
（ｂ１）は、下記一般式（１）で示される有機シラン化合物：

（Ｒ¹は炭素数２以上のアルキル基、炭素数１〜１０のメタクリル酸アルキル基、フェニル基またはシクロヘキシル基を表し、Ｒ^２は水素原子、炭素数２以上の脂肪族炭化水素基を表し、Ｒ^３はそれぞれ、独立して、炭素数１〜８のアルコキシ基、アセトキシ基又は水酸基を表す。ｎは１〜３、ｍは０〜１、ただしｎ＋ｍ≦３である。）
であり、
（ｂ２）は、下記一般式（２）で示される有機シラン化合物：
ＣＨ_３−Ｓｉ−(Ｒ^４)_３ （２）
（Ｒ^４はそれぞれ独立して炭素数１〜８のアルコキシ基、アセトキシ基又は水酸基を表す。）
であり、
（ｂ３）は、下記一般式（３）で示される有機シラン化合物及び環状有機シラン化合物の少なくとも１種：
（ＣＨ_３）_２ −Ｓｉ−（Ｒ^５）_２ （３）
（Ｒ^５はそれぞれ独立して炭素数１〜８のアルコキシ基、アセトキシ基又は水酸基を表す。）
であり、（ｂ３）の量が、該有機シラン化合物（Ｂ）の重量に対して１０質量％〜７０質量％である、［１］又は［２］に記載の重合体エマルジョン組成物。
［６］ 環状有機シラン化合物は、重合中に生成する又は重合反応中に（ｂ３）として添加されたものである。［３］〜［５］に記載の重合体エマルジョン組成物。
［７］ 環状シラン有機化合物は、下記一般式（４）で示される化合物である［１］〜［６］のいずれか１つに記載の重合体エマルジョン。

（Ｒ⁶は炭素数１〜２のアルキル基を表し、ｌは３〜８の整数を表す。）
［８］ 環状有機シラン化合物は、４員環シランと５員環シランを含有する［１］〜［７］のいずれか一つに記載の重合体エマルジョン組成物。
［９］ ４員環シラン／５員環シランの比率が１００／１〜１／１である［８］に記載の重合体エマルジョン組成物。 The present invention has the following aspects.
[1] A polymer emulsion composition obtained from an ethylenically unsaturated monomer system (A) and an organic silane compound (B) and containing 0.02% by mass to 10% by mass of a cyclic organic silane compound.
[2] The ethylenically unsaturated monomer system (A) comprises (a1) 80% by mass to 99.7% by mass of one or more ethylenically unsaturated monomers, and (a2) 0.3% by mass to The polymer emulsion composition according to [1], comprising 20% by mass of one or more unsaturated carboxylic acids.
[3] The organosilane compound (B) includes at least one of the following (b1) to (b3):
(B1) is an organosilane compound represented by the following general formula (1):

(R ¹ represents an alkyl group having 2 or more carbon atoms, an alkyl group having 1 to 10 carbon atoms, a phenyl group or a cyclohexyl group, R ² represents a hydrogen atom, an aliphatic hydrocarbon group having 2 or more carbon atoms, R ³ independently represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group, n is 1 to 3, m is 0 to 1, and n + m ≦ 3.
And
(B2) is an organosilane compound represented by the following general formula (2):
CH ₃ —Si— (R ⁴ ) ₃ (2)
(R ⁴ each independently represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group or a hydroxyl group.)
And
(B3) is at least one of an organosilane compound and a cyclic organosilane compound represented by the following general formula (3):
(CH ₃ ) ₂ —Si— (R ⁵ ) ₂ (3)
(R ⁵ independently represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group or a hydroxyl group.)
The polymer emulsion composition according to [1] or [2].
[4] The organic silane compound (B) contains (b3), and the amount of (b3) is 10% by mass to 70% by mass with respect to the weight of the organic silane compound (B). The polymer emulsion composition described.
[5] The organosilane compound (B) includes the following (b1) to (b3),
(B1) is an organosilane compound represented by the following general formula (1):

(R ¹ represents an alkyl group having 2 or more carbon atoms, an alkyl group having 1 to 10 carbon atoms, a phenyl group or a cyclohexyl group, R ² represents a hydrogen atom, an aliphatic hydrocarbon group having 2 or more carbon atoms, R ³ independently represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group, n is 1 to 3, m is 0 to 1, and n + m ≦ 3.
And
(B2) is an organosilane compound represented by the following general formula (2):
CH ₃ —Si— (R ⁴ ) ₃ (2)
(R ⁴ each independently represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group or a hydroxyl group.)
And
(B3) is at least one of an organosilane compound and a cyclic organosilane compound represented by the following general formula (3):
(CH ₃ ) ₂ —Si— (R ⁵ ) ₂ (3)
(R ⁵ independently represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group or a hydroxyl group.)
The polymer emulsion composition according to [1] or [2], wherein the amount of (b3) is 10% by mass to 70% by mass with respect to the weight of the organosilane compound (B).
[6] The cyclic organosilane compound is produced during polymerization or added as (b3) during the polymerization reaction. The polymer emulsion composition as described in [3]-[5].
[7] The polymer emulsion according to any one of [1] to [6], wherein the cyclic silane organic compound is a compound represented by the following general formula (4).

(R ⁶ represents an alkyl group having 1 to 2 carbon atoms, and l represents an integer of 3 to 8)
[8] The polymer emulsion composition according to any one of [1] to [7], wherein the cyclic organosilane compound contains a 4-membered ring silane and a 5-membered ring silane.
[9] The polymer emulsion composition according to [8], wherein the ratio of 4-membered ring silane / 5-membered ring silane is 100/1 to 1/1.

  The emulsion composition containing the water-based polymer of the present invention is excellent in mechanical stability, has an antifungal effect that does not rot even if stored for a long time without adding a preservative, and functions as a fixed film. Long-term maintenance performance.

  Hereinafter, the present invention will be specifically described. The emulsion composition of the present invention is an acrylic emulsion (hereinafter simply abbreviated as an emulsion) and can be obtained by an ordinary multistage emulsion polymerization method. There is no restriction | limiting in particular regarding the method of emulsion polymerization, A conventionally well-known method can be used.

（Ｒ⁶は炭素数１〜２のアルキル基を表し、ｌは３〜８の整数を表す。）
環状有機シラン化合物は式（４）で示される化合物を原料として添加することができる。また、この環状有機シラン化合物は、式（３）で示される化合物を系中で加水分解して、その後、脱水縮合反応により得ることもできる。
更に、環状有機シラン化合物として４員環シラン（式（４）においてｌが４）と５員環シラン（式（４）においてｌが５の場合）を有することが好ましく、カビ防止効果を得ることができる。エマルジョン組成物中に４員環シランと５員環シランが合わせて０．０２から１０質量％含まれていることが必要である。この範囲が０．０２〜５質量％であればより好ましい。この範囲であると、防カビ性を得ながらも基材密着性を得ることができる点で好ましい。また、４員環と５員環の割合（４員環／５員環）、防カビ効果と長期安定性の観点から、４員環／５員環の比率が１００／１〜１／１であることが好ましい。この範囲はさらに好ましくは、１００／１〜１０／１である。 The polymer emulsion composition of the present invention contains 0.02% by mass to 10% by mass of a cyclic organosilane compound. This cyclic organic silane compound may be a cyclic organic silane compound used as a raw material, or may be a cyclic organic silane compound produced by a reaction.
The cyclic organosilane compound is preferably a compound represented by the following general formula (4).

(R ⁶ represents an alkyl group having 1 to 2 carbon atoms, and l represents an integer of 3 to 8)
The cyclic organosilane compound can be added using a compound represented by the formula (4) as a raw material. This cyclic organosilane compound can also be obtained by hydrolyzing the compound represented by the formula (3) in the system and then dehydrating condensation reaction.
Furthermore, it is preferable to have a 4-membered ring silane (l is 4 in formula (4)) and a 5-membered ring silane (when l is 5 in formula (4)) as the cyclic organosilane compound, and to obtain a mold prevention effect. Can do. It is necessary that the emulsion composition contains 0.02 to 10% by mass of 4-membered ring silane and 5-membered ring silane in total. It is more preferable that this range is 0.02 to 5% by mass. This range is preferable in that the adhesion to the substrate can be obtained while obtaining the antifungal property. In addition, the ratio of 4-membered ring to 5-membered ring (4-membered ring / 5-membered ring), the ratio of 4-membered ring / 5-membered ring is 100/1 to 1/1 from the viewpoint of mold prevention effect and long-term stability. Preferably there is. This range is more preferably 100/1 to 10/1.

  In the present invention, the raw materials used will be described.

[Ethylenically unsaturated monomer system (A)]
The ethylenically unsaturated monomer system (A) used in the present invention contains (a1) one or more ethylenically unsaturated monomers and (a2) one or more unsaturated carboxylic acids. Each is exemplified below, but is not particularly limited.

  Specific examples of the (a1) one or more ethylenically unsaturated monomers include (meth) acrylic acid ester monomers, aromatic monomers, hydroxyl group-containing monomers, amide group-containing monomers. And epoxy group-containing monomers.

  Examples of (meth) acrylic acid ester monomers include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and benzyl acrylate. , Phenyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl acrylate, butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, benzyl methacrylate, and phenyl methacrylate. Preferred are butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, and cyclohexyl methacrylate.

  Examples of the aromatic monomer include styrene, vinyl toluene, α-methyl styrene, and the like. Styrene is preferred.

  Examples of the hydroxyl group-containing monomer include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, polyethylene glycol acrylate, and polyethylene glycol methacrylate. Preferred are hydroxyethyl acrylate and hydroxyethyl methacrylate.

  Examples of the amide group-containing monomer include acrylamide, methacrylamide, N, N-methylenebisacrylamide, diacetone acrylamide, diacetone methacrylamide, maleic acid amide, N-methylol acrylamide, N-methylol methacrylamide, N- Mention may be made of methoxymethyl acrylamide, N-methoxymethyl methacrylamide, N-butoxymethyl acrylamide, N-butoxymethyl methacrylamide and the like. Preferred are acrylamide, methacrylamide, and diacetone acrylamide.

  Examples of the epoxy group-containing monomer include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, methyl glycidyl acrylate, and methyl glycidyl methacrylate. Glycidyl methacrylate is preferred.

  In addition to these monomers, monomer components other than those described above can be further used in order to improve various qualities and physical properties required for the acrylic aqueous emulsion of the present invention. As these monomers, other polymerizable monomers copolymerizable with the above-mentioned monomers can be used. For example, various monomers having functional groups such as amino group, sulfonic acid group, and phosphoric acid group, as well as vinyl acetate, vinyl propionate, vinyl versatic acid, vinyl pyrrolidone, methyl vinyl ketone, butadiene, ethylene, propylene, Vinyl chloride, vinylidene chloride and the like can be used as desired.

  Specific examples of the (a2) one or more unsaturated carboxylic acids used in the present invention include, for example, monocarboxylic acids such as acrylic acid, methacrylic acid, itaconic acid half ester, maleic acid half ester, fumaric acid A half ester, crotonic acid, etc. are mentioned, As a dicarboxylic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, etc. are mentioned, 1 or 2 or more selected from these groups can be used. Acrylic acid and methacrylic acid are particularly preferred. Furthermore, it is preferable to use 0.3-10 mass% unsaturated carboxylic acid with respect to the whole ethylenically unsaturated monomer type | system | group (A) used in order to obtain a (meth) acrylic-type polymer emulsion. These unsaturated carboxylic acids act as a catalyst for promoting the hydrolysis reaction and condensation reaction of the organosilane compound (B), or act as a stabilizer.

  The ethylenically unsaturated monomer system (A) used in the present invention comprises (a1) 80% by mass to 99.7% by mass of one or more ethylenically unsaturated monomers and (a2) one or more types of unsaturated monomers. A saturated carboxylic acid is included at 0.3 mass% to 20 mass%. When (a1) is 80% by mass or more and (a2) is 20% by mass or less, the viscosity of the emulsion is not too high, and the polymerization stability is good. When (a1) is 99.7% by mass or less and (a2) is 0.3% by mass or more, the acceleration rate of the hydrolysis reaction and condensation reaction of the organosilane compound (B) is increased, and the emulsion is good. Expresses its stability.

[Organic Silane Compound (B)]
The organosilane compound (B) used as a raw material in the present invention preferably contains at least one of (b1) to (b3). A specific example will be described below.

（Ｒ^１は炭素数２以上のアルキル基、炭素数１〜１０のメタクリル酸アルキル基、フェニル基またはシクロヘキシル基を表し、Ｒ^２は水素原子、炭素数２以上の脂肪族炭化水素基を表し、Ｒ^３はそれぞれ、独立して、炭素数１〜８のアルコキシ基、アセトキシ基又は水酸基を表す。ｎは１〜３、ｍは０〜１、ただしｎ＋ｍ≦３である。） (B1) is an organosilane compound represented by the following general formula (1).

(R ¹ represents an alkyl group having 2 or more carbon atoms, an alkyl group having 1 to 10 carbon atoms, a phenyl group or a cyclohexyl group, R ² represents a hydrogen atom, an aliphatic hydrocarbon group having 2 or more carbon atoms, R ³ independently represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group, n is 1 to 3, m is 0 to 1, and n + m ≦ 3.

  Preferable specific examples of (b1) include phenyltrimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, cyclohexyltrimethoxysilane, dicyclohexyldimethoxysilane, cyclohexyltriethoxysilane, and dicyclohexyl. Diethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, vinylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxy Propyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane Emissions, .gamma.-methacryloxypropyl triethoxysilane, .gamma.-methacryloxypropyltrimethoxysilane such as propyl methyl diethoxy silane and the like, may be used one or more selected from these groups. Particularly preferred are γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane. Furthermore, it is preferable to use 0.1-10 mass% alkoxysilane group containing polymerizable monomer with respect to the whole polymerizable monomer used in order to obtain a (meth) acrylic-type polymer emulsion. In particular, from the viewpoint of polymerization stability, blending stability, and water resistance of the resulting coating film, 0.1 to 5% by mass is preferable.

(B2) is an organosilane compound represented by the following general formula (2).
CH ₃ —Si— (R ₄ ) ₃ (2)
(R ₄ each independently represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group or a hydroxyl group.)
Preferable specific examples of (b2) include methyltrimethoxysilane and methyltriethoxysilane, and may contain two or more of these.

(B3) is at least one of an organosilane compound and a cyclic organosilane compound represented by the following general formula (3).
Formula (3):
(CH ₃ ) ₂ —Si— (R ₅ ) ₂ (3)
(R ₅ independently represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group or a hydroxyl group.)
Preferable specific examples of the organic silane compound of the formula (3) include dimethyldimethoxysilane, dimethyldiethoxysilane and the like.
When an organosilane compound is added as (b3), the amount of the cyclic organosilane compound produced during the polymerization can be controlled by the ratio of (b2) and (b3). When the ratio of (b2) is larger than the ratio of (b3), the generated cyclic organosilane compound is reduced. From the viewpoint of mold prevention and long-term stability of the emulsion, the ratio of (b2) / (b3) is preferably 4.95 / 1 to 7.15 / 10000.

（Ｒ⁶は炭素数１〜２のアルキル基を表し、ｌは３〜８の整数を表わす。）
また環状有機シラン化合物の具体例としては、４員環又はＤ４で表されるオクタメチルシクロテトラシロキサン、テトラメチルテトラビニルシクロテトラシロキサン等、５員環又はＤ５で表されるデカメチルシクロペンタシロキサン等が挙げられる。また、オクタフェニルシクロシロキサン、デカメチルシクロペンタシロキサン、ヘキサメチルシクロトリシロキサン等が例示でき、これらの二種以上を含んでいてもよい。 The cyclic organosilane compound is preferably a compound represented by the following general formula (4).

(R ⁶ represents an alkyl group having 1 to 2 carbon atoms, and l represents an integer of 3 to 8)
Specific examples of the cyclic organosilane compound include 4-membered rings or octamethylcyclotetrasiloxane represented by D4, tetramethyltetravinylcyclotetrasiloxane, etc., 5-membered rings or decamethylcyclopentasiloxane represented by D5, etc. Is mentioned. Moreover, octaphenylcyclosiloxane, decamethylcyclopentasiloxane, hexamethylcyclotrisiloxane and the like can be exemplified, and two or more of these may be included.

Furthermore, it is preferable that the cyclic organic silane compound is at least one of a 4-membered ring silane and a 5-membered ring silane. By including these, an antifungal effect can be obtained.
In order to improve the stability of the emulsion composition of the present invention, the amount of (b3) is preferably 10% by mass to 70% by mass with respect to the weight of the organosilane compound (B).

  In addition, the method of introducing the cyclic organosilane compound is important for the ability to prevent mold. The cyclic organosilane compound produced during the polymerization and / or added as a raw material during the polymerization has an antifungal effect on the emulsion, but when the cyclic organosilane compound is added to the emulsion after the production, May be less effective.

  The organic silane compound (B) further includes isobutyltrimethoxysilane, vinylethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxypropyl. Triethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and the like can be included.

  In the present invention, since the organosilane compound (B) has a specific structure, it has excellent long-term stability and adhesion to the substrate while maintaining high durability, and also has an antifungal effect.

  From the viewpoint of high weather resistance, the weight ratio of the ethylenically unsaturated monomer system (A) to the organosilane compound (B) is preferably 1000/1 to 1/1. Further, the weight ratio of (A) to (B) is preferably 100/1 to 1/1. Within this weight ratio range, the emulsion can be obtained particularly stably, and the water resistance and weather resistance of the film obtained from the emulsion are particularly excellent.

The presence of the above organosilane compound can be known by ²⁹ SiNMR ( ²⁹ Si nuclear magnetic resonance spectrum) or ¹ HNMR (proton nuclear magnetic resonance spectrum). For example, the organosilane compound (b2) can be identified by ²⁹ SiNMR chemical shift showing a peak at −40 to −80 PPM. Further, the organic silane compound (b3) can be identified by a ²⁹ Si NMR chemical shift having a peak at −16 to −26 PPM. The amount of the cyclic organosilane compound can be quantified by gas chromatography.

<Manufacturing method>
As a method for producing the emulsion of the present invention, a conventional multistage emulsion polymerization method can be employed. As a typical example, in the presence of a polymerizable monomer, an emulsifier, a polymerization initiator, and other additive components optionally used in water, a polymerizable monomer having a pH of 4 or less. The body is usually subjected to emulsion polymerization under heating at 60 to 90 ° C., and this step is repeated a plurality of times.

  The emulsifier is not particularly limited, and for example, an anionic emulsifier, a nonionic emulsifier, a cationic emulsifier, an amphoteric emulsifier, a polymer emulsifier, and the like can be used. For example, fatty acid salts such as sodium lauryl sulfate, higher alcohol sulfates, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, polyoxyethylene alkyl ether sulfates, polyoxyethylene polycyclic phenyl ether sulfates, polyoxynonyls Anionic surfactants such as phenyl ether sulfonate, polyoxyethylene-polyoxypropylene glycol ether sulfate, so-called reactive emulsifier having a sulfonic acid group or sulfate ester group and a polymerizable unsaturated double bond in the molecule Polyoxyethylene alkyl ether, polyoxyethylene nonylphenyl ether, sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene block copolymer, Nonionic surfactants such as reactive nonionic surfactants having a skeleton and a polymerizable unsaturated double bond in the molecule; Cationic surfactants such as alkylamine salts and quaternary ammonium salts; (Modified) Polyvinyl alcohol etc. are mentioned. These emulsifiers may be used alone or in combination of several kinds.

  The polymerization method for emulsion polymerization of emulsions is a monomer batch charging method in which monomers are charged in a batch, a monomer dropping method in which monomers are continuously dropped, a monomer, water, and an emulsifier. Can be mixed and emulsified in advance, and a pre-emulsion method in which these are added dropwise, or a combination thereof. The method for using the polymerization initiator is not particularly limited.

  A general radical initiator can be used as the polymerization initiator used for emulsion polymerization of the emulsion. A radical polymerization initiator is one that generates radicals by heat or a reducing substance to cause addition polymerization of a polymerizable monomer. Water-soluble or oil-soluble persulfates, peroxides, azobis compounds are included. Specifically, 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 are mentioned, and water-soluble ones are preferable. When acceleration of the polymerization rate or a low temperature reaction is desired, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbic acid, formaldehyde sulfooxylate salt or the like can be used in combination with the radical polymerization initiator.

In particular, by employing the following production method, an emulsion composition containing a 4-membered ring and a 5-membered ring in a certain range as described above can be obtained.
That is, when the organosilane compound represented by the general formula (3) is used as (b3), the cyclic organosilane produced during the polymerization depends on how to introduce (b2) and (b3) and the order of introduction. The amount of compound can be controlled.

  Specifically, it is preferable that the ratio of (b2) / (b3) raw material input is 4/1 to 1/70. More preferably, it is 2/1 to 1/7. In addition, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, etc. are introduced simultaneously with one or more compounds of (b1), (b2), and (b3) during polymerization, thereby preventing mold and improving long-term stability. The amount of the cyclic organosilane compound having a sex effect can be adjusted.

  Moreover, as a specific example of the order of raw material charging, the amount of cyclic organosilane compound generated is increased by introducing (b2) after introducing (b3) alone. On the contrary, when it is desired to suppress the generation amount of the cyclic organosilane compound, the ratio of (b2) is used more than the ratio of (b3) and introduced simultaneously with (b3).

  For example, thickeners, film-forming aids, plasticizers, antifreezing agents, antifoaming agents, dyes, preservatives, ultraviolet absorbers, light stabilizers, and the like can be arbitrarily blended in the emulsion.

Ultraviolet absorbers include benzophenone series, benzotriazole series, and triazine series. Specific examples of the benzophenone ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and 2-hydroxy-4-n-octate. Xibenzophenone, 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'-carboxybenzo Enon, such as 2-hydroxy-4-stearyloxy benzophenone.
Specific examples of the radical polymerizable benzophenone ultraviolet absorber 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- And (acryloxy-triethoxy) benzophenone.

  Specific examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 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 and polyethylene Condensate with glycol (molecular weight 300) (manufactured by Ciba Geigy Japan, product name: TINUVIN 1130), isooctyl-3- [3- (2H (12) 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) benzoto Azole, 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-1phenylethyl) phenol (manufactured by Nippon Ciba-Geigy Co., Ltd., product name: TINUVIN900).

  Specific examples of radically polymerizable benzotriazole-based ultraviolet 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] Phenyl propionate (Nippon Ciba Geigy Co., Ltd., product name: CGL-104) and the like can be mentioned.

  Specific examples of the triazine-based ultraviolet absorber include TINUVIN 400 (product name, manufactured by Ciba Geigy Japan, Inc.).

  As the light stabilizer, hindered amine light stabilizers are preferable, among them, those having low basicity are more preferable, and those having a base constant (pKb) of 8 or more are particularly preferable. Specific examples of the light stabilizer include 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-butyl malonate, 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-tetra A mixture of methylpiperidine, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidyl-sebacate (Nippon Chi Product made by Geigy Co., Ltd., product name: TINUVIN292), bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, TINUVIN123 (product name, manufactured by Ciba-Geigy Japan), etc. It is done.

  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 2,2,6,6-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 present invention, the ultraviolet absorber and / or the light stabilizer are introduced into the acrylic emulsion by being present during the emulsion polymerization for producing the acrylic emulsion, and the ultraviolet absorber and / or the light stabilizer are used as a film forming aid. A method of introducing by mixing with an acrylic emulsion, etc., mixing an ultraviolet absorber and / or a light stabilizer with a film-forming aid, emulsifying a surfactant and water, and then emulsifying the emulsion. The method of introduce | transducing by adding to is mentioned. In addition, when an ultraviolet absorber and a light stabilizer are used in combination, it exhibits excellent durability due to a synergistic effect. Also, certain pigments and additives have the same effect.

  In the present invention, the pH of the pre-emulsion liquid comprising a carboxyl group-containing polymerizable monomer, another polymerizable monomer and an emulsifier is not particularly limited, but by carrying out emulsion polymerization at a pH of 5 or less, Since the condensation reaction of the organosilane compound (B) occurs rapidly and the condensation reaction can be prevented from proceeding after the emulsion polymerization, the storage stability as a product is improved.

  Examples of the crosslinking agent used in the present invention include compounds having an isocyanate group, compounds having an aziridine ring, compounds having an oxazoline ring, and compounds having a carbodiimide group.

  The compound having an isocyanate group used in the present invention is not particularly limited as long as it has two or more isocyanate groups in the molecule, but 1,6-hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene. Adduct polyisocyanate compounds such as diisocyanate, isophorone diisocyanate, metaxylylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), and trimethylolpropane adducts, burettes, isocyanurates, etc., which are derivatives of these diisocyanates, These isocyanate group-containing polymerizable monomers are homopolymerized by a known polymerization method, copolymerized with other polymerizable monomers, or the like. It can be used et the emulsion.

  As the compound having an isocyanate group used in the present invention, a water-dispersible polyisocyanate compound modified with a nonionic and / or ionic surfactant is suitable from the viewpoint of water-dispersibility. . As such a polyisocyanate compound, any compound obtained by introducing a hydrophilic group by a conventionally known method can be used without particular limitation. For example, a reaction product of an alkoxy polyalkylene glycol and a polyisocyanate compound, a surface active ability Reaction product of vinyl polymer containing nonionic group and isocyanate-reactive group (hydroxyl group, etc.) having polyisocyanate and polyisocyanate compound, reaction product obtained by reacting dialkanolamine, isethionate amine salt Examples thereof include a polyisocyanate compound containing a reaction product of a compound having a sulfonic acid group and an isocyanate reactive group and a polyisocyanate compound. Among these, a polyisocyanate compound containing a reaction product of an alkoxy polyalkylene glycol and a polyisocyanate compound is particularly preferable because of its excellent water dispersibility.

  The dispersoid average particle diameter of the emulsion produced according to the present invention is not particularly limited, but can be effectively utilized if it is in the range of 0.01 to 5000 nm. Further, the solid content is not limited. However, the viscosity is preferably adjusted as appropriate according to the application and formulation from the viewpoint of use conditions such as dilution and storage stability. To maintain long-term dispersion stability of the emulsion, basic substances such as basic organic compounds such as amines such as ammonia and dimethylaminoethanol, and alkali metal salts such as sodium hydroxide and potassium hydroxide are also used. It is preferable to adjust the pH to a range of 5 to 10 using a basic inorganic compound or the like.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited at all by these examples. In addition, the part and% in an Example and a comparative example show a mass part and mass%, respectively.

(1) Evaluation of polymerization stability The (meth) acrylic polymer emulsion obtained after emulsion polymerization is filtered through a 100-mesh filter cloth, and the residue mass is determined by the mass of the (meth) acrylic polymer emulsion. The residue rate was determined.
○: Residual rate is less than 100 ppm Δ: Residual rate is 100 ppm or more and less than 1000 ppm x: A large amount of aggregates are generated

(2) Solid content ratio of (meth) acrylic polymer emulsion This is the dry mass after the (meth) acrylic polymer emulsion was dried at 105 ° C. for 3 hours. More specifically, about 1 g of (meth) acrylic polymer emulsion was accurately weighed in an aluminum dish whose mass was previously known, dried at 105 ° C. for 3 hours with a constant temperature dryer, and then silica gel was added. In a desiccator, allow to cool for 30 minutes and then weigh accurately. The solid content was obtained by dividing the mass after drying of the substance by the mass before drying.

(3) Measurement of particle diameter The average particle diameter of the obtained (meth) acrylic polymer emulsion was measured with a Microtrac particle size distribution meter manufactured by Leeds & Northrup.

(4) Measurement of cyclic organic silane compound The organic cyclic silane compound of the obtained (meth) acrylic polymer emulsion was measured by gas chromatography (CL Sciences, GC 353B) manufactured by Shimadzu Corporation.
The measurement conditions for gas chromatography are shown below.
Quantitative method: External standard method Measurement sample: Dilute latex 10 times with water Standard sample: Dilute benzyl alcohol with distilled water Column: TC5 30m
Temperature setting conditions: inlet temperature 180 ° C, detector temperature 220 ° C, column temperature 200 ° C
Initial column oven temperature: 50 ° C
Setting of temperature raising condition of the column: After holding at 50 ° C. for 8 minutes, the temperature was raised at 8 ° C./minute and kept at 170 ° C. for 7 minutes.
Split ratio: 20
Injection volume: 2 μl

(5) Long-term stability (representative test: mechanical stability test)
The emulsion composition (50 g) was put in a marron dedicated container, set in a maron tester (Maron mechanical stability tester, manufactured by Kumagai Riki Kogyo Co., Ltd.), and stirred for 5 minutes at a load of 15 kg and a rotational speed of 1200 rpm. The material after the Maron test was filtered through an 80 mesh wire net and further washed with water until no cloudy water was produced. The wire mesh leaving the residue is dried in a dryer at 105 ° C. for 30 minutes. The mixture was allowed to cool for 5 minutes or more with a desiccator, and precisely weighed to the fourth decimal place with a balance.
Excellent: 200 mg or less Good: 200-1000 mg
Possible: 1000mg or more

(6) Substrate adhesion test (A) Adhesion test to coated steel sheet: The coating composition was applied to a coated steel sheet coated with a polyester / melamine paint so that the coating composition would be 15 g (dry) / m ^2. It was allowed to stand in an oven at 7 ° C. for 7 minutes and further allowed to stand at room temperature for 1 day. One day later, an adhesion test was conducted according to JISK5400 8.5 adhesive cross-cut tape. Judgment is performed by counting the remaining number of grids, passing 90/100 or higher (◎), 80/100 or higher passing (O), 60-79 / 100 failing (△), and less than 59/100 failing ( X).
Further, the coated plate was immersed in warm water at 60 ° C. for 8 hours, taken up from the immersion, and then left at room temperature for 1 hour to conduct an adhesion test. Judgment is performed by counting the remaining number of grids, passing 90/100 or higher (◎), 80/100 or higher passing (O), 60-79 / 100 failing (△), and less than 59/100 failing ( X).

(B) Adhesion test to ceramic base material: A paint composition was applied to a slate plate at 10 g (dry) / m ² , left in an oven at 80 ° C. for 7 minutes, and then allowed to stand at room temperature for 1 day. I let you. One day later, an adhesion test was conducted according to JISK5400 8.5 adhesive cross-cut tape. Judgment is performed by counting the remaining number of grids, passing 90/100 or higher (◎), 80/100 or higher passing (O), 60-79 / 100 failing (△), and less than 59/100 failing ( X).
Further, the coated plate was immersed in warm water at 60 ° C. for 8 hours, taken up from the immersion, and then left at room temperature for 1 hour to conduct an adhesion test. Judgment is performed by counting the remaining number of grids, passing 90/100 or higher (◎), 80/100 or higher passing (O), 60-79 / 100 failing (△), and less than 59/100 failing ( X).

(7) Antifungal evaluation test (antibacterial activity evaluation test)
In the present invention, an antibacterial activity evaluation test was performed using sensory evaluation. Place the emulsion in a 250 mm plastic cup by the 8th minute and store it in an atmosphere with a temperature of 50 ° C. and a humidity of 90%. The other is stored in an atmosphere of 23 ° C x 50% humidity. One week later, a parameter of 50 was selected arbitrarily, and the odor of each liquid was judged by odor.
◎: No odor of rot ○: No odor of rot △: Little odor of rot ×: Odor of rot

[Example 1]
In a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, water 516 parts, Aqualon KH1025 (ammonium-α-sulfonato-ω-1- (allyloxymethyl) alkyloxypolyoxyethylene: Daiichi Kogyo Seiyaku ( 2.4 parts) was added, the temperature in the reaction vessel was raised to 80 ° C., 15 parts of a 2% aqueous solution of ammonium peroxodisulfate was added, and 5 minutes later, as step (1), methacrylic 110 parts of methyl acid (MMA), 40 parts of cyclohexyl methacrylate (CHMA), 105 parts of butyl methacrylate (BMA), 140 parts of butyl acrylate (BA), 5 parts of methacrylic acid (MAA), 4 parts of Aqualon KH1025, Emulgen 120 parts of 4 parts, 2% aqueous solution of ammonium persulfate 20 parts, and 270 parts of water were prepared and mixed. The liquid was emulsified with a homomixer to obtain a pre-emulsion liquid. 4 parts of γ-methacryloxypropyltrimethoxysilane (SZ6030: manufactured by Toray Dow Corning Silicone Co., Ltd.), methyltrimethoxysilane (SZ6070: manufactured by Toray Dow Corning Silicone Co., Ltd.) 50 parts, 50 parts of dimethyldimethoxysilane (AY43-004: manufactured by Toray Dow Corning Silicone), SH244 (octamethylcyclotetrasiloxane: manufactured by Toray Dow Corning Silicone) 0.45 parts, SH245 (Decamethylcyclopentasiloxane: manufactured by Toray Dow Corning Silicone Co., Ltd.) 0.05 part of a silicone modifier (B) mixed solution and the reaction vessel were allowed to flow 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), 200 parts of water, 150 parts of methyl methacrylate (MMA), 30 parts of cyclohexyl methacrylate (CHMA), 80 parts of butyl methacrylate (BMA), 30 parts of butyl acrylate (BA), methacrylic acid (MAA) 5 parts, acrylic acid (AA) 5 parts, Aqualon KH1025 3 parts, 2% aqueous solution of ammonium persulfate 15 parts emulsified with a homomixer, and the resulting pre-emulsified solution was dropped into the reaction vessel It flowed in from the 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 (3), 150 parts of methyl methacrylate (MMA), 30 parts of cyclohexyl methacrylate (CHMA), 55 parts of butyl methacrylate (BMA), 60 parts of butyl acrylate (BA), 5 parts of methacrylic acid (MAA) 3 parts of Aqualon KH1025, 15 parts of a 2% aqueous solution of ammonium persulfate and 200 parts of water were prepared, and the resulting mixture was emulsified with a homomixer, and the resulting pre-emulsion was γ-methacryloxy 3 parts propyltrimethoxysilane (SZ6030), 30 parts methyltrimethoxysilane (SZ6070), 30 parts dimethyldimethoxysilane (AY43-004), SH244 (octamethylcyclotetrasiloxane: manufactured by Toray Dow Corning Silicone Co., Ltd.) 0.45 part, SH245 (decamethylcyclopenta Loxane: manufactured by Toray Dow Corning Silicone Co., Ltd.) 0.05 part of a silicone modifier (B) mixed with a metal mesh in the Y-shaped tube and mixed into the reaction vessel over 1 hour from the dropping tank Let it flow. 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 2.7. A 25% aqueous ammonia solution was added to the above mixture to adjust the pH to 9, and then filtered 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. Thereafter, water was added to adjust the solid content to 40 to 50%, and the solid content of the obtained emulsion was 46%, the average particle size was 130 nm, and the cyclic organosilane compound was 0.54% by mass (D4: 0.45). (Mass%, D5: 0.09 mass%) containing emulsion. The results are summarized in Table 1.

[Examples 2 to 14]
Table 1 shows the parts by mass of the silicone modifier (B) used in Step (1) and Step (3), the parts by mass of (A), and the like. In addition, the same processing as in Example 1 was performed. The solid content, average particle diameter, amount of cyclic organosilane compound, and the like of the obtained emulsion are also shown in Tables 1 to 3.
[Example 15]
The same raw materials as in Example 14 were subjected to the same treatment except that the cyclic organosilane compounds (SH244 and SH245) were added during the polymerization reaction, not during the polymerization. The solid content, average particle diameter, and cyclic organosilane compound content of the obtained emulsion are shown in Table 3.

[Comparative Examples 1-3]
The same treatment as in Example 1 was performed except that the silicone modifier (B) used in Step (1) and Step (3) was changed to parts by mass shown in Table 3. The solid content, average particle diameter, and cyclic organosilane compound content of the obtained emulsion are shown in Table 3.

Claims (9)

  A polymer emulsion composition obtained from an ethylenically unsaturated monomer system (A) and an organic silane compound (B) and containing 0.02% by mass to 10% by mass of a cyclic organic silane compound.   The ethylenically unsaturated monomer system (A) is (a1) 80% by mass to 99.7% by mass of one or more ethylenically unsaturated monomers, and (a2) 0.3% by mass to 20% by mass. The polymer emulsion composition according to claim 1, comprising one or more unsaturated carboxylic acids. The organosilane compound (B) includes at least one of the following (b1) to (b3),
(B1) is an organosilane compound represented by the following general formula (1):

(R ¹ represents an alkyl group having 2 or more carbon atoms, an alkyl group having 1 to 10 carbon atoms, a phenyl group or a cyclohexyl group, R ² represents a hydrogen atom, an aliphatic hydrocarbon group having 2 or more carbon atoms, R ³ independently represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group or a hydroxyl group, n is 1 to 3, m is 0 to 1, and n + m ≦ 3.
And
(B2) is an organosilane compound represented by the following general formula (2):
CH ₃ —Si— (R ⁴ ) ₃ (2)
(R ⁴ each independently represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group or a hydroxyl group.)
And
(B3) is at least one of an organosilane compound and a cyclic organosilane compound represented by the following general formula (3):
(CH ₃ ) ₂ —Si— (R ⁵ ) ₂ (3)
(R ⁵ independently represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group or a hydroxyl group.)
The polymer emulsion composition according to claim 1 or 2, wherein   The weight according to claim 3, wherein the organosilane compound (B) contains (b3), and the amount of (b3) is 10% by mass to 70% by mass with respect to the weight of the organosilane compound (B). Combined emulsion composition. The organosilane compound (B) includes the following (b1) to (b3),
(B1) is an organosilane compound represented by the following general formula (1):

(R ¹ represents an alkyl group having 2 or more carbon atoms, an alkyl group having 1 to 10 carbon atoms, a phenyl group or a cyclohexyl group, R ² represents a hydrogen atom, an aliphatic hydrocarbon group having 2 or more carbon atoms, R ³ independently represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group or a hydroxyl group, n is 1 to 3, m is 0 to 1, and n + m ≦ 3.
And
(B2) is an organosilane compound represented by the following general formula (2):
CH ₃ —Si— (R ⁴ ) ₃ (2)
(R ⁴ each independently represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group or a hydroxyl group.)
And
(B3) is at least one of an organosilane compound and a cyclic organosilane compound represented by the following general formula (3):
(CH ₃ ) ₂ —Si— (R ⁵ ) ₂ (3)
(R ⁵ independently represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group or a hydroxyl group.)
The polymer emulsion composition according to claim 1 or 2, wherein the amount of (b3) is 10% by mass to 70% by mass with respect to the weight of the organosilane compound (B).   The polymer emulsion composition according to any one of claims 3 to 5, wherein the cyclic organic silane compound is produced during polymerization or added as (b3) during the polymerization reaction. The polymer emulsion according to any one of claims 1 to 6, wherein the cyclic silane organic compound is a compound represented by the following general formula (4).

(R ⁶ represents an alkyl group having 1 to 2 carbon atoms, and l represents an integer of 3 to 8)   The polymer emulsion composition according to any one of claims 1 to 7, wherein the cyclic organosilane compound contains a 4-membered ring silane and a 5-membered ring silane.   The polymer emulsion composition according to claim 8, wherein the ratio of 4-membered ring silane / 5-membered ring silane is 100/1 to 1/1.