JP2011046783A - Aqueous emulsion resin composition and coating obtained by blending the same - Google Patents

Aqueous emulsion resin composition and coating obtained by blending the same Download PDF

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JP2011046783A
JP2011046783A JP2009194540A JP2009194540A JP2011046783A JP 2011046783 A JP2011046783 A JP 2011046783A JP 2009194540 A JP2009194540 A JP 2009194540A JP 2009194540 A JP2009194540 A JP 2009194540A JP 2011046783 A JP2011046783 A JP 2011046783A
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weight
parts
resin composition
aqueous emulsion
emulsion resin
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Yasuhiro Nakagawa
康宏 中川
Jiro Uchida
二朗 内田
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Resonac Holdings Corp
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Showa Denko KK
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Priority to JP2009194540A priority Critical patent/JP2011046783A/en
Priority to CN2010800296373A priority patent/CN102471391A/en
Priority to PCT/JP2010/064183 priority patent/WO2011024759A1/en
Priority to SG2012006292A priority patent/SG178152A1/en
Publication of JP2011046783A publication Critical patent/JP2011046783A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous emulsion resin composition excellent in weather resistance, low staining, and long-term shelf stability. <P>SOLUTION: The aqueous emulsion resin composition is obtained by performing emulsion polymerization of an unsaturated monomer composition including (A) γ-methacryloxypropyltrimethoxysilane, (B) cyclohexylmethacrylate, and (C) at least one unsaturated monomer selected from the group consisting of methyl methacrylate, butyl(meth)acrylate, and 2-ethylhexyl(meth)acrylate in the presence of a radically reactive surfactant, wherein 0.1-2 wt.% of (A) γ-methacryloxypropyltrimethoxysilane is contained in the unsaturated monomer composition, and 25-75 wt.% of (B) cyclohexylmethacrylate is contained in the unsaturated monomer composition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は、水性エマルジョン樹脂組成物およびそれを配合した塗料に関する。   TECHNICAL FIELD The present invention relates to an aqueous emulsion resin composition and a coating material containing the same.

現在、建物や構造物には、それらの美観保護のため、耐候性および耐汚染性に優れる塗料が塗装されている。このような塗料として、１〜３個の加水分解性アルコキシル基を有するアルキルアルコキシシラン化合物もしくはその加水分解物と、４個の加水分解性アルコキシル基を有するアルコキシシラン化合物もしくはその加水分解物と、末端がＯＨ基であるポリアルキレングリコール鎖を有する非イオン性化合物とが特定の割合で存在する下で、シランカップリング剤を０．１質量％〜２質量％含む不飽和単量体組成物を乳化重合して得られる水性エマルジョン樹脂組成物が提案されている（例えば、特許文献１を参照）。しかしながら、水性エマルジョン樹脂組成物は、耐候性および耐汚染性が良好であるものの、長期の保存安定性が不十分であった。   Currently, buildings and structures are painted with paints that are excellent in weather resistance and stain resistance in order to protect their aesthetics. As such a paint, an alkylalkoxysilane compound having 1 to 3 hydrolyzable alkoxyl groups or a hydrolyzate thereof, an alkoxysilane compound having 4 hydrolyzable alkoxyl groups or a hydrolyzate thereof, and a terminal An unsaturated monomer composition containing 0.1% by mass to 2% by mass of a silane coupling agent is emulsified in the presence of a nonionic compound having a polyalkylene glycol chain in which is an OH group. An aqueous emulsion resin composition obtained by polymerization has been proposed (see, for example, Patent Document 1). However, the aqueous emulsion resin composition has good weather resistance and stain resistance, but has long-term storage stability.

特開２００８−１２０９０４号公報JP 2008-120904 A

従って、本発明が解決しようとする課題は、耐候性、耐汚染性および長期の保存安定性に優れる水性エマルジョン樹脂組成物並びにそれを配合した塗料を提供することにある。   Therefore, the problem to be solved by the present invention is to provide an aqueous emulsion resin composition excellent in weather resistance, stain resistance and long-term storage stability, and a paint containing the same.

そこで、本発明者らは、鋭意検討した結果、特定の組成を有する不飽和単量体組成物を、特定の界面活性剤の存在下で乳化重合して得られる水性エマルジョン樹脂組成物が、耐候性および耐汚染性に優れるだけでなく、長期の保存安定性にも優れることを見出し、本発明を完成させるに至った。
即ち、本発明は、（Ａ）γ−メタクリロキシプロピルトリメトキシシランと、（Ｂ）メタクリル酸シクロヘキシルと、（Ｃ）メタクリル酸メチル、（メタ）アクリル酸ブチルおよび（メタ）アクリル酸−２−エチルヘキシルからなる群から選択される少なくとも１つの不飽和単量体とを含む不飽和単量体組成物を、ラジカル反応性界面活性剤の存在下で乳化重合して得られる水性エマルジョン樹脂組成物であって、（Ａ）γ−メタクリロキシプロピルトリメトキシシランが、不飽和単量体組成物中に０．１重量％〜２重量％含まれ、且つ（Ｂ）メタクリル酸シクロヘキシルが、不飽和単量体組成物中に２５重量％〜７５重量％含まれる水性エマルジョン樹脂組成物である。 Therefore, as a result of intensive studies, the present inventors have determined that an aqueous emulsion resin composition obtained by emulsion polymerization of an unsaturated monomer composition having a specific composition in the presence of a specific surfactant has a weather resistance. As a result, the present invention has been completed.
That is, the present invention relates to (A) γ-methacryloxypropyltrimethoxysilane, (B) cyclohexyl methacrylate, (C) methyl methacrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. An aqueous emulsion resin composition obtained by emulsion polymerization of an unsaturated monomer composition containing at least one unsaturated monomer selected from the group consisting of in the presence of a radical reactive surfactant. (A) γ-methacryloxypropyltrimethoxysilane is contained in the unsaturated monomer composition in an amount of 0.1 wt% to 2 wt%, and (B) cyclohexyl methacrylate is an unsaturated monomer. An aqueous emulsion resin composition contained in an amount of 25% to 75% by weight in the composition.

本発明によれば、耐候性、耐汚染性および長期保存安定性に優れる水性エマルジョン樹脂組成物を提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, the water-based emulsion resin composition which is excellent in a weather resistance, stain resistance, and long-term storage stability can be provided.

以下、本発明を詳細に説明する。
本発明の水性エマルジョン樹脂組成物は、（Ａ）成分としてのγ−メタクリロキシプロピルトリメトキシシランと、（Ｂ）成分としてのメタクリル酸シクロヘキシルと、（Ｃ）成分としてのメタクリル酸メチル、（メタ）アクリル酸ブチルおよび（メタ）アクリル酸−２−エチルヘキシルからなる群から選択される少なくとも１つの不飽和単量体とを必須成分として含む不飽和単量体組成物を、ラジカル反応性界面活性剤の存在下で乳化重合して得られるものである。本発明では、これらの（Ａ）〜（Ｃ）成分が相乗的に作用することにより、耐候性および耐汚染性を向上させることができるだけでなく、長期の保存安定性も著しく向上させることができる。 Hereinafter, the present invention will be described in detail.
The aqueous emulsion resin composition of the present invention comprises (γ) -methacryloxypropyltrimethoxysilane as component (A), cyclohexyl methacrylate as component (B), methyl methacrylate as component (C), (meth) An unsaturated monomer composition containing, as an essential component, at least one unsaturated monomer selected from the group consisting of butyl acrylate and (meth) acrylate-2-ethylhexyl is used as a radical-reactive surfactant. It is obtained by emulsion polymerization in the presence. In the present invention, these components (A) to (C) act synergistically to improve weatherability and stain resistance as well as significantly improve long-term storage stability. .

（Ａ）成分であるγ−メタクリロキシプロピルトリメトキシシランは、３つの加水分解性アルコキシリル基と１つの不飽和基を併せ持ち、その高い自己架橋性により、本発明の水性エマルジョン樹脂組成物に優れた耐候性および耐汚染性を付与することができる。
γ−メタクリロキシプロピルトリメトキシシランは、不飽和単量体組成物中に０．１重量％〜２重量％含まれることが必須であり、０．２重量％〜１重量％含まれることが好ましい。γ−メタクリロキシプロピルトリメトキシシランの含有量が、０．１重量％未満であると耐候性および耐汚染性が劣り、２重量％を超えると重合安定性および造膜性が劣る。 (A) component γ-methacryloxypropyltrimethoxysilane has three hydrolyzable alkoxylyl groups and one unsaturated group, and is excellent in the aqueous emulsion resin composition of the present invention due to its high self-crosslinking property. Weather resistance and stain resistance can be imparted.
It is essential that γ-methacryloxypropyltrimethoxysilane is contained in the unsaturated monomer composition in an amount of 0.1 wt% to 2 wt%, and preferably 0.2 wt% to 1 wt%. . When the content of γ-methacryloxypropyltrimethoxysilane is less than 0.1% by weight, weather resistance and stain resistance are inferior, and when it exceeds 2% by weight, polymerization stability and film-forming property are inferior.

（Ｂ）成分であるメタクリル酸シクロヘキシルは、本発明の水性エマルジョン樹脂組成物に耐候性および耐汚染性を主に付与することができる。
メタクリル酸シクロヘキシルは、不飽和単量体組成物中に２５重量％〜７５重量％含まれることが必須であり、２５重量％〜７０重量％含まれることが好ましい。メタクリル酸シクロヘキシルの含有量が、２５重量％未満であると耐候性および耐汚染性が劣り、メタクリル酸シクロヘキシルの含有量が、７５重量％を超えると重合安定性および造膜性が劣る。 The component (B), cyclohexyl methacrylate, can mainly impart weather resistance and stain resistance to the aqueous emulsion resin composition of the present invention.
It is essential that cyclohexyl methacrylate is contained in the unsaturated monomer composition in an amount of 25% by weight to 75% by weight, and preferably 25% by weight to 70% by weight. When the content of cyclohexyl methacrylate is less than 25% by weight, the weather resistance and stain resistance are inferior. When the content of cyclohexyl methacrylate exceeds 75% by weight, the polymerization stability and the film-forming property are inferior.

（Ｃ）成分である不飽和単量体は、メタクリル酸メチル、（メタ）アクリル酸ブチルおよび（メタ）アクリル酸−２−エチルヘキシルからなる群から選択される少なくとも１つである。（Ｃ）成分は、本発明の水性エマルジョン樹脂組成物に耐候性および耐汚染性を主に付与することができる。
（Ｃ）成分は、不飽和単量体組成物中に３０重量％〜７０重量％含まれていることが好ましく、３５重量％〜６８重量％含まれていることがより好ましい。 The unsaturated monomer as component (C) is at least one selected from the group consisting of methyl methacrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. The component (C) can mainly impart weather resistance and stain resistance to the aqueous emulsion resin composition of the present invention.
Component (C) is preferably contained in the unsaturated monomer composition in an amount of 30% to 70% by weight, and more preferably 35% to 68% by weight.

本発明の効果を損なわない範囲で、（Ａ）〜（Ｃ）成分の以外の種々の不飽和単量体を不飽和単量体組成物に配合してもよい。このような不飽和単量体としては、アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｉｓｏ−ブチル、（メタ）アクリル酸ｔｅｒｔ−ブチル、アクリル酸シクロヘキシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸イソボルニル等の炭素原子が１〜１８個の直鎖状、分岐鎖状もしくは環状のアルキル鎖を有する（メタ）アクリル酸エステル、スチレン、α−メチルスチレン、ｐ−メチルスチレン、エチルビニルベンゼン等の芳香族ビニル化合物、ビニルピロリドン等の複素環式ビニル化合物、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル等の（メタ）アクリル酸ヒドロキシアルキル、エチレングリコール（メタ）アクリレート、ブチレングリコール（メタ）アクリレート等のポリアルキレンレングリコール（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリレート等のアルキルアミノ（メタ）アクリレート、ギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、バーサチック酸ビニル（商品名）等のビニルエステル化合物、エチレン、プロピレン、ブチレン、イソブチレン等のモノオレフィン化合物、ブタジエン、イソプレン、クロロプレン等の共役ジオレフィン化合物、アクリル酸、メタクリル酸、クロトン酸、シトラコン酸、イタコン酸、マレイン酸、無水マレイン酸、フマル酸等のα，β−不飽和モノまたはジカルボン酸、フタル酸モノヒドロキシエチル（メタ）アクリレート、シュウ酸モノヒドロキシプロピル（メタ）アクリレート等のカルボキシル基含有ビニル化合物、１，１，１−トリメチルアミンメタクリルイミド等のアミンイミド基含有ビニル化合物、アクリロニトリル、メタクリロニトリル等のシアン化ビニル化合物、（メタ）アクリルアミド、Ｎ−メチルアクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド等のアミド基もしくは置換アミド基含有α，β−エチレン性不飽和化合物、アクロレイン、ダイアセトンアクリルアミド、ビニルメチルケトン、ダイアセトンアクリレート等のカルボニル基含有α，β−エチレン性不飽和化合物、スルホン酸アリル、ｐ−スチレンスルホン酸ナトリウム等のスルホン酸基含有α，β−エチレン性不飽和化合物、３−（２Ｈ−ベンゾトリアゾール−２−イル）−４−ヒドロキシフェネチル＝メタクリラート等のエチレン性不飽和基含有紫外線吸収剤、１，２，２，６，６−ペンタメチル−４−ピペリジルメタクリレート等エチレン性不飽和基含有光安定剤、γ−メタクリロキシプロピルトリエトキシシラン、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン等のγ−メタクリロキシプロピルトリメトキシシラン以外の不飽和基を有するシランカップリング剤、さらに、グリシジル（メタ）アクリレート、３，４−エポキシシクロヘキシルメチル（メタ）アクリレート、グリシジルビニルエーテル、グリシジル（メタ）アリルエーテル、３，４−エポキシシクロヘキシル（メタ）アクリレート等のエポキシ基含有α，β−エチレン性不飽和化合物、エチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、アリル（メタ）アクリレート、ジビニルベンゼン、ジアリルフタレート等の多官能ビニル化合物等が挙げられる。エポキシ基含有α，β−エチレン性不飽和化合物及び多官能ビニル化合物は、それ自身同士を架橋させるか、もしくは活性水素基を持つエチレン性不飽和化合物成分と組み合わせて架橋させることが可能であり、またはカルボニル基含有α，β−エチレン性不飽和化合物（特にケト基含有のものに限る）を導入し、特に２つ以上のヒドラジド基を有する化合物；シュウ酸ジヒドラジド、コハク酸ジヒドラジド、アジピン酸ジヒドラジド、ポリアクリル酸ヒドラジド等のポリヒドラジン化合物と組み合わせて架橋させることも可能である。   You may mix | blend various unsaturated monomers other than (A)-(C) component with an unsaturated monomer composition in the range which does not impair the effect of this invention. Examples of such unsaturated monomers include methyl acrylate, ethyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl acrylate, and lauryl (meth) acrylate. (Meth) acrylic acid ester having 1-18 carbon atoms, such as stearyl (meth) acrylate, isobornyl (meth) acrylate, etc., having a linear, branched or cyclic alkyl chain, styrene, α-methyl Aromatic vinyl compounds such as styrene, p-methylstyrene and ethyl vinyl benzene, heterocyclic vinyl compounds such as vinyl pyrrolidone, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate (meta) ) Hydroxyalkyl acrylate, ethylene glycol (meth) acrylate, butyre Polyalkylene glycol (meth) acrylate such as glycol (meth) acrylate, alkylamino (meth) acrylate such as N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, vinyl formate , Vinyl ester compounds such as vinyl acetate, vinyl propionate and vinyl versatate (trade name), monoolefin compounds such as ethylene, propylene, butylene and isobutylene, conjugated diolefin compounds such as butadiene, isoprene and chloroprene, acrylic acid and methacrylic acid Α, β-unsaturated mono- or dicarboxylic acids such as acid, crotonic acid, citraconic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, monohydroxyethyl (meth) acrylate phthalate, monohydric oxalic acid Carboxyl group-containing vinyl compounds such as xylpropyl (meth) acrylate, amine imide group-containing vinyl compounds such as 1,1,1-trimethylamine methacrylamide, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, (meth) acrylamide, N-methyl Amide or substituted amide group-containing α, β-ethylenically unsaturated compounds such as acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, acrolein, diacetone acrylamide, vinylmethyl Carbonyl group-containing α, β-ethylenically unsaturated compounds such as ketone and diacetone acrylate, sulfonic acid group-containing α, β-ethylenically unsaturated compounds such as allyl sulfonate and sodium p-styrenesulfonate, 3- (2H -Benzotriazol-2-yl) -4-hydroxyphenethyl = ethylenically unsaturated group-containing ultraviolet absorbers such as methacrylate, ethylenically unsaturated groups such as 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate Containing light stabilizer, γ-methacryloxypropyltriethoxysilane, vinyltriethoxysilane, silane coupling agent having an unsaturated group other than γ-methacryloxypropyltrimethoxysilane such as vinyltris (β-methoxyethoxy) silane, and , Glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl vinyl ether, glycidyl (meth) allyl ether, 3,4-epoxycyclohexyl (meth) acrylate-containing α, β-ethylenic group Desaturation And polyfunctional vinyl compounds such as ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, divinylbenzene, diallyl phthalate, and the like. The epoxy group-containing α, β-ethylenically unsaturated compound and the polyfunctional vinyl compound can be crosslinked by themselves or in combination with an ethylenically unsaturated compound component having an active hydrogen group, Or a carbonyl group-containing α, β-ethylenically unsaturated compound (especially limited to those containing a keto group), particularly a compound having two or more hydrazide groups; oxalic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, It is also possible to crosslink in combination with a polyhydrazine compound such as polyacrylic acid hydrazide.

更には、必要に応じて、乳化重合中或いは乳化重合終了後にラジカル反応性を有さない架橋性化合物、例えば、テトラメトキシシラン、テトラエトキシシラン、メチルトリメトキシシラン等のアルキルシリケート、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセロールポリグリシジルエーテル、ビスフェノールＡグリシジルエーテル等の多官能エポキシ化合物等を添加し、架橋させることも可能である。   Furthermore, if necessary, a crosslinkable compound having no radical reactivity during emulsion polymerization or after completion of emulsion polymerization, for example, alkyl silicates such as tetramethoxysilane, tetraethoxysilane, and methyltrimethoxysilane, ethylene glycol diglycidyl It is also possible to add polyfunctional epoxy compounds such as ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, bisphenol A glycidyl ether and the like to crosslink.

また、塗膜表面のブロッキング防止および成膜性の点から、使用する不飽和単量体組成物の理論ガラス転移温度（以下、Ｔｇと略すことがある）は、０℃〜５０℃の範囲であることが好ましい。なお、本発明における理論ガラス転移温度は、下記式から算出した値である。
１／Ｔｇ（Ｋ）＝Ｗ１／Ｔ１＋Ｗ２／Ｔ２＋Ｗ３／Ｔ３＋・・・＋Ｗｎ／Ｔｎ
Ｔｇ（℃）＝Ｔｇ（Ｋ）−２７３
式中、Ｗ１、Ｗ２、Ｗ３・・・Ｗｎは、不飽和単量体組成物に対する各不飽和単量体の割合（重量％）であり、Ｔ１、Ｔ２、Ｔ３・・・Ｔｎは、各不飽和単量体の単独重合体のガラス転移温度（絶対温度（Ｋ））である。ここで、各不飽和単量体の単独重合体のガラス転移温度は、Polymer Hand Book（Second Edition, J. Brandrup・E. H. Immergut 編）による値である。 The theoretical glass transition temperature (hereinafter sometimes abbreviated as Tg) of the unsaturated monomer composition to be used is in the range of 0 ° C. to 50 ° C. Preferably there is. In addition, the theoretical glass transition temperature in this invention is the value computed from the following formula.
1 / Tg (K) = W 1 / T 1 + W 2 / T 2 + W 3 / T 3 +... + W n / T n
Tg (° C.) = Tg (K) -273
In the formula, W 1 , W 2 , W 3 ... W n are ratios (% by weight) of each unsaturated monomer to the unsaturated monomer composition, and T 1 , T 2 , T 3. · · T n is the glass transition temperature of the homopolymer of the respective unsaturated monomer (absolute temperature (K)). Here, the glass transition temperature of the homopolymer of each unsaturated monomer is a value according to Polymer Hand Book (Second Edition, edited by J. Brandrup / EH Immergut).

本発明では、（Ａ）〜（Ｃ）成分および必要に応じて配合されるその他の不飽和単量体を乳化重合する際にラジカル反応性界面活性剤を使用することが必須である。ラジカル反応性界面活性剤は、本発明の水性エマルジョン樹脂組成物に耐候性および耐汚染性を主に付与することができる。ラジカル反応性界面活性剤は、ラジカル反応性を有するものであれば特に制限されるものではないが、具体的には、アデカリアソープ（登録商標、株式会社ＡＤＥＫＡ製）ＳＥ−１０Ｎ、ＳＲ−１０、ＳＲ−２０、ＳＲ−３０、ＥＲ−２０、ＥＲ−３０、アクアロン（登録商標、第一工業製薬株式会社製）ＨＳ−１０、ＫＨ−５、ＫＨ−１０、エレミノール(登録商標、三洋化成工業株式会社製)ＪＳ−２０、エマルゲン（登録商標、花王株式会社製）ＰＤ−１０４、ＰＤ−４２０、ＰＤ−４３０等が挙げられる。
ラジカル反応性界面活性剤の使用量は、使用する不飽和単量体組成物に対して、０．５重量％〜５重量％であることが好ましい。ラジカル反応性界面活性剤の使用量が少な過ぎると重合安定性が低下する場合があり、一方、多過ぎると耐水性が低下する場合がある。これらのラジカル反応性界面活性剤は、基本的に不飽和単量体を乳化させる目的で乳化重合前或いは乳化重合中に添加することが必須であるが、乳化重合後のエマルジョンに安定性を付与する目的で後添加してもよい。 In the present invention, it is essential to use a radical reactive surfactant when emulsion polymerization of the components (A) to (C) and other unsaturated monomers blended as necessary. The radical-reactive surfactant can mainly impart weather resistance and stain resistance to the aqueous emulsion resin composition of the present invention. The radical reactive surfactant is not particularly limited as long as it has radical reactivity. Specifically, Adeka soap (registered trademark, manufactured by ADEKA Corporation) SE-10N, SR-10 SR-20, SR-30, ER-20, ER-30, Aqualon (registered trademark, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) HS-10, KH-5, KH-10, Eleminol (registered trademark, Sanyo Chemical Industries) JS-20, Emalgen (registered trademark, manufactured by Kao Corporation) PD-104, PD-420, PD-430 and the like.
It is preferable that the usage-amount of a radical reactive surfactant is 0.5 to 5 weight% with respect to the unsaturated monomer composition to be used. If the amount of the radical-reactive surfactant used is too small, the polymerization stability may decrease, while if too large, the water resistance may decrease. These radical-reactive surfactants are basically required to be added before or during emulsion polymerization for the purpose of emulsifying unsaturated monomers, but give stability to emulsions after emulsion polymerization. It may be added later for the purpose.

また、非反応性界面活性剤を上記したラジカル反応性界面活性剤と併用してもよい。併用できる非反応性界面活性剤としては、例えば、ドデシルベンゼンスルホン酸ナトリウム、ドデシル硫酸ナトリウム等のアニオン性界面活性剤、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンノニルフェニルエーテル等のノニオン性界面活性剤、セシルトリメチルアンモニウムブロミド、ラウリルピリジニウムクロリド等のカチオン性界面活性剤、ラウリルベタイン等の両性界面活性剤が挙げられる。これらの非反応性界面活性剤は、不飽和単量体を乳化させる目的で乳化重合前或いは乳化重合中に添加してもよいし、乳化重合後のエマルジョンに安定性を付与する目的で後添加してもよい。   Further, a non-reactive surfactant may be used in combination with the radical reactive surfactant described above. Examples of non-reactive surfactants that can be used in combination include anionic surfactants such as sodium dodecylbenzenesulfonate and sodium dodecylsulfate, nonionic surfactants such as polyoxyethylene lauryl ether and polyoxyethylene nonylphenyl ether, Examples include cationic surfactants such as ceyltrimethylammonium bromide and laurylpyridinium chloride, and amphoteric surfactants such as laurylbetaine. These non-reactive surfactants may be added before or during emulsion polymerization for the purpose of emulsifying unsaturated monomers, or post-added for the purpose of imparting stability to the emulsion after emulsion polymerization. May be.

また、乳化重合において使用することができる重合開始剤としては、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩系開始剤、２，２’−アゾビス（２−メチルプロピオンアミジン）ジ塩酸塩等の水溶性アゾ系開始剤、ｔ−ブチルヒドロパーオキシド、クメンヒドロパーオキシド等の有機過酸化物類、過酸化水素等が挙げられる。これらの重合開始剤は、単独で使用してもよいし、２種以上を混合して使用してもよい。重合開始剤の使用量は、通常、使用する不飽和単量体組成物に対して、０．１重量％〜１重量％である。   Examples of the polymerization initiator that can be used in the emulsion polymerization include water-soluble persulfate-based initiators such as potassium persulfate and ammonium persulfate, and 2,2′-azobis (2-methylpropionamidine) dihydrochloride. Azo initiators, organic peroxides such as t-butyl hydroperoxide and cumene hydroperoxide, and hydrogen peroxide. These polymerization initiators may be used alone or in combination of two or more. The usage-amount of a polymerization initiator is 0.1 to 1 weight% normally with respect to the unsaturated monomer composition to be used.

また、乳化重合においては、必要に応じてこれら重合開始剤と共に還元剤を使用してもよい。このような還元剤としては、アスコルビン酸、酒石酸、クエン酸、ブドウ糖、ホルムアルデヒドスルホキシラート金属塩等の還元性有機化合物、チオ硫酸ナトリウム、亜硫酸ナトリウム、重亜硫酸ナトリウム、メタ重亜硫酸ナトリウム等の還元性無機化合物等が挙げられる。還元剤の使用量は、本発明の効果を損なわない範囲で適宜決定すればよい。   Moreover, in emulsion polymerization, you may use a reducing agent with these polymerization initiators as needed. Such reducing agents include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, glucose, formaldehyde sulfoxylate metal salts, reducing properties such as sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium metabisulfite An inorganic compound etc. are mentioned. What is necessary is just to determine the usage-amount of a reducing agent suitably in the range which does not impair the effect of this invention.

また、乳化重合においては、必要に応じて連鎖移動剤を使用してもよい。このような連鎖移動剤としては、ｎ−ドデシルメルカプタン、ｔｅｒｔ−ドデシルメルカプタン、ｎ−ブチルメルカプタン、２−エチルヘキシルチオグリコレート、２−メルカプトエタノール、β−メルカプトプロピオン酸等が挙げられる。連鎖移動剤の使用量は、本発明の効果を損なわない範囲で適宜決定すればよい。   In the emulsion polymerization, a chain transfer agent may be used as necessary. Examples of such chain transfer agents include n-dodecyl mercaptan, tert-dodecyl mercaptan, n-butyl mercaptan, 2-ethylhexyl thioglycolate, 2-mercaptoethanol, β-mercaptopropionic acid and the like. What is necessary is just to determine the usage-amount of a chain transfer agent suitably in the range which does not impair the effect of this invention.

本発明における乳化重合は、通常、約５℃〜約１００℃、好ましくは約５０℃〜９０℃の温度条件下で行われる。反応時間は、特に制限されることはなく、各成分の配合量および反応温度等に応じて適宜調整すればよい。   The emulsion polymerization in the present invention is usually performed under a temperature condition of about 5 ° C to about 100 ° C, preferably about 50 ° C to 90 ° C. The reaction time is not particularly limited, and may be appropriately adjusted according to the blending amount of each component, the reaction temperature, and the like.

乳化重合して得られた水性エマルジョン樹脂組成物に酸又は塩基を、ｐＨが４〜１０になるように添加して中和し、重合体の表面電荷を高くすることで、水性エマルジョン樹脂組成物に安定性を付与することができる。使用することができる一般的な酸としては、酢酸、乳酸、塩酸、燐酸、硫酸等が挙げられる。また、使用することができる一般的な塩基としては、トリエチルアミン、アンモニア、ジエタノールアミン、ジエチルアミノエタノール等のアミン化合物、水酸化カリウム、水酸化ナトリウム、水酸化リチウム等のアルカリ金属水酸化物が挙げられる。   An aqueous emulsion resin composition is obtained by adding an acid or a base to an aqueous emulsion resin composition obtained by emulsion polymerization so as to have a pH of 4 to 10 and neutralizing it to increase the surface charge of the polymer. Can be provided with stability. Common acids that can be used include acetic acid, lactic acid, hydrochloric acid, phosphoric acid, sulfuric acid and the like. Examples of a general base that can be used include amine compounds such as triethylamine, ammonia, diethanolamine, and diethylaminoethanol, and alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, and lithium hydroxide.

本発明の塗料は、上記した水性エマルジョン樹脂組成物を含むものである。本発明の塗料には、増粘剤、消泡剤、顔料（体質顔料、着色顔料、中空バルーン、遮熱顔料など）、分散剤、湿潤剤、光安定剤、紫外線吸収剤、防腐剤、抗菌剤等を適宜添加することができる。本発明の塗料は、建築塗料、遮熱塗料、断熱塗料、サイジングボード用塗料、ロードマーキング塗料、モルタル被服材などの様々なコーティング剤として使用することができる。また、紙、繊維、金属、木材、セラミックなどの被覆できるものにも本発明の塗料を使用することが可能であり、その手法に関しても限定されない。   The coating material of the present invention contains the above-described aqueous emulsion resin composition. The paint of the present invention includes thickeners, antifoaming agents, pigments (external pigments, colored pigments, hollow balloons, heat shielding pigments, etc.), dispersants, wetting agents, light stabilizers, UV absorbers, antiseptics, antibacterial agents An agent or the like can be appropriately added. The paint of the present invention can be used as various coating agents such as architectural paints, heat-shielding paints, heat-insulating paints, sizing board paints, road marking paints, and mortar clothing materials. Moreover, it is possible to use the coating material of this invention also for what can be coat | covered, such as paper, a fiber, a metal, wood, and a ceramic, It is not limited regarding the method.

以下、実施例および比較例により本発明を具体的に説明する。また、実施例および比較例で得られたエマルジョンの物性は、以下に示す方法により評価した。   Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The physical properties of the emulsions obtained in the examples and comparative examples were evaluated by the methods shown below.

（１）水性エマルジョン樹脂組成物の性状
（１−１）不揮発分
予め重量が測定された水性エマルジョン樹脂組成物を１０５℃で１時間乾燥させ、揮発残分の重量を測定した。初期の重量と揮発残分の重量から不揮発分の割合（重量％）を計算した。
（１−２）粘度
水性エマルジョン樹脂組成物の粘度は、ＢＭ型粘度計を用いて２３℃、６０ｒｐｍにおいて測定した。
（１−３）ｐＨ
水性エマルジョン樹脂組成物のｐＨは、ｐＨメーターを用いて測定した。
（１−４）最低造膜温度（以下、ＭＦＴと略すことがある）
熱勾配式最低造膜温度測定装置を用いて測定した。また、水性エマルジョン樹脂組成物を５０℃で１ヶ月間放置した後のＭＦＴも同様に測定した。 (1) Properties of Aqueous Emulsion Resin Composition (1-1) Nonvolatile Content The aqueous emulsion resin composition whose weight was previously measured was dried at 105 ° C. for 1 hour, and the weight of the volatile residue was measured. From the initial weight and the weight of the volatile residue, the ratio of nonvolatile content (% by weight) was calculated.
(1-2) Viscosity The viscosity of the aqueous emulsion resin composition was measured at 23 ° C. and 60 rpm using a BM viscometer.
(1-3) pH
The pH of the aqueous emulsion resin composition was measured using a pH meter.
(1-4) Minimum film-forming temperature (hereinafter sometimes abbreviated as MFT)
It measured using the thermal gradient type minimum film-forming temperature measuring apparatus. The MFT after the aqueous emulsion resin composition was allowed to stand at 50 ° C. for 1 month was also measured in the same manner.

（２）長期保存安定性の評価
（１−４）で測定した水性エマルジョン樹脂組成物の初期のＭＦＴと放置後のＭＦＴからＭＦＴの変化率を計算し、下記評価基準に従って評価した。
○：ＭＦＴの変化率が１０％以下である
×：ＭＦＴの変化率が１０％を超える (2) Evaluation of long-term storage stability The change rate of MFT was calculated from the initial MFT of the aqueous emulsion resin composition measured in (1-4) and the MFT after standing, and evaluated according to the following evaluation criteria.
○: Change rate of MFT is 10% or less ×: Change rate of MFT exceeds 10%

（３）耐候性および耐汚染性の評価
（３−１）グロス塗料の調製
脱イオン水８２．６重量部、増粘剤としてのナトロゾール２５０ＨＲ（ハーキュレース製）０．８重量部、中和剤としてのアンモニア水０．２重量部、防腐剤としてのアモルデンＦＳ−１４Ｄ（大和化学工業株式会社製）１．１重量部、分散剤としてのポイズ５２１（花王株式会社製）４．２重量部、消泡剤としてのＳＮデフォーマー３７１（サンノプコ株式会社製）１．１重量部、酸化チタンとしてのタイペークＣＲ−９７（石原産業製）２１０重量部を容器中でホモディスパーを用いて約２０００ｒｐｍで撹拌しながら上記順に仕込み、更に約２０００ｒｐｍで１時間撹拌した。その後、１２０メッシュのテフロン（登録商標）メッシュで濾過し、固形分濃度７０重量％（酸化チタンを固形分として計算）のミルベース３００重量部を得た。
別容器に、得られたミルベース３００重量部、水性エマルジョン樹脂組成物６００重量部（不揮発分５０重量％の場合。不揮発分が５０重量％以外の場合は、それぞれの不揮発分に応じて、３００重量部の樹脂が含まれるように添加量を設定した）、造膜助剤としてのＣＳ−１２（チッソ株式会社製）をα重量部（α＝ＭＦＴ÷５×６）、粘性調整剤としてのアデカノールＵＨ−４２０（株式会社ＡＤＥＫＡ製）１重量部を仕込み、ホモディスパーを用いて約２０００ｒｐｍで１０分間撹拌した。その後、１５０メッシュのテフロン（登録商標）メッシュで濾過し、固形分濃度５３．４重量％、顔料濃度１５．５体積％（酸化チタンの比重を４．２、水性エマルジョン樹脂組成物の比重を１．１として計算した）のグロス塗料９５５重量部を得た。 (3) Evaluation of weather resistance and stain resistance (3-1) Preparation of gloss paint 82.6 parts by weight of deionized water, 0.8 part by weight of Natrozole 250HR (made by Hercules) as a thickener, as a neutralizer 0.2 parts by weight of aqueous ammonia, 1.1 parts by weight of Amorden FS-14D (manufactured by Daiwa Chemical Industries) as a preservative, 4.2 parts by weight of Poise 521 (manufactured by Kao Corporation) as a dispersant While stirring 1.1 parts by weight of SN deformer 371 (manufactured by San Nopco Co., Ltd.) as a foaming agent and 210 parts by weight of Taipei CR-97 (manufactured by Ishihara Sangyo) as titanium oxide at about 2000 rpm using a homodisper in a container. It charged in the order mentioned above, and also stirred at about 2000 rpm for 1 hour. Thereafter, the mixture was filtered through a 120-mesh Teflon (registered trademark) mesh to obtain 300 parts by weight of a mill base having a solid content of 70% by weight (calculated using titanium oxide as a solid content).
In a separate container, 300 parts by weight of the obtained mill base and 600 parts by weight of the aqueous emulsion resin composition (when the nonvolatile content is 50% by weight. When the nonvolatile content is other than 50% by weight, 300% by weight depending on each nonvolatile content. The addition amount was set so as to include a part of resin), CS-12 (made by Chisso Corporation) as a film-forming aid was α parts by weight (α = MFT ÷ 5 × 6), and Adecanol as a viscosity modifier. 1 part by weight of UH-420 (manufactured by ADEKA Co., Ltd.) was charged, and stirred at about 2000 rpm for 10 minutes using a homodisper. Thereafter, the mixture is filtered through a 150 mesh Teflon (registered trademark) mesh, the solid content concentration is 53.4% by weight, the pigment concentration is 15.5% by volume (the specific gravity of titanium oxide is 4.2, the specific gravity of the aqueous emulsion resin composition is 1). 195 parts by weight of a gloss paint (calculated as .1).

（３−２）塗板の作製
得られたグロス塗料に水を添加して約８００ｍＰａ・ｓ（ＢＨ型粘度計、２０ｒｐｍ、２３℃）の粘度に調整した。この塗料をシーラー処理が予め施されたフレキ板にスプレーを用いて１５０ｇ／ｍ2×２回吹きした後、２３℃、６５％ＲＨで１週間養生し、塗板を得た。上記操作を繰り返して塗板を合計２枚作製した。 (3-2) Preparation of coated plate Water was added to the obtained gloss paint to adjust the viscosity to about 800 mPa · s (BH viscometer, 20 rpm, 23 ° C.). This paint was sprayed onto a flexible board pretreated with a sealer at 150 g / m 2 × 2 times using a spray, and then cured at 23 ° C. and 65% RH for 1 week to obtain a coated board. The above operation was repeated to produce a total of two coated plates.

（３−３）耐候性の評価
作製した塗板の１枚をメタリングウエザーメーター（スガ試験機）で試験し、４００ｈｒ照射後の光沢保持率を測定した。メタリングウエザーメーターの条件は、ブラックパネル温度６３℃、湿度５０％ＲＨ、照度１．５５ｋＷ／ｍ2、照射２時間→照射＋降雨２分（３サイクル）→結露２時間（雰囲気３０℃、９５％ＲＨ、塗板２５℃）の８時間サイクル試験とした。耐候性を下記基準に従って評価した。
○：光沢保持率が７０％以上である
△：光沢保持率が５０％以上７０％未満である
×：光沢保持率が５０％未満である (3-3) Evaluation of weather resistance One of the produced coated plates was tested with a metering weather meter (Suga test machine), and the gloss retention after 400 hr irradiation was measured. The conditions of the metering weather meter are: black panel temperature 63 ° C., humidity 50% RH, illuminance 1.55 kW / m 2 , irradiation 2 hours → irradiation + rainfall 2 minutes (3 cycles) → condensation 2 hours (atmosphere 30 ° C., 95 % RH, coated plate 25 ° C.). The weather resistance was evaluated according to the following criteria.
◯: Gloss retention is 70% or more Δ: Gloss retention is 50% or more and less than 70% ×: Gloss retention is less than 50%

（３−４）耐汚染性の評価
作製した塗板のもう一枚を屋外に３ヶ月間暴露（兵庫県たつの市、南向き４５°）し、暴露前後の色差（ΔＥ）を測定した。耐汚染性を下記基準に従って評価した。
○：ΔＥが４未満である
△：ΔＥが４以上８未満である
×：ΔＥが８以上である (3-4) Evaluation of stain resistance Another piece of the prepared coated plate was exposed outdoors for 3 months (Tatsuno City, Hyogo, 45 ° southward), and the color difference (ΔE) before and after exposure was measured. Contamination resistance was evaluated according to the following criteria.
○: ΔE is less than 4 Δ: ΔE is 4 or more and less than 8 ×: ΔE is 8 or more

＜実施例１＞
撹拌機、温度計および還流凝縮機を備えた重合装置内に、２００重量部の脱イオン水および０．２重量部のアデカリアソープＳＲ−１０（アニオン性反応性界面活性剤、株式会社ＡＤＥＫＡ製）を入れ、窒素置換を十分に行った後、７５℃に昇温した。
２５８重量部の脱イオン水、９．８重量部のアデカリアソープＳＲ−１０、１１８重量部のメタクリル酸メチル、２００重量部のメタクリル酸シクロヘキシル、１６７重量部のアクリル酸−２−エチルヘキシル、５重量部のγ−メタクリロキシプロピルトリメトキシシランおよび１０重量部のメタクリル酸をホモミキサーにて予め混合乳化したものを用意し、重合装置内の温度を７５℃に保ちながら、その乳化物の一部（５重量％）を重合装置内に加えた。
次いで、重合装置内に０．２重量部の過硫酸カリウムを加えて重合を開始し、８０℃で１５分反応させた。さらに、重合装置内の温度を８０℃に保ちながら、先の乳化物の残り（９５重量％）および５０重量部の２％過硫酸カリウム水溶液を４時間掛けて重合装置内に滴下した。さらに、８０℃で２時間反応させ、その後、室温（２５℃）に冷却した。最後に３．５重量部のアンモニア水を入れてｐＨを調整し、実施例１の水性エマルジョン樹脂組成物を得た。なお、実施例１における不飽和単量体組成物の理論Ｔｇは１５℃である。得られた水性エマルジョン樹脂組成物の性状は、不揮発分５０．３重量％、粘度（ＢＭ型粘度計、６０ｒｐｍ、２３℃）１７０ｍＰａ・ｓ、ｐＨ９．０、ＭＦＴ４７℃であった。 <Example 1>
In a polymerization apparatus equipped with a stirrer, a thermometer, and a reflux condenser, 200 parts by weight of deionized water and 0.2 parts by weight of Adekalia Soap SR-10 (anionic reactive surfactant, manufactured by ADEKA Corporation) ) And after sufficient nitrogen substitution, the temperature was raised to 75 ° C.
258 parts by weight of deionized water, 9.8 parts by weight of ADEKA rear soap SR-10, 118 parts by weight of methyl methacrylate, 200 parts by weight of cyclohexyl methacrylate, 167 parts by weight of -2-ethylhexyl acrylate, 5% by weight A portion of γ-methacryloxypropyltrimethoxysilane and 10 parts by weight of methacrylic acid previously mixed and emulsified with a homomixer were prepared, and while maintaining the temperature in the polymerization apparatus at 75 ° C., a part of the emulsion ( 5% by weight) was added into the polymerization apparatus.
Subsequently, 0.2 weight part potassium persulfate was added in the polymerization apparatus, polymerization was started, and it was made to react at 80 degreeC for 15 minutes. Further, while maintaining the temperature in the polymerization apparatus at 80 ° C., the remaining emulsion (95% by weight) and 50 parts by weight of 2% potassium persulfate aqueous solution were dropped into the polymerization apparatus over 4 hours. Furthermore, it was made to react at 80 degreeC for 2 hours, and it cooled to room temperature (25 degreeC) after that. Finally, 3.5 parts by weight of aqueous ammonia was added to adjust the pH, and the aqueous emulsion resin composition of Example 1 was obtained. The theoretical Tg of the unsaturated monomer composition in Example 1 is 15 ° C. The properties of the obtained aqueous emulsion resin composition were a non-volatile content of 50.3% by weight, a viscosity (BM type viscometer, 60 rpm, 23 ° C.) 170 mPa · s, pH 9.0, and MFT 47 ° C.

＜実施例２＞
実施例１の乳化物の代わりに、２５８重量部の脱イオン水、９．８重量部のアデカリアソープＳＲ−１０、２２．５重量部のメタクリル酸メチル、３００重量部のメタクリル酸シクロヘキシル、１６０重量部のアクリル酸−２−エチルヘキシル、２．５重量部のγ−メタクリロキシプロピルトリメトキシシラン、１０重量部のメタクリル酸および５重量部のメタクリル酸−２−ヒドロキシエチルからなる乳化物を用いた以外は、実施例１と同様の操作を行い、実施例２の水性エマルジョン樹脂組成物を得た。なお、実施例２における不飽和単量体組成物の理論Ｔｇは２０℃である。得られた水性エマルジョン樹脂組成物の性状は、不揮発分５０．４重量％、粘度（ＢＭ型粘度計、６０ｒｐｍ、２３℃）１９０ｍＰａ・ｓ、ｐＨ８．８、ＭＦＴ４６℃であった。 <Example 2>
Instead of the emulsion of Example 1, 258 parts by weight of deionized water, 9.8 parts by weight of Adekari Soap SR-10, 22.5 parts by weight of methyl methacrylate, 300 parts by weight of cyclohexyl methacrylate, 160 An emulsion consisting of 2 parts by weight of 2-ethylhexyl acrylate, 2.5 parts by weight of γ-methacryloxypropyltrimethoxysilane, 10 parts by weight of methacrylic acid and 5 parts by weight of 2-hydroxyethyl methacrylate was used. Except for the above, the same operation as in Example 1 was performed to obtain an aqueous emulsion resin composition of Example 2. The theoretical Tg of the unsaturated monomer composition in Example 2 is 20 ° C. The properties of the obtained aqueous emulsion resin composition were a non-volatile content of 50.4% by weight, a viscosity (BM type viscometer, 60 rpm, 23 ° C.) 190 mPa · s, pH 8.8, and MFT 46 ° C.

＜実施例３＞
実施例１の乳化物の代わりに、２３５．５重量部の脱イオン水、９．８重量部のアデカリアソープＳＲ−１０、５５重量部のメタクリル酸メチル、１５０重量部のメタクリル酸シクロヘキシル、１５０重量部のメタクリル酸−ｎ−ブチル、１２８．５重量部のアクリル酸−ｎ−ブチル、１．５重量部のγ−メタクリロキシプロピルトリメトキシシラン、１２．５重量部の８０％アクリル酸および５重量部のジアセトンアクリルアミドからなる乳化物を用い、冷却後に３．５重量部のアンモニア水と、２．６重量部のアジピン酸ジヒドラジドを１８重量部の脱イオン水で溶解したものとを添加した以外は、実施例１と同様の操作を行い、実施例３の水性エマルジョン樹脂組成物を得た。なお、実施例３における不飽和単量体組成物の理論Ｔｇは２０℃である。得られた水性エマルジョン樹脂組成物の性状は、不揮発分５１．１重量％、粘度（ＢＭ型粘度計、６０ｒｐｍ、２３℃）３３０ｍＰａ・ｓ、ｐＨ７．８、ＭＦＴ３５℃であった。 <Example 3>
Instead of the emulsion of Example 1, 235.5 parts by weight of deionized water, 9.8 parts by weight of Adekari Soap SR-10, 55 parts by weight of methyl methacrylate, 150 parts by weight of cyclohexyl methacrylate, 150 Parts by weight n-butyl methacrylate, 128.5 parts by weight n-butyl acrylate, 1.5 parts by weight γ-methacryloxypropyltrimethoxysilane, 12.5 parts by weight 80% acrylic acid and 5 parts by weight An emulsion composed of parts by weight of diacetone acrylamide was used, and after cooling, 3.5 parts by weight of ammonia water and 2.6 parts by weight of adipic acid dihydrazide dissolved in 18 parts by weight of deionized water were added. Except for the above, the same operation as in Example 1 was performed to obtain an aqueous emulsion resin composition of Example 3. The theoretical Tg of the unsaturated monomer composition in Example 3 is 20 ° C. The properties of the obtained aqueous emulsion resin composition were a non-volatile content of 51.1% by weight, a viscosity (BM type viscometer, 60 rpm, 23 ° C.) 330 mPa · s, pH 7.8, and MFT 35 ° C.

＜実施例４＞
実施例１のアデカリアソープＳＲ−１０の代わりに、アクアロンＫＨ−１０（第一工業製薬株式会社製）を用いた以外は、実施例１と同様の操作を行い、実施例４の水性エマルジョン樹脂組成物を得た。なお、実施例４における不飽和単量体組成物の理論Ｔｇは１５℃である。そして、得られた水性エマルジョン樹脂組成物の性状は、不揮発分５０．３重量％、粘度（ＢＭ型粘度計、６０ｒｐｍ、２３℃）１５０ｍＰａ・ｓ、ｐＨ８．９、ＭＦＴ４８℃であった。 <Example 4>
The same procedure as in Example 1 was performed except that Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.) was used instead of Adekaria soap SR-10 in Example 1, and the aqueous emulsion resin in Example 4 was used. A composition was obtained. The theoretical Tg of the unsaturated monomer composition in Example 4 is 15 ° C. The properties of the obtained aqueous emulsion resin composition were a non-volatile content of 50.3% by weight, a viscosity (BM viscometer, 60 rpm, 23 ° C.) 150 mPa · s, pH 8.9, and MFT 48 ° C.

＜比較例１＞
撹拌機、温度計および還流凝縮機を備えた重合装置内に、２５０重量部の脱イオン水および５重量部のエマルゲン１４７（ポリオキシエチレンラウリルエーテル、花王株式会社製）を入れ、窒素置換を十分に行った後、７５℃に昇温した。重合装置内の温度を７５℃に保ちながら、７５重量部のメチルトリメトキシシラン（ＭＴＭＳ）および５０重量部のテトラエトキシシラン（ＴＥＯＳ）を加え、３０分保持した。さらに、４４０重量部の脱イオン水、１０重量部のアクアロンＫＨ−１０、２２３重量部のメタクリル酸メチル、７５重量部のメタクリル酸シクロヘキシル、１９０重量部のアクリル酸−２−エチルヘキシル、２重量部のγ−メタクリロキシプロピルトリメトキシシランおよび１０重量部のメタクリル酸をホモミキサーにて予め混合乳化したものを用意し、重合装置内の温度を７５℃に保ちながら、その乳化物の一部（５重量％）を重合装置内に加えた。
次いで、重合装置内に０．２重量部の過硫酸カリウムを加えて重合を開始し、８０℃で１５分反応させた。さらに、重合装置内の温度を８０℃に保ちながら、先の乳化物の残り（９５重量％）および５０重量部の２％過硫酸カリウム水溶液を４時間掛けて重合装置内に滴下した。さらに、８０℃で２時間反応させ、その後、室温（２５℃）に冷却した。最後に３．５重量部のアンモニア水を入れてｐＨを調整し、比較例１の水性エマルジョン樹脂組成物を得た。なお、比較例１における不飽和単量体組成物の理論Ｔｇは１０℃である。得られた水性エマルジョン樹脂組成物の性状は、不揮発分４１．８重量％、粘度（ＢＭ型粘度計、６０ｒｐｍ、２３℃）６０ｍＰａ・ｓ、ｐＨ５．３、ＭＦＴ３８℃であった。 <Comparative Example 1>
In a polymerization apparatus equipped with a stirrer, a thermometer, and a reflux condenser, 250 parts by weight of deionized water and 5 parts by weight of Emulgen 147 (polyoxyethylene lauryl ether, manufactured by Kao Corporation) are sufficiently substituted with nitrogen. The temperature was raised to 75 ° C. While maintaining the temperature in the polymerization apparatus at 75 ° C., 75 parts by weight of methyltrimethoxysilane (MTMS) and 50 parts by weight of tetraethoxysilane (TEOS) were added and held for 30 minutes. In addition, 440 parts by weight of deionized water, 10 parts by weight Aqualon KH-10, 223 parts by weight methyl methacrylate, 75 parts by weight cyclohexyl methacrylate, 190 parts by weight acrylate-2-ethylhexyl acrylate, 2 parts by weight A mixture of γ-methacryloxypropyltrimethoxysilane and 10 parts by weight of methacrylic acid previously mixed and emulsified with a homomixer was prepared, and a part of the emulsion (5 wt. %) Was added to the polymerization apparatus.
Subsequently, 0.2 weight part potassium persulfate was added in the polymerization apparatus, polymerization was started, and it was made to react at 80 degreeC for 15 minutes. Further, while maintaining the temperature in the polymerization apparatus at 80 ° C., the remaining emulsion (95% by weight) and 50 parts by weight of 2% potassium persulfate aqueous solution were dropped into the polymerization apparatus over 4 hours. Furthermore, it was made to react at 80 degreeC for 2 hours, and it cooled to room temperature (25 degreeC) after that. Finally, 3.5 parts by weight of aqueous ammonia was added to adjust the pH, and the aqueous emulsion resin composition of Comparative Example 1 was obtained. The theoretical Tg of the unsaturated monomer composition in Comparative Example 1 is 10 ° C. The properties of the obtained aqueous emulsion resin composition were a non-volatile content of 41.8% by weight, a viscosity (BM type viscometer, 60 rpm, 23 ° C.), 60 mPa · s, pH 5.3, and MFT of 38 ° C.

＜比較例２＞
撹拌機、温度計および還流凝縮機を備えた重合装置内に、２００重量部の脱イオン水および０．２重量部のアデカリアソープＳＲ−１０を入れ、窒素置換を十分に行った後、７５℃に昇温した。２６０重量部の脱イオン水、９．８重量部のアデカリアソープＳＲ−１０、１２１重量部のメタクリル酸メチル、２００重量部のメタクリル酸シクロヘキシル、１６９重量部のアクリル酸−２−エチルヘキシルおよび１０重量部のメタクリル酸をホモミキサーにて予め混合乳化したものを用意し、重合装置内の温度を７５℃に保ちながら、その乳化物の一部（５重量％）を重合装置内に加えた。
次いで、重合装置内に０．２重量部の過硫酸カリウムを加えて重合を開始し、８０℃で１５分反応させた。さらに、重合装置内の温度を８０℃に保ちながら、先の乳化物の残り（９５重量％）および５０重量部の２％過硫酸カリウム水溶液を４時間掛けて重合装置内に滴下した。さらに、８０℃で２時間反応させ、その後、室温（２５℃）に冷却した。最後に３．５重量部のアンモニア水を入れてｐＨを調整し、比較例２の水性エマルジョン樹脂組成物を得た。なお、比較例２における不飽和単量体組成物の理論Ｔｇは１５℃である。得られた水性エマルジョン樹脂組成物の性状は、不揮発分５０．２重量％、粘度（ＢＭ型粘度計、６０ｒｐｍ、２３℃）１５０ｍＰａ・ｓ、ｐＨ８．９、ＭＦＴ４６℃であった。 <Comparative Example 2>
In a polymerization apparatus equipped with a stirrer, a thermometer, and a reflux condenser, 200 parts by weight of deionized water and 0.2 part by weight of Adeka Soap SR-10 were placed, and after sufficient nitrogen substitution, 75 The temperature was raised to ° C. 260 parts by weight of deionized water, 9.8 parts by weight of ADEKA rear soap SR-10, 121 parts by weight of methyl methacrylate, 200 parts by weight of cyclohexyl methacrylate, 169 parts by weight of -2-ethylhexyl acrylate and 10% by weight A part of the methacrylic acid previously mixed and emulsified with a homomixer was prepared, and a part (5% by weight) of the emulsion was added to the polymerization apparatus while maintaining the temperature in the polymerization apparatus at 75 ° C.
Subsequently, 0.2 weight part potassium persulfate was added in the polymerization apparatus, polymerization was started, and it was made to react at 80 degreeC for 15 minutes. Further, while maintaining the temperature in the polymerization apparatus at 80 ° C., the remaining emulsion (95% by weight) and 50 parts by weight of 2% potassium persulfate aqueous solution were dropped into the polymerization apparatus over 4 hours. Furthermore, it was made to react at 80 degreeC for 2 hours, and it cooled to room temperature (25 degreeC) after that. Finally, 3.5 parts by weight of aqueous ammonia was added to adjust the pH, and an aqueous emulsion resin composition of Comparative Example 2 was obtained. The theoretical Tg of the unsaturated monomer composition in Comparative Example 2 is 15 ° C. The properties of the obtained aqueous emulsion resin composition were a non-volatile content of 50.2 wt%, a viscosity (BM type viscometer, 60 rpm, 23 ° C.) 150 mPa · s, pH 8.9, MFT 46 ° C.

＜比較例３＞
比較例２の乳化物の代わりに、２６０重量部の脱イオン水、９．８重量部のアデカリアソープＳＲ−１０、３０５．５重量部のメタクリル酸メチル、１８３重量部のアクリル酸−２−エチルヘキシル、１．５重量部のγ−メタクリロキシプロピルトリメトキシシランおよび１０重量部のメタクリル酸からなる乳化物を用いた以外は、比較例２と同様の操作を行い、比較例３の水性エマルジョン樹脂組成物を得た。なお、比較例３における不飽和単量体組成物の理論Ｔｇは１５℃である。得られた水性エマルジョン樹脂組成物の性状は、不揮発分５０．１重量％、粘度（ＢＭ型粘度計、６０ｒｐｍ、２３℃）１９０ｍＰａ・ｓ、ｐＨ９．０、ＭＦＴ４２℃であった。 <Comparative Example 3>
Instead of the emulsion of Comparative Example 2, 260 parts by weight of deionized water, 9.8 parts by weight of Adekari Soap SR-10, 305.5 parts by weight of methyl methacrylate, 183 parts by weight of acrylic acid-2- An aqueous emulsion resin of Comparative Example 3 was prepared in the same manner as in Comparative Example 2 except that an emulsion comprising ethylhexyl, 1.5 parts by weight of γ-methacryloxypropyltrimethoxysilane and 10 parts by weight of methacrylic acid was used. A composition was obtained. The theoretical Tg of the unsaturated monomer composition in Comparative Example 3 is 15 ° C. The properties of the obtained aqueous emulsion resin composition were a non-volatile content of 50.1% by weight, a viscosity (BM type viscometer, 60 rpm, 23 ° C.) 190 mPa · s, pH 9.0, and MFT 42 ° C.

＜比較例４＞
撹拌機、温度計および還流凝縮機を備えた重合装置内に、１９９．４重量部の脱イオン水および０．８重量部のニューレックスＲ−２５（アニオン性非反応性界面活性剤、日油株式会社製）を入れ、窒素置換を十分に行った後、７５℃に昇温した。２３０．６重量部の脱イオン水、３９．２重量部のニューレックスＲ−２５、１３１重量部のメタクリル酸メチル、２００重量部のメタクリル酸シクロヘキシル、１５４重量部のアクリル酸−２−エチルヘキシル、５重量部のγ−メタクリロキシプロピルトリメトキシシランおよび１０重量部のメタクリル酸をホモミキサーにて予め混合乳化したものを用意し、重合装置内の温度を７５℃に保ちながら、その乳化物の一部（５重量％）を重合装置内に加えた。
次いで、重合装置内に０．２重量部の過硫酸カリウムを加えて重合を開始し、８０℃で１５分反応させた。さらに、重合装置内の温度を８０℃に保ちながら、先の乳化物の残り（９５重量％）および５０重量部の２％過硫酸カリウム水溶液を４時間掛けて重合装置内に滴下した。さらに、８０℃で２時間反応させ、その後、室温（２５℃）に冷却した。最後に３．５重量部のアンモニア水を入れてｐＨを調整し、比較例４の水性エマルジョン樹脂組成物を得た。なお、比較例４にける不飽和単量体組成物の理論Ｔｇは２０℃である。得られた水性エマルジョン樹脂組成物の性状は、不揮発分５０．２重量％、粘度（ＢＭ型粘度計、６０ｒｐｍ、２３℃）１６０ｍＰａ・ｓ、ｐＨ９．２、ＭＦＴ４９℃であった。 <Comparative example 4>
In a polymerization apparatus equipped with a stirrer, a thermometer and a reflux condenser, 199.4 parts by weight of deionized water and 0.8 parts by weight of Newlex R-25 (anionic non-reactive surfactant, NOF) Co., Ltd.) was added and nitrogen substitution was sufficiently performed, and then the temperature was raised to 75 ° C. 230.6 parts by weight deionized water, 39.2 parts by weight Neulex R-25, 131 parts by weight methyl methacrylate, 200 parts by weight cyclohexyl methacrylate, 154 parts by weight acrylate-2-ethylhexyl acrylate, 5 Prepare a mixture of emulsified parts by weight of γ-methacryloxypropyltrimethoxysilane and 10 parts by weight of methacrylic acid using a homomixer in advance, and maintain a temperature in the polymerization apparatus at 75 ° C. (5 wt%) was added into the polymerization apparatus.
Subsequently, 0.2 weight part potassium persulfate was added in the polymerization apparatus, polymerization was started, and it was made to react at 80 degreeC for 15 minutes. Further, while maintaining the temperature in the polymerization apparatus at 80 ° C., the remaining emulsion (95% by weight) and 50 parts by weight of 2% potassium persulfate aqueous solution were dropped into the polymerization apparatus over 4 hours. Furthermore, it was made to react at 80 degreeC for 2 hours, and it cooled to room temperature (25 degreeC) after that. Finally, 3.5 parts by weight of aqueous ammonia was added to adjust the pH, and an aqueous emulsion resin composition of Comparative Example 4 was obtained. The theoretical Tg of the unsaturated monomer composition in Comparative Example 4 is 20 ° C. The properties of the obtained aqueous emulsion resin composition were a non-volatile content of 50.2% by weight, a viscosity (BM type viscometer, 60 rpm, 23 ° C.) 160 mPa · s, pH 9.2, and MFT 49 ° C.

＜比較例５＞
比較例２の乳化物の代わりに、２６０重量部の脱イオン水、９．８重量部のアデカリアソープＳＲ−１０、２００重量部のメタクリル酸シクロヘキシル、２８５重量部のアクリル酸エチル、５重量部のγ−メタクリロキシプロピルトリメトキシシランおよび１０重量部のメタクリル酸からなる乳化物を用いた以外は、比較例２と同様の操作を行い、比較例５の水性エマルジョン樹脂組成物を得た。なお、比較例５における不飽和単量体組成物の理論Ｔｇは１５℃である。得られた水性エマルジョン樹脂組成物の性状は、不揮発分４９．９重量％、粘度（ＢＭ型粘度計、６０ｒｐｍ、２３℃）１６０ｍＰａ・ｓ、ｐＨ８．９、ＭＦＴ２８℃であった。 <Comparative Example 5>
Instead of the emulsion of Comparative Example 2, 260 parts by weight of deionized water, 9.8 parts by weight of Adekari Soap SR-10, 200 parts by weight of cyclohexyl methacrylate, 285 parts by weight of ethyl acrylate, 5 parts by weight The aqueous emulsion resin composition of Comparative Example 5 was obtained in the same manner as in Comparative Example 2 except that an emulsion composed of γ-methacryloxypropyltrimethoxysilane and 10 parts by weight of methacrylic acid was used. The theoretical Tg of the unsaturated monomer composition in Comparative Example 5 is 15 ° C. The properties of the obtained aqueous emulsion resin composition were a non-volatile content of 49.9% by weight, a viscosity (BM type viscometer, 60 rpm, 23 ° C.) 160 mPa · s, pH 8.9, and MFT 28 ° C.

＜比較例６＞
撹拌機、温度計および還流凝縮機を備えた重合装置内に、２００重量部の脱イオン水および０．２重量部のアデカリアソープＳＲ−１０を入れ、窒素置換を十分に行った後、７５℃に昇温した。２８５重量部の脱イオン水、９．８重量部のアデカリアソープＳＲ−１０、１０５重量部のメタクリル酸メチル、２００重量部のメタクリル酸シクロヘキシル、１６０重量部のアクリル酸−２−エチルヘキシル、１０重量部のメタクリル酸および２５重量部のγ−メタクリロキシプロピルトリメトキシシランをホモミキサーにて予め混合乳化したものを用意し、重合装置内の温度を７５℃に保ちながら、その乳化物の一部（５重量％）を重合装置内に加えた。
次いで、重合装置内に０．２重量部の過硫酸カリウムを加えて重合を開始し、８０℃で１５分反応させた。さらに、重合装置内の温度を８０℃に保ちながら、先の乳化物の残り（９５重量％）および５０重量部の２％過硫酸カリウム水溶液を４時間掛けて重合装置内に滴下した。さらに、８０℃で２時間反応させ、その後、室温（２５℃）に冷却した。最後に３．５重量部のアンモニア水を入れてｐＨを調整し、比較例６の水性エマルジョン樹脂組成物を得た。なお、比較例６における不飽和単量体組成物の理論Ｔｇは１５℃である。得られた水性エマルジョン樹脂組成物の性状は、不揮発分５０．２重量％、粘度（ＢＭ型粘度計、６０ｒｐｍ、２３℃）１４０ｍＰａ・ｓ、ｐＨ８．９、ＭＦＴ９０℃超であった。 <Comparative Example 6>
In a polymerization apparatus equipped with a stirrer, a thermometer, and a reflux condenser, 200 parts by weight of deionized water and 0.2 part by weight of Adeka Soap SR-10 were placed, and after sufficient nitrogen substitution, 75 The temperature was raised to ° C. 285 parts by weight of deionized water, 9.8 parts by weight of ADEKA rear soap SR-10, 105 parts by weight of methyl methacrylate, 200 parts by weight of cyclohexyl methacrylate, 160 parts by weight of 2-ethylhexyl acrylate, 10 parts by weight Prepared by mixing and emulsifying a part of methacrylic acid and 25 parts by weight of γ-methacryloxypropyltrimethoxysilane in advance with a homomixer, and maintaining a temperature in the polymerization apparatus at 75 ° C., a part of the emulsion ( 5% by weight) was added into the polymerization apparatus.
Subsequently, 0.2 weight part potassium persulfate was added in the polymerization apparatus, polymerization was started, and it was made to react at 80 degreeC for 15 minutes. Further, while maintaining the temperature in the polymerization apparatus at 80 ° C., the remaining emulsion (95% by weight) and 50 parts by weight of 2% potassium persulfate aqueous solution were dropped into the polymerization apparatus over 4 hours. Furthermore, it was made to react at 80 degreeC for 2 hours, and it cooled to room temperature (25 degreeC) after that. Finally, 3.5 parts by weight of aqueous ammonia was added to adjust the pH, and an aqueous emulsion resin composition of Comparative Example 6 was obtained. The theoretical Tg of the unsaturated monomer composition in Comparative Example 6 is 15 ° C. The properties of the obtained aqueous emulsion resin composition were a non-volatile content of 50.2% by weight, a viscosity (BM type viscometer, 60 rpm, 23 ° C.) 140 mPa · s, pH 8.9, and MFT over 90 ° C.

＜比較例７＞
比較例２の乳化物の代わりに、２６０重量部の脱イオン水、９．８重量部のアデカリアソープＳＲ−１０、１２．５重量部のメタクリル酸メチル、４７５重量部のメタクリル酸シクロヘキシル、２．５重量部のγ−メタクリロキシプロピルトリメトキシシランおよび１０重量部のメタクリル酸からなる乳化物を用い、比較例２と同様の操作を行ったところ、反応途中で凝集を起こし、ゲル化した。なお、比較例７における不飽和単量体組成物の理論Ｔｇは８５℃である。 <Comparative Example 7>
Instead of the emulsion of Comparative Example 2, 260 parts by weight of deionized water, 9.8 parts by weight of ADEKA rear soap SR-10, 12.5 parts by weight of methyl methacrylate, 475 parts by weight of cyclohexyl methacrylate, 2 When an operation similar to that of Comparative Example 2 was performed using an emulsion composed of 5 parts by weight of γ-methacryloxypropyltrimethoxysilane and 10 parts by weight of methacrylic acid, aggregation occurred during the reaction and gelation occurred. The theoretical Tg of the unsaturated monomer composition in Comparative Example 7 is 85 ° C.

実施例１〜４および比較例１〜７で得られた水性エマルジョン樹脂組成物の耐候性、耐汚染性および長期保存安定性についての評価結果を表１および２に示した。なお、表中の略号「ＭＭＡ」はメタクリル酸メチル、「２ＥＨＡ」はアクリル酸−２−エチルヘキシル、「ＭＡａ」はメタクリル酸、「２ＨＥＭＡ」はメタクリル酸−２−ヒドロキシエチル、「ｎＢＭＡ」はメタクリル酸−ｎ−ブチル、「ｎＢＡ」はアクリル酸−ｎ−ブチル、「Ａａ」はアクリル酸、「ＤＡＡｍ」はジアセトンアクリルアミド、「ＥｔＡ」はアクリル酸エチル、「ＭＴＭＳ」はメチルトリメトキシシラン、「ＴＥＯＳ」はテトラエトキシシランを表す。   Tables 1 and 2 show the evaluation results of the weather resistance, stain resistance and long-term storage stability of the aqueous emulsion resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 7. In the table, the abbreviation “MMA” is methyl methacrylate, “2EHA” is 2-ethylhexyl acrylate, “MAa” is methacrylic acid, “2HEMA” is 2-hydroxyethyl methacrylate, and “nBMA” is methacrylic acid. N-butyl, “nBA” is acrylic acid n-butyl, “Aa” is acrylic acid, “DAAm” is diacetone acrylamide, “EtA” is ethyl acrylate, “MTMS” is methyltrimethoxysilane, “TEOS” "Represents tetraethoxysilane.

Figure 2011046783
Figure 2011046783

Figure 2011046783
Figure 2011046783

実施例１〜４で得られた水性エマルジョン樹脂組成物を用いた塗料は、耐候性、耐汚染性および長期保存安定性に優れることが分かる。それに対して、特許文献１の水分散性樹脂組成物に相当する比較例１は、耐候性および耐汚染性に優れるものの、長期保存安定性が劣ることが分かる。比較例２は、（Ａ）成分を配合していないため、耐候性および耐汚染性に劣ることが分かる。比較例３は、（Ｂ）成分を配合していないため、耐候性および耐汚染性に劣ることが分かる。比較例４は、ラジカル反応性界面活性剤を使用していないため、耐候性および耐汚染性に劣ることが分かる。比較例５は、（Ｃ）成分を配合していないため、耐候性および耐汚染性に劣ることが分かる。比較例６は、（Ａ）成分の配合量が過剰であるため、成膜性が著しく低下し、評価を行えなかった。比較例７は、（Ｂ）成分の配合量が過剰であるため、重合安定性が低下し、各評価を行えなかった。   It can be seen that the coatings using the aqueous emulsion resin compositions obtained in Examples 1 to 4 are excellent in weather resistance, stain resistance and long-term storage stability. On the other hand, Comparative Example 1 corresponding to the water-dispersible resin composition of Patent Document 1 is excellent in weather resistance and stain resistance, but is inferior in long-term storage stability. Since Comparative Example 2 does not contain the component (A), it can be seen that it is inferior in weather resistance and stain resistance. Since the comparative example 3 does not mix | blend (B) component, it turns out that it is inferior to a weather resistance and stain resistance. It can be seen that Comparative Example 4 is inferior in weather resistance and stain resistance because no radical reactive surfactant is used. Since the comparative example 5 does not mix | blend (C) component, it turns out that it is inferior to a weather resistance and stain resistance. In Comparative Example 6, since the blending amount of the component (A) was excessive, the film formability was remarkably lowered and evaluation could not be performed. In Comparative Example 7, since the blending amount of the component (B) was excessive, the polymerization stability was lowered and each evaluation could not be performed.

Claims (2)

（Ａ）γ−メタクリロキシプロピルトリメトキシシランと、（Ｂ）メタクリル酸シクロヘキシルと、（Ｃ）メタクリル酸メチル、（メタ）アクリル酸ブチルおよび（メタ）アクリル酸−２−エチルヘキシルからなる群から選択される少なくとも１つの不飽和単量体とを含む不飽和単量体組成物を、ラジカル反応性界面活性剤の存在下で乳化重合して得られる水性エマルジョン樹脂組成物であって、
（Ａ）γ−メタクリロキシプロピルトリメトキシシランが、不飽和単量体組成物中に０．１〜２重量％含まれ、且つ（Ｂ）メタクリル酸シクロヘキシルが、不飽和単量体組成物中に２５〜７５重量％含まれる水性エマルジョン樹脂組成物。 (A) γ-methacryloxypropyltrimethoxysilane; (B) cyclohexyl methacrylate; (C) methyl methacrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate An aqueous emulsion resin composition obtained by emulsion polymerization of an unsaturated monomer composition containing at least one unsaturated monomer in the presence of a radical reactive surfactant,
(A) γ-methacryloxypropyltrimethoxysilane is contained in the unsaturated monomer composition in an amount of 0.1 to 2% by weight, and (B) cyclohexyl methacrylate is contained in the unsaturated monomer composition. An aqueous emulsion resin composition containing 25 to 75% by weight. 請求項１に記載の水性エマルジョン樹脂組成物が配合された塗料。   A paint containing the aqueous emulsion resin composition according to claim 1.
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