JPH0925381A - Aqueous emulsion and flame-retardant coating material - Google Patents
Aqueous emulsion and flame-retardant coating materialInfo
- Publication number
- JPH0925381A JPH0925381A JP17481895A JP17481895A JPH0925381A JP H0925381 A JPH0925381 A JP H0925381A JP 17481895 A JP17481895 A JP 17481895A JP 17481895 A JP17481895 A JP 17481895A JP H0925381 A JPH0925381 A JP H0925381A
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- polymer
- aqueous emulsion
- emulsifier
- emulsion
- dispersoid
- Prior art date
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は水性エマルジョンお
よびそれを用いた難燃性塗料に関する。TECHNICAL FIELD The present invention relates to an aqueous emulsion and a flame-retardant coating material using the same.
【０００２】[0002]
【従来の技術】近年、エマルジョン型水性塗料の技術的
進歩は非常にめざましいものがある。エマルジョン型水
性塗料は主成分としてバインダーと顔料からなってお
り、さらに塗料の塗膜性能の向上を目的とする各種の添
加剤を含んでいる。塗料の重要な特性である塗膜性能を
決定するのはバインダーであり、用途別に要求される多
様な特性を実現されるため、水性エマルジョンの改良、
高機能化が続けられてきた。このような多種多様な要求
特性に対し、アクリル酸エステルあるいはメタクリル酸
エステル系単量体からなる重合体（以下アクリル系重合
体と略記する）を分散質とする水性エマルジョンは、皮
膜柔軟性、各種官能基導入による高機能化および耐候性
等の点で広い応用範囲があるため、塗料用バインダーと
して主流となってきている。2. Description of the Related Art In recent years, technological advances in emulsion type water-based paints have been extremely remarkable. The emulsion-type water-based paint is composed of a binder and a pigment as main components, and further contains various additives for the purpose of improving the coating film performance of the paint. It is the binder that determines the coating film performance, which is an important property of the paint, and because it achieves the various properties required for each application, improvement of the aqueous emulsion,
Higher functionality has been continued. In response to such a wide variety of required properties, an aqueous emulsion having a dispersoid of a polymer (hereinafter referred to as an acrylic polymer) composed of an acrylic acid ester or a methacrylic acid ester-based monomer has various film flexibility and various properties. Since it has a wide range of applications in terms of functionalization by introducing functional groups and weather resistance, it has become the mainstream as a binder for paints.
【０００３】しかし、アクリル系重合体は、燃えやすい
ため、難燃性が要求される塗料のバインダーとしては、
それ単独では使用することが困難である。そこで、難燃
性塗料のバインダーとして、各種の難燃化技術が応用さ
れており、例えば、りん酸エステル、含ハロゲン燐酸エ
ステル、ハロゲン化合物等の添加型難燃剤やハロゲンを
含有する単量体の共重合等の反応性難燃剤が一般的に併
用されている。難燃性の低いアクリル系重合体にこのよ
うな難燃剤を導入する場合、目標の難燃性のレベルには
相当量の難燃剤の添加が必要となることから、塗膜性能
への悪影響、コスト問題、難燃剤がハロゲン化物の場合
における環境問題などがある。一方、水性エマルジョン
の分散質が酢酸ビニル系単量体からなる重合体の場合に
は、アクリル系重合体に比べて、比較的難燃性が高くな
るが、耐水性、耐候性、Ｔｇの調整、各種官能基導入に
よる高機能化等が劣るという欠点がある。However, since acrylic polymers are easily burned, they are suitable as binders for paints that require flame retardancy.
It is difficult to use by itself. Therefore, various flame-retardant technologies have been applied as binders for flame-retardant paints, for example, addition-type flame retardants such as phosphoric acid esters, halogen-containing phosphoric acid esters, and halogen compounds, and halogen-containing monomers. Reactive flame retardants such as copolymers are generally used together. When such a flame retardant is introduced into a low flame retardant acrylic polymer, it is necessary to add a considerable amount of the flame retardant to the target flame retardancy level, which adversely affects the coating performance. There are cost issues and environmental issues when the flame retardant is a halide. On the other hand, when the dispersoid of the aqueous emulsion is a polymer composed of a vinyl acetate monomer, the flame retardancy is relatively higher than that of an acrylic polymer, but the water resistance, weather resistance and Tg are adjusted. However, there is a drawback that the functionalization by introducing various functional groups is poor.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、上記の問題
点を解消し、耐水性および塗膜の柔軟性等の各種の塗膜
性能に優れ、しかも難燃性の良好な塗料用バインダーと
して好適な水性エマルジョンならびに該水性エマルジョ
ンを用いた難燃性塗料を提供することを目的とするもの
である。DISCLOSURE OF THE INVENTION The present invention solves the above problems and provides a coating binder excellent in various coating performances such as water resistance and flexibility of coating and having good flame retardancy. It is an object of the present invention to provide a suitable aqueous emulsion and a flame-retardant paint using the aqueous emulsion.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記課題
を解決するために鋭意研究を重ねた結果、下記の発明を
見出し、本発明を完成させるに至った。 （１）分散質がビニルエステル系重合体（Ａ）ならびに
メタクリル酸エステル単位、アクリル酸エステル単位お
よびスチレン系単量体単位のうちの少なくとも一種から
なる重合体（Ｂ）からなり、重合体（Ａ）は主として分
散質の中心部に存在し、重合体（Ｂ）は主として分散質
の周辺部に存在し、重合体（Ａ）と重合体（Ｂ）との重
量比率が９：１〜１：９であり、分散剤が５０重量％以
上の乳化剤からなる分散剤である水性エマルジョン。 （２）分散剤が乳化剤およびポリビニルアルコールから
なり、それらの重量比率が５：５〜９：１である上記
（１）記載の水性エマルジョン。 （３）乳化剤およびポリビニルアルコールからなる分散
剤の存在下で、酢酸ビニルを含む単量体を乳化重合して
ビニルエステル系重合体（Ａ）を製造し、しかる後にメ
タクリル酸エステル、アクリル酸エステルおよびスチレ
ン系単量体のうちの少なくとも一種の単量体を、連鎖移
動剤の存在下で、乳化剤からなる分散剤を連続的または
間欠的に添加して乳化重合することにより重合体（Ｂ）
を製造することを特徴とする上記（２）記載の水性エマ
ルジョンの製造方法。 （４）上記（１）または（２）記載の水性エマルジョン
を含有する難燃性塗料。As a result of intensive studies to solve the above problems, the present inventors have found the following invention and completed the present invention. (1) The dispersoid comprises a vinyl ester polymer (A) and a polymer (B) comprising at least one of a methacrylic acid ester unit, an acrylic acid ester unit and a styrene monomer unit, and the polymer (A ) Is mainly present in the central part of the dispersoid, the polymer (B) is mainly present in the peripheral part of the dispersoid, and the weight ratio of the polymer (A) to the polymer (B) is 9: 1 to 1: 1. 9, wherein the dispersant is a dispersant comprising 50% by weight or more of an emulsifier. (2) The aqueous emulsion according to (1) above, wherein the dispersant comprises an emulsifier and polyvinyl alcohol, and their weight ratio is 5: 5 to 9: 1. (3) In the presence of a dispersant consisting of an emulsifier and polyvinyl alcohol, a vinyl acetate-containing monomer is emulsion-polymerized to produce a vinyl ester polymer (A), and then a methacrylic acid ester, an acrylic acid ester and Polymer (B) obtained by emulsion-polymerizing at least one monomer selected from styrenic monomers by continuously or intermittently adding a dispersant consisting of an emulsifier in the presence of a chain transfer agent.
The method for producing an aqueous emulsion according to (2) above, which comprises: (4) A flame-retardant paint containing the aqueous emulsion according to (1) or (2).
【０００６】[0006]
【発明の実施の形態】本発明の水性エマルジョンは、上
述の如き分散質および分散剤からなる。ここで、分散質
は、ビニルエステル系重合体（Ａ）ならびにメタクリル
酸エステル単位、アクリル酸エステル単位およびスチレ
ン系単量体単位のうちの少なくとも一種からなる重合体
（Ｂ）から構成される１個の分散質の集合体である。BEST MODE FOR CARRYING OUT THE INVENTION The aqueous emulsion of the present invention comprises a dispersoid and a dispersant as described above. Here, the dispersoid is one composed of a vinyl ester polymer (A) and a polymer (B) consisting of at least one of a methacrylic acid ester unit, an acrylic acid ester unit and a styrene monomer unit. It is an aggregate of dispersoids.
【０００７】ビニルエステル系重合体（Ａ）としては、
様々なものが挙げられるが、一般には酢酸ビニル，プロ
ピオン酸ビニル，ピバリン酸ビニル，炭素数８〜１０の
３級カルボン酸のビニルエステル（例えばシェル化学社
製，商品名：Ｖｅｏｖａ１０），ステアリン酸ビニル、
さらにはギ酸ビニル，バレリン酸ビニル，カプリン酸ビ
ニル，ラウリン酸ビニル，安息香酸ビニル等のビニルエ
ステル単位を主体とする（共）重合体である。中でも酢
酸ビニルを主体とする（共）重合体が、難燃性能の点か
ら好ましい。これらのビニルエステル単位に３０重量％
以下のエチレン，塩化ビニルなどの共重合可能な単量体
単位や少量のカルボキシル基あるいはアミド基等の官能
基を持つ単量体単位を共重合したものも含まれる。As the vinyl ester polymer (A),
Various compounds can be mentioned, but in general, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl ester of tertiary carboxylic acid having 8 to 10 carbon atoms (for example, Shell Chemical Co., trade name: Veova10), vinyl stearate. ,
Further, it is a (co) polymer mainly composed of vinyl ester units such as vinyl formate, vinyl valerate, vinyl caprate, vinyl laurate and vinyl benzoate. Of these, a (co) polymer mainly containing vinyl acetate is preferable from the viewpoint of flame retardancy. 30% by weight of these vinyl ester units
Also included are those obtained by copolymerizing the following copolymerizable monomer units such as ethylene and vinyl chloride and a small amount of monomer units having a functional group such as a carboxyl group or an amide group.
【０００８】次に、重合体（Ｂ）は、アクリル酸エステ
ル単位、メタクリル酸エステル単位およびスチレン系単
量体単位のうちの少なくとも一種からなる重合体であ
る。重合体（Ｂ）を構成するアクリル酸エステル単位と
しては、アクリル酸メチル、アクリル酸エチル、アクリ
ル酸ｎ−プロピル、アクリル酸ｉ−プロピル、アクリル
酸ｎ−ブチル、アクリル酸ｉ−ブチル、アクリル酸ｔ−
ブチル、アクリル酸２−エチルヘキシル、アクリル酸ド
デシル、アクリル酸オクタデシル等が挙げられ、メタク
リル酸エステル単位としては、メタクリル酸メチル、メ
タクリル酸エチル、メタクリル酸ｎ−プロピル、メタク
リル酸ｉ−プロピル、メタクリル酸ｎ−ブチル、メタク
リル酸ｉ−ブチル、メタクリル酸ｔ−ブチル、メタクリ
ル酸２−エチルヘキシル、メタクリル酸ドデシル、メタ
クリル酸オクタデシル等が挙げられ、スチレン系単量体
単位としては、スチレン、α−メチルスチレン、Ｐ−メ
チルスチレンスルホン酸およびそのナトリウム、カリウ
ム塩等が挙げられる。これらは、単独あるいは２種以上
併用して用いられる。Next, the polymer (B) is a polymer comprising at least one of an acrylic acid ester unit, a methacrylic acid ester unit and a styrene monomer unit. Examples of acrylic acid ester units constituting the polymer (B) include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate and t-acrylate. −
Examples thereof include butyl, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, and the like, and as the methacrylate unit, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-methacrylate. -Butyl, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate and the like can be mentioned, and as the styrene-based monomer unit, styrene, α-methylstyrene, P -Methylstyrene sulfonic acid and its sodium and potassium salts and the like. These may be used alone or in combination of two or more.
【０００９】その他、エチレン、プロピレン、イソブテ
ン等のオレフィン類、塩化ビニル、塩化ビニリデン、フ
ッ化ビニル、フッ化ビニリデン等のハロゲン化オレフィ
ン類、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、ピバリン酸ビニル等のビニルエ
ステル類、アクリル酸、メタクリル酸、アクリルアミ
ド、メタクリルアミド、Ｎ−メチロールアクリルアミ
ド、Ｎ，Ｎ−ジメチルアクリルアミド、アクリルアミド
−２−メチルプロパンスルホン酸およびそのナトリウム
塩のアクリルアミド系単量体類、アクリロニトリル、メ
タクリロニトリル等のニトリル類、酢酸アリル、塩化ア
リル等のアリル化合物、Ｎ−ビニルピロリドン、エチレ
ングリコールジメタクリレート、ジビニルベンゼン等の
多官能性不飽和単量体等を３０重量％以下上記の単量体
に併用して用いて重合体（Ｂ）を構成することもでき
る。In addition, olefins such as ethylene, propylene and isobutene, halogenated olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride, vinyl formate, vinyl acetate and vinyl propionate,
Vinyl esters such as vinyl versatate and vinyl pivalate, acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, acrylamide-2-methylpropanesulfonic acid and its sodium salt, acrylamide. System monomers, nitriles such as acrylonitrile and methacrylonitrile, allyl compounds such as allyl acetate and allyl chloride, polyfunctional unsaturated monomers such as N-vinylpyrrolidone, ethylene glycol dimethacrylate and divinylbenzene. The polymer (B) can also be constituted by using together with the above monomers in an amount of 30% by weight or less.
【００１０】本発明の水性エマルジョンの分散質は、重
合体（Ａ）および重合体（Ｂ）からなる１個の分散質の
集合体であり、重合体（Ａ）は主として分散質の中心部
に存在し、重合体（Ｂ）は主として分散質の周辺部に存
在する二層構造となっている。すなわち、重合体（Ａ）
は主として（具体的には７０重量％以上、好ましくは８
０重量％以上、特に好ましくは９０重量％以上）分散質
の中心部に存在し、重合体（Ｂ）は主として（具体的に
は７０重量％以上、好ましくは８０重量％以上、特に好
ましくは９０重量％以上）分散質の周辺部に存在する構
成となっている。分散質を構成する重合体（Ａ）および
重合体（Ｂ）の形状は、必ずしも球状に限らず、種々の
形状となることができる。分散質における重合体（Ａ）
と重合体（Ｂ）との重量比率は９：１〜１：９、好まし
くは８：２〜２：８である。重合体（Ａ）の重量比率
が、重合体（Ａ）と重合体（Ｂ）の合計量に対して９０
重量％を超えると、その水性エマルジョンを用いて得ら
れる塗料塗膜の柔軟性のコントロールが困難であり、逆
に、１０重量％を下回ると、塗料塗膜の難燃性が低下す
る等の問題が生じる。The dispersoid of the aqueous emulsion of the present invention is an aggregate of one dispersoid composed of the polymer (A) and the polymer (B), and the polymer (A) is mainly present in the central part of the dispersoid. The polymer (B) is present and has a two-layer structure mainly present in the peripheral portion of the dispersoid. That is, the polymer (A)
Mainly (specifically 70% by weight or more, preferably 8% by weight)
0% by weight or more, particularly preferably 90% by weight or more) is present in the central part of the dispersoid, and the polymer (B) is mainly (specifically 70% by weight or more, preferably 80% by weight or more, particularly preferably 90% by weight). (% By weight or more) The composition is present in the periphery of the dispersoid. The shapes of the polymer (A) and the polymer (B) that form the dispersoid are not necessarily spherical, but can be various shapes. Polymer in dispersoid (A)
And the polymer (B) have a weight ratio of 9: 1 to 1: 9, preferably 8: 2 to 2: 8. The weight ratio of the polymer (A) is 90 with respect to the total amount of the polymer (A) and the polymer (B).
If it exceeds 10% by weight, it is difficult to control the flexibility of the coating film obtained by using the aqueous emulsion, and if it is less than 10% by weight, the flame retardancy of the coating film decreases. Occurs.
【００１１】本発明の水性エマルジョンは、上記の分散
質と分散剤を含有するものであり、分散剤としては、５
０重量％以上の乳化剤からなる分散剤が用いられる。乳
化剤としては、従来公知のアニオン性、カチオン性、非
イオン性あるいは両性の界面活性剤が用いられ、単独あ
るいは二種以上が併用される。また、上記のイオン性の
異なる界面活性剤は、目的に応じて適宜選定され、必要
に応じて分子内に二重結合を有する共重合性界面活性剤
を用いることができる。本発明の分散剤としては、乳化
剤にポリビニルアルコール（以下ＰＶＡと略記する）を
併用してもよい。ＰＶＡとしては、従来公知のものが充
当され、例えば、けん化度８０〜９９モル％，重合度２
００〜８０００のＰＶＡや主鎖，側鎖あるいは分子末端
に官能基が導入された所謂変性ＰＶＡも好適である。乳
化剤およびＰＶＡからなる分散剤においては、それらの
重量比率は５：５〜９：１であることが好ましい。乳化
剤が分散剤の総量に対して５０重量％を下回る場合に
は、重合安定性が低下する上、塗料塗膜の耐水性が低下
する。分散剤の使用量（乳化剤とＰＶＡの合計量）とし
ては特に制限はないが、分散質（重合体（Ａ）と重合体
（Ｂ）の合計量）１００重量部に対して０．２〜５０重
量部が好ましく、１〜１０重量部が特に好ましい。The aqueous emulsion of the present invention contains the above dispersoid and a dispersant, and the dispersant is 5
A dispersant consisting of 0% by weight or more of an emulsifier is used. As the emulsifier, conventionally known anionic, cationic, nonionic or amphoteric surfactants are used, and they may be used alone or in combination of two or more. Further, the above-mentioned surfactants having different ionic properties are appropriately selected according to the purpose, and if necessary, a copolymerizable surfactant having a double bond in the molecule can be used. As the dispersant of the present invention, polyvinyl alcohol (hereinafter abbreviated as PVA) may be used in combination with the emulsifier. As the PVA, conventionally known ones are used, for example, a saponification degree of 80 to 99 mol% and a polymerization degree of 2
PVA of 0 to 8000 and so-called modified PVA having a functional group introduced in the main chain, side chain or molecular end are also suitable. In the dispersant consisting of the emulsifier and PVA, their weight ratio is preferably 5: 5 to 9: 1. When the emulsifier is less than 50% by weight based on the total amount of the dispersant, the polymerization stability is lowered and the water resistance of the paint film is lowered. The amount of the dispersant used (the total amount of the emulsifier and PVA) is not particularly limited, but is 0.2 to 50 per 100 parts by weight of the dispersoid (the total amount of the polymer (A) and the polymer (B)). Part by weight is preferred and 1 to 10 parts by weight is particularly preferred.
【００１２】本発明の水性エマルジョンの分散質の平均
粒径は特に制限はないが、０．１〜２μｍが好ましく、
0.１５〜1.５μｍがより好ましい。水性エマルジョンの
分散質濃度は、各種の状況により適宜選定すればよい
が、４０〜６５重量％が好ましく、４５〜５５重量％が
より好ましい。The average particle size of the dispersoid of the aqueous emulsion of the present invention is not particularly limited, but is preferably 0.1 to 2 μm,
0.15-1.5 μm is more preferable. The dispersoid concentration of the aqueous emulsion may be appropriately selected according to various situations, but is preferably 40 to 65% by weight, more preferably 45 to 55% by weight.
【００１３】本発明の水性エマルジョンは、上記の分散
質が乳化剤５０重量％の分散剤によって分散安定化され
たものである。また、本発明の水性エマルジョンには、
所望により各種の水性エマルジョンを添加することがで
きる。かかる水性エマルジョンとしては、酢酸ビニルエ
マルジョン，エチレン−酢酸ビニル共重合体エマルジョ
ン，ポリクロロプレンエマルジョン，ポリブタジエンエ
マルジョン，スチレン−ブタジエン共重合体エマルジョ
ン，ブタジエン−アクリロニトリル共重合体エマルジョ
ン，ブチルゴムエマルジョン，ポリアクリル酸エステル
エマルジョン，ポリ塩化ビニルエマルジョン，ポリ塩化
ビニリデンエマルジョン等が挙げられる。The aqueous emulsion of the present invention is obtained by dispersing and stabilizing the above dispersoid with a dispersant containing 50% by weight of an emulsifier. In addition, the aqueous emulsion of the present invention,
If desired, various aqueous emulsions can be added. Examples of the aqueous emulsion include vinyl acetate emulsion, ethylene-vinyl acetate copolymer emulsion, polychloroprene emulsion, polybutadiene emulsion, styrene-butadiene copolymer emulsion, butadiene-acrylonitrile copolymer emulsion, butyl rubber emulsion, polyacrylic ester emulsion. , Polyvinyl chloride emulsion, polyvinylidene chloride emulsion and the like.
【００１４】本発明の難燃性塗料は、上記水性エマルジ
ョンをバインダーとして、各種無機質や顔料を配合する
ことにより調製される。無機質や顔料としては、特に制
限はなく、各種の天然顔料、合成無機顔料および合成有
機顔料を使用することができる。具体的には、着色顔料
（チタン白、鉄黄、群青、カドミウムイエロー、ベンガ
ラ、クロムイエロー、カーボンブラック、シアニン系顔
料、アゾ系顔料、トリフェニルメタン系顔料、キノリン
系顔料、アントラキノン系顔料、フタロシアニン系顔料
など）、体質顔料（硫酸バリウム、炭酸カルシウム、カ
オリン、タルク、シリカ、アルミナ、パーライト、硅砂
など）、特殊顔料（錆止め顔料、発光顔料、示温顔料な
ど）、繊維状またはリン片状の特殊無機顔料（アスベス
ト、ロックウール、マイカなど）などが挙げられ、これ
ら顔料は単独で用いても良いし、二種以上を組み合わせ
て使用しても良い。The flame-retardant paint of the present invention is prepared by blending various inorganic substances and pigments using the above aqueous emulsion as a binder. The inorganic substances and pigments are not particularly limited, and various natural pigments, synthetic inorganic pigments and synthetic organic pigments can be used. Specifically, coloring pigments (titanium white, iron yellow, ultramarine blue, cadmium yellow, red iron oxide, chrome yellow, carbon black, cyanine pigments, azo pigments, triphenylmethane pigments, quinoline pigments, anthraquinone pigments, phthalocyanines. Type pigments), extender pigments (barium sulfate, calcium carbonate, kaolin, talc, silica, alumina, perlite, silica sand, etc.), special pigments (rust preventive pigments, luminescent pigments, thermochromic pigments, etc.), fibrous or flaky specials Examples thereof include inorganic pigments (asbestos, rock wool, mica, etc.), and these pigments may be used alone or in combination of two or more kinds.
【００１５】顔料や無機質の配合量としては特に制限は
ないが、水性エマルジョンの固形物１００重量部に対し
て４０〜４００重量部が好ましく、６０〜３００重量部
がより好ましい。顔料の添加量が４０重量部未満では塗
膜の難燃性の低下やふくれが発生する問題があり、一
方、４００重量部を越えると塗膜の造膜性が低下した
り、柔軟性や弾性を失うことがある。The amount of the pigment or the inorganic compound is not particularly limited, but is preferably 40 to 400 parts by weight, more preferably 60 to 300 parts by weight, based on 100 parts by weight of the solid matter of the aqueous emulsion. If the amount of pigment added is less than 40 parts by weight, the flame retardancy of the coating film may deteriorate and blistering may occur. On the other hand, if it exceeds 400 parts by weight, the film-forming property of the coating film may deteriorate and the flexibility and elasticity may be reduced. May be lost.
【００１６】本発明の難燃性塗料には、各種の難燃剤を
配合することができる。例えば、難燃剤としてはトリク
レジルホスフェート、クレジルフェニルホスフェート、
トリフェニルホスフェート、ジフェニルオクチルホスフ
ェート、トリブチルホスフェート等のりん酸エステル、
トリス（β−クロルエチル）ホスフェート、トリス（ジ
クロルプロピル）ホスフェート、トリス（２、３−ジブ
ロムプロピル）ホスフェート、トリス（ブロムクロルプ
ロピル）ホスフェート等の含ハロゲンりん酸エステル、
塩素化パラフィン、塩素化ポリエチレン、塩素化ポリフ
ェニル、臭素化ポリフェニル等のハロゲン化合物が挙げ
られ、難燃助剤として三酸化アンチモン、酒石酸アンチ
モンカリ、トリフェニルスチレン等が挙げられる。Various flame retardants can be added to the flame-retardant paint of the present invention. For example, as the flame retardant, tricresyl phosphate, cresyl phenyl phosphate,
Phosphoric acid esters such as triphenyl phosphate, diphenyl octyl phosphate, tributyl phosphate,
Halogen-containing phosphates such as tris (β-chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (bromochloropropyl) phosphate,
Examples thereof include halogen compounds such as chlorinated paraffin, chlorinated polyethylene, chlorinated polyphenyl, and brominated polyphenyl, and flame retardant aids such as antimony trioxide, antimony potassium tartrate, and triphenylstyrene.
【００１７】本発明の難燃性塗料には、本発明の目的を
損なわない範囲で、所望により通常の水性エマルジョン
型塗料を調製する際に用いられる各種の添加成分、例え
ば、メチルセルロース、カルボキシメチルセルロース、
ＰＶＡ、ポリアクリル酸塩、ポリアクリルアミド、ポリ
ビニルピロリドンなどの増粘剤、トリポリリン酸塩、ヘ
キサメタリン酸塩などの縮合リン酸塩、アニオン性、ノ
ニオン性あるいはカチオン性などの界面活性剤、スチレ
ン−無水マレイン酸半エステル塩共重合体、ジイソブチ
レン−無水マレイン酸半エステル塩共重合体などの分散
剤、さらには、消泡剤、防ばい剤、防腐剤、造膜助剤、
老化防止剤、凍結防止剤などを添加することができる。In the flame-retardant coating material of the present invention, various additive components, such as methyl cellulose and carboxymethyl cellulose, which are used in the preparation of a usual aqueous emulsion type coating material, if desired, are used within a range not impairing the object of the present invention.
Thickeners such as PVA, polyacrylates, polyacrylamides and polyvinylpyrrolidones, condensed phosphates such as tripolyphosphates and hexametaphosphates, anionic, nonionic or cationic surfactants, styrene-maleic anhydride Dispersants such as acid half-ester salt copolymers, diisobutylene-maleic anhydride half-ester salt copolymers, and further, defoaming agents, antifungal agents, preservatives, film-forming aids,
Antiaging agents, antifreezing agents and the like can be added.
【００１８】本発明の塗料は、ロール、コテ、刷毛、ス
プレーガンなどを用いて、一般的な方法で塗工される。
そして、布、紙、木材、合板、コンクリート、モルタ
ル、ＡＬＣ板、フレキシブル板、金属板などからなる壁
面、床面、天井面などの様々な面に対して好適に使用す
ることができる。この際、下地との密着性、防水性、耐
候性、美観などの改良を目的として、下地処理剤、上塗
り剤などを使用することもできる。The paint of the present invention is applied by a general method using a roll, a trowel, a brush, a spray gun or the like.
Further, it can be suitably used for various surfaces such as wall surfaces, floor surfaces, and ceiling surfaces made of cloth, paper, wood, plywood, concrete, mortar, ALC plate, flexible plate, metal plate and the like. At this time, for the purpose of improving the adhesion to the base, waterproofness, weather resistance, aesthetics, etc., a base treatment agent, a top coat agent, etc. can be used.
【００１９】本発明の水性エマルジョンを製造するにあ
たっては、様々な手法が考えられるが、なかでも効率よ
く、しかも高品質の水性エマルジョンが製造できる方法
は、乳化剤（必要に応じてＰＶＡを併用）の存在下で、
酢酸ビニルを含む単量体を乳化重合してビニルエステル
系重合体（Ａ）を製造する第一段階と、しかる後にメタ
クリル酸エステル、アクリル酸エステルおよびスチレン
系単量体のうちの少なくとも一種の単量体を連鎖移動剤
の存在下で、乳化剤からなる分散剤を連続的または間欠
的に添加して乳化重合することにより重合体（Ｂ）を製
造する第二段階とからなる二段重合法が好ましい。Various methods are conceivable for producing the aqueous emulsion of the present invention. Among them, the most efficient method for producing a high-quality aqueous emulsion is to use an emulsifier (PVA is optionally used in combination). In the presence of
A first step of producing a vinyl ester polymer (A) by emulsion-polymerizing a vinyl acetate-containing monomer, followed by at least one monomer selected from methacrylic acid ester, acrylic acid ester and styrene monomer. A two-stage polymerization method comprising a second step of producing a polymer (B) by emulsion-polymerizing a monomer by continuously or intermittently adding a dispersant consisting of an emulsifier in the presence of a chain transfer agent. preferable.
【００２０】第一段階では、実質的にビニルエステル系
モノマーの重合を完結するのが望ましいが、７０％程度
の重合転化率で第二段階の重合に移行しても差し支えな
い。また第一段階，第二段階とも、必ずしも同一の重合
反応器で重合する必要はなく、予め別にビニルエステル
系重合体の水性エマルジョンを調製し、これを、メタク
リル酸エステル、アクリル酸エステルおよびスチレン系
単量体のうち少なくとも一種の乳化（共）重合を行う前
に、重合系に添加するいわゆるシード重合の手法で製造
することもできる。なお、この乳化重合における開始剤
としては、特に制限はないが、例えば過酸化水素，クメ
ンヒドロパーオキシド，ｔ−ブチルヒドロパーオキシ
ド，過硫酸塩（カリウム，ナトリウムあるいはアンモニ
ウム塩），過酢酸ｔ−ブチル，過安息香酸ｔ−ブチル等
の酸化性物質が単独あるいはロンガリットやｌ（エル）
−アスコルビン酸等の還元性物質などとのレドックス開
始剤系で好ましく用いられる。In the first stage, it is desirable to substantially complete the polymerization of the vinyl ester-based monomer, but it is possible to shift to the second stage polymerization at a polymerization conversion rate of about 70%. Further, it is not always necessary to carry out the polymerization in the same polymerization reactor in both the first step and the second step. An aqueous emulsion of a vinyl ester polymer is separately prepared in advance, and this is prepared with a methacrylic acid ester, an acrylic acid ester and a styrene type polymer. It can also be produced by a so-called seed polymerization technique in which at least one of the monomers is added to the polymerization system before emulsion (co) polymerization. The initiator in this emulsion polymerization is not particularly limited, but examples thereof include hydrogen peroxide, cumene hydroperoxide, t-butyl hydroperoxide, persulfates (potassium, sodium or ammonium salts), peracetic acid t-. Oxidizing substances such as butyl and t-butyl perbenzoate alone or Rongalit or l (L)
-It is preferably used in a redox initiator system with a reducing substance such as ascorbic acid.
【００２１】本発明の二段重合法では、乳化剤（必要に
応じてＰＶＡを併用）からなる分散剤の存在下で、第一
段階および第二段階の乳化重合を行うことが必要であ
る。なお、ここで使用する乳化剤およびＰＶＡは、本発
明の水性エマルジョンの欄において説明したものが使用
される。分散剤の使用量（乳化剤とＰＶＡの合計量）
は、特に制限はないが、第一段階の重合体（Ａ）と第二
段階の共重合体（Ｂ）の合計量に対して０．２〜５０重
量％、好ましくは１〜１０重量％の範囲である。この分
散剤は、第一段階と第二段階に分けて用いられる。第一
段階と第二段階に用いられる分散剤の比率は、特に制限
されるものではないが、通常、１０：９０〜９９：１の
割合で分割される。第一段階の分散剤の割合が１０重量
％より少ない場合、あるいは、第二段階の分散剤の割合
が１重量％より少ない場合には、第一段階および第二段
階での重合安定性が低下するため好ましくない。また、
第一段階における分散剤の添加方法は、初期仕込み時に
全量を加えてもよく、また一部を重合系に連続的あるい
は間欠的に加えてもよい。また、第二段階における分散
剤の添加方法は、重合系に連続的あるいは間欠的に添加
する方法が好ましい。第二段階の初期に分散剤を一括で
添加する場合には、重合安定性が低下したり、本発明の
目的である二層構造エマルジョンを得ることが難しくな
る。In the two-step polymerization method of the present invention, it is necessary to carry out the emulsion polymerization of the first step and the second step in the presence of a dispersant consisting of an emulsifier (PVA is optionally used together). As the emulsifier and PVA used here, those described in the section of the aqueous emulsion of the present invention are used. Amount of dispersant used (total amount of emulsifier and PVA)
Is not particularly limited, but is 0.2 to 50% by weight, preferably 1 to 10% by weight based on the total amount of the first stage polymer (A) and the second stage copolymer (B). It is a range. This dispersant is used by dividing it into a first stage and a second stage. The ratio of the dispersant used in the first step and the second step is not particularly limited, but is usually divided at a ratio of 10:90 to 99: 1. If the proportion of the first-stage dispersant is less than 10% by weight, or if the proportion of the second-stage dispersant is less than 1% by weight, the polymerization stability in the first and second stages is reduced. It is not preferable because Also,
Regarding the method of adding the dispersant in the first step, the whole amount may be added at the time of initial charging, or a part thereof may be continuously or intermittently added to the polymerization system. Further, the method of adding the dispersant in the second step is preferably a method of continuously or intermittently adding it to the polymerization system. When the dispersant is added all at once in the initial stage of the second step, the polymerization stability is lowered and it is difficult to obtain the two-layer structure emulsion which is the object of the present invention.
【００２２】本発明の水性エマルジョンの製造方法にお
いて、第二段階のメタクリル酸エステル、アクリル酸エ
ステルおよびスチレン系単量体のうちの少なくとも一種
の単量体の乳化重合は、連鎖移動剤の存在下で行うこと
が必要である。連鎖移動剤としては、連鎖移動が起こる
ものであれば特に制限はないが、連鎖移動の効率の点で
メルカプト基を有する化合物が好ましい。メルカプト基
を有する化合物としては、ｎ−オクチルメルカプタン、
ｎ−ドデシルメルカプタン、ｔ−ドデシルメルカプタン
等のアルキルメルカプタン、２−メルカプトエタノー
ル、３−メルカプトプロピオン酸等が挙げられる。連鎖
移動剤の添加量は、連鎖移動剤の効率にもよるが、通
常、第二段階において用いられる単量体１００重量部に
対して、０．００１〜５重量部が好ましい。連鎖移動剤
が０．００１重量部より少ない場合には重合安定性が低
下し、５重量部を越える場合には第二段階で生成する重
合体（Ｂ）の分子量が低下し、塗膜強度等に影響を及ぼ
すため好ましくない。連鎖移動剤の重合系への添加方法
は特に制限はなく、第二段階の初期に一括して添加する
方法や、連続的あるいは間欠的に逐次添加する方法等が
選択できる。In the method for producing an aqueous emulsion of the present invention, the emulsion polymerization of at least one of the methacrylic acid ester, the acrylic acid ester and the styrenic monomer in the second step is carried out in the presence of a chain transfer agent. It is necessary to do in. The chain transfer agent is not particularly limited as long as it causes chain transfer, but a compound having a mercapto group is preferable in terms of chain transfer efficiency. Examples of the compound having a mercapto group include n-octyl mercaptan,
Examples thereof include alkyl mercaptans such as n-dodecyl mercaptan and t-dodecyl mercaptan, 2-mercaptoethanol, 3-mercaptopropionic acid and the like. The amount of the chain transfer agent added is usually 0.001 to 5 parts by weight with respect to 100 parts by weight of the monomer used in the second step, although it depends on the efficiency of the chain transfer agent. When the amount of the chain transfer agent is less than 0.001 part by weight, the polymerization stability is lowered, and when it exceeds 5 parts by weight, the molecular weight of the polymer (B) produced in the second step is lowered, and the coating strength etc. It is not preferable because it affects the The method of adding the chain transfer agent to the polymerization system is not particularly limited, and a method of adding it all at once in the initial stage of the second step, a method of adding it continuously or intermittently, and the like can be selected.
【００２３】本発明の二段重合法の第一段階で用いるビ
ニルエステル系モノマーは、ビニルエステル系重合体
（Ａ）の原料となるものであり、その種類については、
このビニルエステル系重合体（Ａ）の種類に対応したも
のとすればよい。また、第二段階で用いるメタクリル酸
エステル、アクリル酸エステルおよびスチレン系単量体
についても、重合体（Ｂ）の原料となるものであり、そ
の種類や使用割合については、重合体（Ｂ）の種類や組
成に対応したものとすればよい。さらに、第一段階で製
造すべきビニルエステル系重合体（Ａ）と第二段階で製
造すべき重合体（Ｂ）の重量比率についても、本発明の
水性エマルジョンにおける重合体（Ａ）と重合体（Ｂ）
との重量比率に対応するように選定すればよい。The vinyl ester-based monomer used in the first stage of the two-step polymerization method of the present invention is a raw material for the vinyl ester-based polymer (A).
What corresponds to the kind of the vinyl ester polymer (A) may be used. Further, the methacrylic acid ester, acrylic acid ester, and styrene-based monomer used in the second step are also raw materials of the polymer (B), and the types and the usage ratios of the polymer (B) are It may be adapted to the type and composition. Further, regarding the weight ratio of the vinyl ester polymer (A) to be produced in the first step and the polymer (B) to be produced in the second step, the polymer (A) and the polymer in the aqueous emulsion of the present invention (B)
It may be selected so as to correspond to the weight ratio of.
【００２４】本発明の水性エマルジョンは、難燃性塗料
用のバインダーとして好適に用いることができるが、そ
の他、ポリエチレン、ポリプロピレン等の疎水性被着体
用接着剤、粘着剤、難燃性を要求されない一般の塗料用
バインダー、不織布等の繊維バインダー、モルタル混和
剤等にも使用することができる。The aqueous emulsion of the present invention can be suitably used as a binder for flame-retardant paints, but in addition, an adhesive for hydrophobic adherends such as polyethylene and polypropylene, an adhesive, and flame retardancy are required. It can also be used as an ordinary binder for paints, a fiber binder for non-woven fabrics, a mortar admixture, and the like.
【００２５】[0025]
【実施例】以下、実施例および比較例を挙げて本発明を
さらに具体的に説明する。尚、実施例および比較例中、
「部」および「％」は特に断りのない限り重量基準を示
すものとする。 実施例１ （１）第一段階 攪拌機，窒素導入管，各種薬剤注入ポンプが具備された
オートクレーブに、平均重合度５５０，けん化度８８モ
ル％の部分けん化ＰＶＡ（ＰＶＡ−１）２部をイオン交
換水６５部で加熱溶解した後、非イオン性乳化剤（ノニ
ポール２００、三洋化成製）１部を添加した。それに酢
酸ビニル４５部を添加し、窒素置換後、エチレンを３０
ｋｇ／ｃｍ2 まで加圧し、６０℃まで昇温した。１％過
酸化水素水溶液とロンガリット水溶液を連続的に添加し
重合を開始した。２時間後、残存酢酸ビニル濃度が３％
に低下した時点で第一段階（エチレン−酢酸ビニル共重
合エマルジョン）を終了した。 （２）第二段階 次いで、メチルメタクリレート（ＭＭＡ）／２−エチル
ヘキシルアクリレート（２−ＥＨＡ）＝１０／９０（重
量比）の混合モノマー５０部にｎ−ドデシルメルカプタ
ンを０．１部を添加し、それを２時間かけて連続的に添
加した。この間、１％過酸化水素水溶液とロンガリット
水溶液を連続的に添加した。なお、重合中に、非イオン
性乳化剤（ノニポール２００、三洋化成製）の１０％水
溶液２０部を２時間かけて添加した。得られた水性エマ
ルジョンの固形分濃度は５２. ５％、粘度は１１００ｍ
Ｐａ・ｓ（ミリパスカル秒）であった。The present invention will be described more specifically below with reference to examples and comparative examples. In Examples and Comparative Examples,
“Parts” and “%” are based on weight unless otherwise specified. Example 1 (1) First Step 2 parts of partially saponified PVA (PVA-1) having an average degree of polymerization of 550 and a degree of saponification of 88 mol% was ion-exchanged in an autoclave equipped with a stirrer, a nitrogen introduction tube, and various chemical injection pumps. After heating and dissolving with 65 parts of water, 1 part of a nonionic emulsifier (Nonipol 200, manufactured by Sanyo Kasei) was added. To it, 45 parts of vinyl acetate was added, and after replacement with nitrogen, ethylene was added to 30 parts.
The pressure was increased to kg / cm 2 and the temperature was raised to 60 ° C. Polymerization was initiated by continuously adding a 1% hydrogen peroxide aqueous solution and a Rongalit aqueous solution. After 2 hours, the residual vinyl acetate concentration is 3%
The first stage (ethylene-vinyl acetate copolymer emulsion) was terminated when the temperature dropped to 1. (2) Second stage Next, 0.1 part of n-dodecyl mercaptan was added to 50 parts of a mixed monomer of methyl methacrylate (MMA) / 2-ethylhexyl acrylate (2-EHA) = 10/90 (weight ratio), It was added continuously over 2 hours. During this period, a 1% hydrogen peroxide aqueous solution and a Rongalit aqueous solution were continuously added. During the polymerization, 20 parts of a 10% aqueous solution of a nonionic emulsifier (Nonipol 200, manufactured by Sanyo Kasei) was added over 2 hours. The resulting aqueous emulsion has a solid content concentration of 52.5% and a viscosity of 1100 m.
It was Pa · s (millipascal second).
【００２６】（３）難燃性塗料性能 次に上記水性エマルジョンを用いて、以下の条件により
塗料を作成し試験を行った。結果を表１に示す。 〔塗料配合〕水性エマルジョンに炭酸カルシウム（ホワ
イトンＰ−３０、東洋ファインケミカル製）を固形分比
率で４０／６０に混合し、水を加えて固形分濃度６５％
の塗料を作成した。 〔塗膜の作成〕クラフト紙に塗布量５００ｇ／ｍ2 で上
記塗料を刷毛塗りし、２０℃，６５％ＲＨ下で３日間乾
燥させて塗膜を得た。 〔試験方法〕 ・塗膜状態：塗膜表面の状態を目視観察すると共に、手
で折曲げた状態を観察した。評価は３段階で行った。 Ａ：折曲げてもヒビ、剥離等がなく良好 Ｂ：折曲げると塗膜にひびが入る Ｃ：折曲げると、塗膜が剥離する ・塗膜耐水性：塗膜を２０℃水に２４時間浸漬後、表面
を指で擦った時の状態を観察した。評価は３段階で行っ
た。 Ａ：再乳化なし良好 Ｂ：わずかに再乳化する Ｃ：再乳化し塗膜が崩壊する ・塗膜難燃性：アルコールランプの炎から１ｃｍの所に
塗膜表面を近づけた場合の、塗膜状態を観察した。評価
は３段階で行った。 Ａ：１分以上着火せず、着火しても炎が消えやすい Ｂ：１分以上着火しないが、着火すると激しく燃える Ｃ：１未満に着火し、激しく燃える(3) Flame-retardant paint performance Next, using the above aqueous emulsion, a paint was prepared under the following conditions and tested. The results are shown in Table 1. [Coating composition] Calcium carbonate (Whiten P-30, manufactured by Toyo Fine Chemical Co., Ltd.) was mixed with an aqueous emulsion at a solid content ratio of 40/60, and water was added to solid content concentration of 65%.
Created the paint. [Preparation of coating film] A kraft paper was coated with the above coating composition at a coating amount of 500 g / m 2 and dried at 20 ° C. and 65% RH for 3 days to obtain a coating film. [Test method] -Coating state: The state of the coating film surface was visually observed and the state of being bent by hand was also observed. The evaluation was performed in three stages. A: Good even when bent, without cracks or peeling. B: Cracks in the coating when bent. C: When peeled, the coating peels.-Water resistance of coating: 24 hours in 20 ° C water. After the immersion, the state when the surface was rubbed with a finger was observed. The evaluation was performed in three stages. A: Good without re-emulsification B: Slightly re-emulsified C: Re-emulsified and the coating film disintegrated ・ Coating flame retardancy: Coating film when the surface of the coating was brought 1 cm away from the flame of the alcohol lamp The condition was observed. The evaluation was performed in three stages. A: The flame does not ignite for more than 1 minute, and the flame easily disappears even if ignited. B: It does not ignite for more than 1 minute, but it burns violently when ignited.
【００２７】実施例２ （１）第一段階 実施例１で用いたオートクレーブに、実施例１と同じ
（ＰＶＡ−１）０．５部をイオン交換水７５部に溶解
し、それにアニオン性乳化剤（サンデットＢＬ、三洋化
成製）０．１部と非イオン性乳化剤（ノニポール４０
０、三洋化成性）２部を添加した。酢酸ビニルを８部と
ＶｅｏＶａー１０（シェル製）２．８を添加し、窒素置
換後、６０℃，３０ｋｇ／ｃｍ2 のエチレン加圧下、過
硫酸カリウムとロンガリット水溶液を添加し、重合を開
始した。次いで、酢酸ビニルを３２部とＶｅｏＶａー１
０を１１．２部を混合したものを３時間かけて連続添加
し、重合系のモノマー濃度が１％になるまで重合した。 （２）第二段階 次いで、スチレン（Ｓｔ）４部、ｎ−ブチルアクリレー
ト（ＢＡ）３５部、アクリル酸（ＡＡ）１部の混合モノ
マーにｔ−ドデシルメルカプタン０．１部を添加したも
のを２時間かけて連続添加し、重合した。なお、アニオ
ン性乳化剤（サンデットＢＬ）０．２部と非イオン性乳
化剤（ノニポール４００）を１０部のイオン交換水に溶
解したものを重合中に添加した。得られた水性エマルジ
ョンの固形分濃度は５２. ０％、粘度は４５０ｍＰａ・
ｓであった。得られた水性エマルジョンを用いて、実施
例１と同様に塗料を作成し、性能を評価した。結果を表
１に示す。Example 2 (1) First Step In the autoclave used in Example 1, 0.5 part of the same (PVA-1) as in Example 1 was dissolved in 75 parts of deionized water, and an anionic emulsifier ( Sandet BL, Sanyo Chemical Co., Ltd. 0.1 part and nonionic emulsifier (Nonipol 40)
0, Sanyo Kasei) was added. After adding 8 parts of vinyl acetate and VeoVa-10 (manufactured by Shell) 2.8 and purging with nitrogen, potassium persulfate and an aqueous solution of Rongalit were added under the pressure of ethylene at 60 ° C. and 30 kg / cm 2 to start the polymerization. . Next, 32 parts of vinyl acetate and VeoVa-1
A mixture of 11.2 parts of 0 was continuously added over 3 hours, and polymerization was performed until the monomer concentration of the polymerization system became 1%. (2) Second Step Next, 2 parts of a mixture of 0.1 parts of t-dodecyl mercaptan to a mixed monomer of 4 parts of styrene (St), 35 parts of n-butyl acrylate (BA) and 1 part of acrylic acid (AA) was added. Polymerization was carried out by continuously adding over time. In addition, 0.2 part of an anionic emulsifier (Sandet BL) and a nonionic emulsifier (Nonipol 400) dissolved in 10 parts of ion-exchanged water were added during polymerization. The obtained aqueous emulsion has a solid content concentration of 52.0% and a viscosity of 450 mPa.
s. Using the obtained aqueous emulsion, a paint was prepared in the same manner as in Example 1 and the performance was evaluated. The results are shown in Table 1.
【００２８】実施例３ 実施例２の第一段階において、（ＰＶＡ−１）を用いな
い以外は、実施例２と同様にして水性エマルジョンを得
た。得られた水性エマルジョンの固形分濃度は５１. ６
％、粘度は２５０ｍＰａ・ｓであった。得られた水性エ
マルジョンを用いて、実施例１と同様に塗料を作成し、
性能を評価した。結果を表１に示す。Example 3 An aqueous emulsion was obtained in the same manner as in Example 2 except that (PVA-1) was not used in the first step of Example 2. The solid concentration of the obtained aqueous emulsion is 51.6.
%, The viscosity was 250 mPa · s. A coating composition was prepared in the same manner as in Example 1 using the obtained aqueous emulsion,
The performance was evaluated. The results are shown in Table 1.
【００２９】比較例１ 実施例１の第一段階において、（ＰＶＡ−１）４部を用
いた以外は、実施例１と同様にして、水性エマルジョン
を得た。得られた水性エマルジョンの固形分濃度は５
２. ７％、粘度は４８００ｍＰａ・ｓであった。得られ
た水性エマルジョンを用いて、実施例１と同様に塗料を
作成し、性能を評価した。結果を表１に示す。Comparative Example 1 An aqueous emulsion was obtained in the same manner as in Example 1 except that 4 parts of (PVA-1) was used in the first step of Example 1. The resulting aqueous emulsion has a solid content of 5
The viscosity was 2.7% and the viscosity was 4800 mPa · s. Using the obtained aqueous emulsion, a paint was prepared in the same manner as in Example 1 and the performance was evaluated. The results are shown in Table 1.
【００３０】比較例２ 還流冷却器、滴下ロート、温度計、窒素吹込口、撹拌機
を備えたガラス製容器に、（ＰＶＡ−１）２部と非イオ
ン性乳化剤（ノニポール２００、三洋化成製）３部をイ
オン交換水９０部に完全溶解させた。窒素置換後、メチ
ルメタクリレート（ＭＭＡ）／２−エチルヘキシルアク
リレート（２−ＥＨＡ）＝１０／９０（重量比）の混合
モノマー１０部とｎ−ドデシルメルカプタン０．０２部
を添加し、７０℃に昇温し、１％過硫酸カリウム５部を
添加して重合を開始した。その後、メチルメタクリレー
ト（ＭＭＡ）／２−エチルヘキシルアクリレート（２−
ＥＨＡ）＝１０／９０（重量比）の混合モノマー９０部
にｎ−ドデシルメルカプタンを０．１８部を添加したも
のを、２時間かけて連続的に添加した。得られた水性エ
マルジョンは、固形分濃度５２．２％、粘度４３０ｍＰ
ａ．ｓであった。得られた水性エマルジョンを用いて、
実施例１と同様に塗料を作成し、性能を評価した。結果
を表１に示す。Comparative Example 2 2 parts of (PVA-1) and a nonionic emulsifier (Nonipol 200, manufactured by Sanyo Kasei) were placed in a glass container equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen inlet, and a stirrer. 3 parts was completely dissolved in 90 parts of ion-exchanged water. After nitrogen substitution, 10 parts of a mixed monomer of methyl methacrylate (MMA) / 2-ethylhexyl acrylate (2-EHA) = 10/90 (weight ratio) and 0.02 part of n-dodecyl mercaptan were added, and the temperature was raised to 70 ° C. Then, 5 parts of 1% potassium persulfate was added to initiate polymerization. Then, methyl methacrylate (MMA) / 2-ethylhexyl acrylate (2-
A mixture of 90 parts of a mixed monomer (EHA) = 10/90 (weight ratio) and 0.18 part of n-dodecyl mercaptan was continuously added over 2 hours. The obtained aqueous emulsion has a solid content concentration of 52.2% and a viscosity of 430 mP.
a. s. Using the obtained aqueous emulsion,
A paint was prepared in the same manner as in Example 1 and its performance was evaluated. The results are shown in Table 1.
【００３１】比較例３ 攪拌機，窒素導入管，各種薬剤注入ポンプが具備された
オートクレーブに、（ＰＶＡ−１）２部をイオン交換水
６５部で加熱溶解した後、非イオン性乳化剤（ノニポー
ル２００、三洋化成製）１部を添加した。それに酢酸ビ
ニル４．５部、メタクリル酸メチル０．５部、アクリル
酸２−エチルヘキシル４．５部、ｎ−ドデシルメルカプ
タン０．０１部を添加し、窒素置換後、エチレンを３０
ｋｇ／ｃｍ2 まで加圧し、６０℃まで昇温した。１％過
酸化水素水溶液とロンガリット水溶液を連続的に添加し
重合を開始した。重合開始後、酢酸ビニル４０．５部、
メタクリル酸メチル４．５部、アクリル酸２−エチルヘ
キシル４０．５部、ｎ−ドデシルメルカプタン０．０９
部を２時間かけて連続的に添加した。また、重合中、非
イオン性乳化剤（ノニポール２００、三洋化成製）２０
％水溶液１０部を２時間かけて添加した。得られた水性
エマルジョンは、固形分濃度５２．３％、粘度８５０ｍ
Ｐａ．ｓであった。得られた水性エマルジョンを用い
て、実施例１と同様に塗料を作成し、性能を評価した。
結果を表１に示す。Comparative Example 3 2 parts of (PVA-1) was heated and dissolved with 65 parts of ion-exchanged water in an autoclave equipped with a stirrer, a nitrogen introduction tube, and various chemical injection pumps, and then a nonionic emulsifier (Nonipol 200, 1 part of Sanyo Kasei) was added. 4.5 parts of vinyl acetate, 0.5 parts of methyl methacrylate, 4.5 parts of 2-ethylhexyl acrylate, and 0.01 parts of n-dodecyl mercaptan were added thereto, and after nitrogen substitution, ethylene was added to 30 parts.
The pressure was increased to kg / cm 2 and the temperature was raised to 60 ° C. Polymerization was initiated by continuously adding a 1% hydrogen peroxide aqueous solution and a Rongalit aqueous solution. After the initiation of polymerization, 40.5 parts of vinyl acetate,
Methyl methacrylate 4.5 parts, 2-ethylhexyl acrylate 40.5 parts, n-dodecyl mercaptan 0.09
Parts were added continuously over 2 hours. During the polymerization, a nonionic emulsifier (Nonipol 200, manufactured by Sanyo Kasei) 20
% Aqueous solution was added over 2 hours. The obtained aqueous emulsion has a solid content concentration of 52.3% and a viscosity of 850 m.
Pa. s. Using the obtained aqueous emulsion, a paint was prepared in the same manner as in Example 1 and the performance was evaluated.
The results are shown in Table 1.
【００３２】比較例４ 攪拌機，窒素導入管，各種薬剤注入ポンプが具備された
オートクレーブに、（ＰＶＡ−１）２部をイオン交換水
６５部で加熱溶解した後、非イオン性乳化剤（ノニポー
ル２００、三洋化成製）３部を添加した。それに酢酸ビ
ニル９０部を添加し、窒素置換後、エチレンを３０ｋｇ
／ｃｍ2 まで加圧し、６０℃まで昇温した。１％過酸化
水素水溶液とロンガリット水溶液を連続的に添加し重合
を開始した。重合開始３時間後、残存酢酸ビニル濃度が
０．９％となり重合を終了した。得られた水性エマルジ
ョンは、固形分濃度５２．５％、粘度１０００ｍＰａ．
ｓであった。得られた水性エマルジョンを用いて、実施
例１と同様に塗料を作成し、性能を評価した。結果を表
１に示す。Comparative Example 4 In an autoclave equipped with a stirrer, a nitrogen introducing tube, and various chemical injection pumps, 2 parts of (PVA-1) was heated and dissolved with 65 parts of ion-exchanged water, and then a nonionic emulsifier (Nonipol 200, Sanyo Kasei) 3 parts were added. Add 90 parts of vinyl acetate to it and replace with nitrogen, then add 30 kg of ethylene.
The pressure was increased to / cm 2 and the temperature was raised to 60 ° C. Polymerization was initiated by continuously adding a 1% hydrogen peroxide aqueous solution and a Rongalit aqueous solution. Three hours after the initiation of the polymerization, the residual vinyl acetate concentration reached 0.9% and the polymerization was completed. The obtained aqueous emulsion had a solid content concentration of 52.5% and a viscosity of 1000 mPa.s.
s. Using the obtained aqueous emulsion, a paint was prepared in the same manner as in Example 1 and the performance was evaluated. The results are shown in Table 1.
【００３３】[0033]
【表１】 [Table 1]
【００３４】[0034]
【発明の効果】本発明の水性エマルジョンは、難燃性塗
料用のバインダーをはじめとして、疎水性被着体用接着
剤、粘着剤、難燃性を要求されない一般の塗料用バイン
ダー、繊維バインダー、モルタル混和剤等の各種の用途
に供される。特に難燃性塗料用バインダーとして用いた
場合には、塗膜の難燃性および耐水性が飛躍的に向上し
たものが得られる。The aqueous emulsion of the present invention includes a binder for a flame-retardant paint, an adhesive for a hydrophobic adherend, a pressure-sensitive adhesive, a binder for a general paint which does not require flame retardancy, a fiber binder, It is used for various purposes such as mortar admixtures. In particular, when it is used as a binder for flame-retardant paint, a coating film having dramatically improved flame retardancy and water resistance can be obtained.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｆ 18/08 ＭＬＥ Ｃ０８Ｆ 18/08 ＭＬＥ 20/18 ＭＬＹ 20/18 ＭＬＹ Ｃ０８Ｌ 33/06 ＬＪＧ Ｃ０８Ｌ 33/06 ＬＪＧ Ｃ０９Ｄ 5/00 ＰＰＵ Ｃ０９Ｄ 5/00 ＰＰＵ 5/18 ＰＱＰ 5/18 ＰＱＰ 133/06 ＰＦＸ 133/06 ＰＦＸ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C08F 18/08 MLE C08F 18/08 MLE 20/18 MLY 20/18 MLY C08L 33/06 LJG C08L 33 / 06 LJG C09D 5/00 PPU C09D 5/00 PPU 5/18 PQP 5/18 PQP 133/06 PFX 133/06 PFX
Claims (4)
ならびにメタクリル酸エステル単位、アクリル酸エステ
ル単位およびスチレン系単量体単位のうちの少なくとも
一種からなる重合体（Ｂ）からなり、重合体（Ａ）は主
として分散質の中心部に存在し、重合体（Ｂ）は主とし
て分散質の周辺部に存在し、重合体（Ａ）と重合体
（Ｂ）との重量比率が９：１〜１：９であり、分散剤が
５０重量％以上の乳化剤からなる分散剤である水性エマ
ルジョン。1. The dispersoid is a vinyl ester polymer (A).
And a polymer (B) consisting of at least one of a methacrylic acid ester unit, an acrylic acid ester unit and a styrene-based monomer unit, wherein the polymer (A) is mainly present in the central part of the dispersoid, (B) is mainly present in the peripheral part of the dispersoid, the weight ratio of the polymer (A) to the polymer (B) is 9: 1 to 1: 9, and the dispersant is composed of 50% by weight or more of an emulsifier. An aqueous emulsion that is a dispersant.
ールからなり、それらの重量比率が５：５〜９：１であ
る請求項１記載の水性エマルジョン。2. The aqueous emulsion according to claim 1, wherein the dispersant comprises an emulsifier and polyvinyl alcohol, and their weight ratio is 5: 5 to 9: 1.
なる分散剤の存在下で、酢酸ビニルを含む単量体を乳化
重合してビニルエステル系重合体（Ａ）を製造し、しか
る後にメタクリル酸エステル、アクリル酸エステルおよ
びスチレン系単量体のうちの少なくとも一種の単量体
を、連鎖移動剤の存在下で、乳化剤からなる分散剤を連
続的または間欠的に添加して乳化重合することにより重
合体（Ｂ）を製造することを特徴とする請求項２記載の
水性エマルジョンの製造方法。3. A vinyl ester-based polymer (A) is produced by emulsion-polymerizing a vinyl acetate-containing monomer in the presence of an emulsifier and a dispersant composed of polyvinyl alcohol. A polymer (B) is prepared by emulsion-polymerizing at least one monomer selected from ester and styrenic monomers by continuously or intermittently adding a dispersant consisting of an emulsifier in the presence of a chain transfer agent. ) Is manufactured, The manufacturing method of the aqueous emulsion of Claim 2 characterized by the above-mentioned.
ンを含有する難燃性塗料。4. A flame-retardant paint containing the aqueous emulsion according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17481895A JP3590457B2 (en) | 1995-07-11 | 1995-07-11 | Method for producing aqueous emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17481895A JP3590457B2 (en) | 1995-07-11 | 1995-07-11 | Method for producing aqueous emulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0925381A true JPH0925381A (en) | 1997-01-28 |
| JP3590457B2 JP3590457B2 (en) | 2004-11-17 |
Family
ID=15985206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17481895A Expired - Fee Related JP3590457B2 (en) | 1995-07-11 | 1995-07-11 | Method for producing aqueous emulsion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3590457B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000169657A (en) * | 1998-12-08 | 2000-06-20 | Kuraray Co Ltd | Emulsion for flame-retarded foam sheet |
| JP2003105007A (en) * | 2001-09-28 | 2003-04-09 | Nippon Synthetic Chem Ind Co Ltd:The | Process for producing acrylic emulsion |
| JP2006124682A (en) * | 2004-09-29 | 2006-05-18 | Nippon Synthetic Chem Ind Co Ltd:The | Aqueous emulsion and application thereof |
| WO2007060960A1 (en) * | 2005-11-24 | 2007-05-31 | Nichigo-Mowinyl Co., Ltd. | Re-emulsifiable resin powder, aqueous emulsion and adhesive composition using same |
| WO2008133375A1 (en) * | 2007-04-27 | 2008-11-06 | Youngwoo Chemtech Co., Ltd. | Acrylic acid ester copolymer composition and redispersible powders |
| WO2009011334A1 (en) * | 2007-07-18 | 2009-01-22 | Nichigo-Mowinyl Co., Ltd. | Aqueous synthetic resin emulsion, re-emulsifiable emulion powder, and adhesive composition containing the same |
| JP2012214580A (en) * | 2011-03-31 | 2012-11-08 | Dainippon Toryo Co Ltd | Adhesive composition and method of manufacturing the same |
| CN103265659A (en) * | 2013-05-14 | 2013-08-28 | 武汉理工大学 | Polyvinyl acetate/polystyrene composite emulsion with high covering power polyvinyl and preparation method thereof |
| JP2013241584A (en) * | 2012-04-27 | 2013-12-05 | Dainippon Toryo Co Ltd | Flame-retardant aqueous coating composition, and flame-retardant coating film and building board using the same |
-
1995
- 1995-07-11 JP JP17481895A patent/JP3590457B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000169657A (en) * | 1998-12-08 | 2000-06-20 | Kuraray Co Ltd | Emulsion for flame-retarded foam sheet |
| JP2003105007A (en) * | 2001-09-28 | 2003-04-09 | Nippon Synthetic Chem Ind Co Ltd:The | Process for producing acrylic emulsion |
| JP2006124682A (en) * | 2004-09-29 | 2006-05-18 | Nippon Synthetic Chem Ind Co Ltd:The | Aqueous emulsion and application thereof |
| WO2007060960A1 (en) * | 2005-11-24 | 2007-05-31 | Nichigo-Mowinyl Co., Ltd. | Re-emulsifiable resin powder, aqueous emulsion and adhesive composition using same |
| WO2008133375A1 (en) * | 2007-04-27 | 2008-11-06 | Youngwoo Chemtech Co., Ltd. | Acrylic acid ester copolymer composition and redispersible powders |
| WO2009011334A1 (en) * | 2007-07-18 | 2009-01-22 | Nichigo-Mowinyl Co., Ltd. | Aqueous synthetic resin emulsion, re-emulsifiable emulion powder, and adhesive composition containing the same |
| JP2012214580A (en) * | 2011-03-31 | 2012-11-08 | Dainippon Toryo Co Ltd | Adhesive composition and method of manufacturing the same |
| JP2013241584A (en) * | 2012-04-27 | 2013-12-05 | Dainippon Toryo Co Ltd | Flame-retardant aqueous coating composition, and flame-retardant coating film and building board using the same |
| CN103265659A (en) * | 2013-05-14 | 2013-08-28 | 武汉理工大学 | Polyvinyl acetate/polystyrene composite emulsion with high covering power polyvinyl and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3590457B2 (en) | 2004-11-17 |
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