JPH0778154B2 - Method for producing aqueous fluorinated acrylic copolymer emulsion and composition thereof - Google Patents
Method for producing aqueous fluorinated acrylic copolymer emulsion and composition thereofInfo
- Publication number
- JPH0778154B2 JPH0778154B2 JP3264266A JP26426691A JPH0778154B2 JP H0778154 B2 JPH0778154 B2 JP H0778154B2 JP 3264266 A JP3264266 A JP 3264266A JP 26426691 A JP26426691 A JP 26426691A JP H0778154 B2 JPH0778154 B2 JP H0778154B2
- Authority
- JP
- Japan
- Prior art keywords
- acrylic copolymer
- emulsion
- monomer
- aqueous emulsion
- fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は水媒体中に分散した▲撥
▼水性と▲撥▼油性に優れた含フッ素(メタ)アクリル
系(メタクリル系およびアクリル系を併せてアクリル系
と略記する)共重合体水性エマルジョンの製造方法及び
その組成物に関する。FIELD OF THE INVENTION The present invention relates to a fluorine-containing (meth) acrylic type (methacrylic type and acrylic type are abbreviated as acrylic type) dispersed in an aqueous medium and excellent in water repellency and oil repellency. The present invention relates to a method for producing an aqueous copolymer emulsion and its composition.
【0002】[0002]
【従来の技術】フッ素を含有する樹脂は、▲撥▼水▲撥
▼油性を示すこと、耐熱耐薬品性に優れている防汚効果
が大きい等の理由から、繊維加工剤、接着剤、紙加工剤
等に利用されてきた。又、近年は長期の耐候性に富むこ
とから、塗料業界でもその利用を考えている。2. Description of the Related Art Fluorine-containing resins are used for fiber processing agents, adhesives, papers, because they are highly water-repellent, oil-repellent, and have excellent heat and chemical resistance and a great antifouling effect. It has been used as a processing agent. Further, in recent years, since it has excellent long-term weather resistance, it is considered to be used in the paint industry.
【0003】これらフッ素を含有する樹脂を製造する方
法には、テトラフルオロオレフイン、トリフルオロルオ
レフイン、フッ化ビニリデンなどのフッ化オレフィン系
単量体を重合する方法と、フルオロアルキル基を含有す
るα、β−エチレン性不飽和単量体を重合する方法とが
あるが、前者は常温では気体の単量体であるために高圧
で重合しなければならない不便がある。従って、常圧重
合では後者のフルオロアルキル基を含有するα、β−エ
チレン性不飽和単量体がフッ素を含有する樹脂の製造に
用いられている。Methods for producing these fluorine-containing resins include a method of polymerizing a fluorinated olefinic monomer such as tetrafluoroolefin, trifluorofluoroine, vinylidene fluoride, and a fluoroalkyl group-containing α, There is a method of polymerizing a β-ethylenically unsaturated monomer, but the former is inconvenient to polymerize at a high pressure because it is a gaseous monomer at room temperature. Therefore, in atmospheric polymerization, the latter α, β-ethylenically unsaturated monomer containing a fluoroalkyl group is used for producing a resin containing fluorine.
【0004】フルオロアルキル基を含有するα、β−エ
チレン性不飽和単量体としては、フルオロアルキルアク
リレートやフルオロアルキルメタクリレート(アクリレ
ート単量体とメタクリレート単量体を併せてアクリレー
ト系単量体と略記する)が普通用いられている。しか
し、この単量体の価格は非常に高いため、出来るだけ少
量の使用でフッ素特有の性質を樹脂に付与させることが
望まれている。又、一方フルオロアルキル基を含有する
樹脂フイルムの▲撥▼水▲撥▼油性は界面において空気
側にフルオロアルキル基が整然と配列することによって
発現すると言われ、長鎖のフロオロアルキル基の方が効
果的であることが知られている。しかし、フルオロアル
キル基は結晶性を有するために鎖長があまりに長くなる
と、常温で固体の単量体となり、他の溶剤に溶解しなく
なることから、炭素数6〜12のアルキル基を有するパ
ーフルオロアルキルアクリレート系単量体が普通に用い
られている。Examples of the α, β-ethylenically unsaturated monomer containing a fluoroalkyl group include fluoroalkyl acrylate and fluoroalkyl methacrylate (the acrylate monomer and the methacrylate monomer are collectively referred to as an acrylate-based monomer. Is usually used. However, since the price of this monomer is very high, it is desired to give the resin the properties peculiar to fluorine by using as little amount as possible. On the other hand, the water / oil / oil repellency of the resin film containing a fluoroalkyl group is said to be exhibited by the orderly arrangement of the fluoroalkyl groups on the air side at the interface, and the long-chain fluoroalkyl group is more preferable. It is known to be effective. However, since the fluoroalkyl group has crystallinity, if the chain length becomes too long, it will become a solid monomer at room temperature and will not dissolve in other solvents, so a perfluoro group having an alkyl group having 6 to 12 carbon atoms will be obtained. Alkyl acrylate monomers are commonly used.
【0005】単量体の重合方法及び樹脂の供給は環境や
人体の安全性から水を媒体としたエマルジョンが望まれ
ている。しかし、炭素数6〜12のアルキル基を有する
パーフルオロアルキルアクリレート系単量体の水ヘの溶
解度は極めて小さいことから水相を経由して反応の場
(粒子)へ単量体が供給される通常の乳化重合法によっ
てフルオロアルキル基を含有する樹脂エマルジョンを得
ることは困難であった。そのために特殊な方法が提案さ
れてきた。For the method of polymerizing the monomer and the supply of the resin, an emulsion using water as a medium is desired in view of the safety of the environment and the human body. However, since the solubility of the perfluoroalkyl acrylate-based monomer having an alkyl group having 6 to 12 carbon atoms in water is extremely low, the monomer is supplied to the reaction field (particles) via the aqueous phase. It has been difficult to obtain a resin emulsion containing a fluoroalkyl group by a usual emulsion polymerization method. Therefore, a special method has been proposed.
【0006】例えば、米国特許3062765号は、フ
ルオロアルキル基を有するメタクリレート系単量体を溶
解させ得る親水性有機溶媒を水に混和し、水相への単量
体の溶解度を増すことによって乳化重合を行おうとする
ものである。しかし、この方法では、比較的多量の親水
性有機溶媒が必要なことから環境や人体ヘの安全性の問
題が解決できなかった。また親水性有機溶媒を含むこと
からエマルジョンの安定性に問題が残り、安定性を改良
するために特殊なフッ素系界面活性剤を用いたり、界面
活性剤の使用量を増加させたりすれば、エマルジョンの
発泡性が発生したり得られたフイルムの耐水性が悪化す
る傾向が大きい。この様に、水だけを媒体にして乳化重
合によりフルオロアルキル基を含有する樹脂エマルジョ
ンを得ることは困難であったため、特開平2−1476
01号に記載された発明では、有機溶媒中でラジカル重
合したフルオロアルキル基を含有する樹脂の有機溶剤溶
液に水を加えて自己分散させた後、有機媒体を留去させ
てフルオロアルキル基を含有する樹脂エマルジョンを得
ている。For example, US Pat. No. 3,062,765 discloses emulsion polymerization by mixing a hydrophilic organic solvent capable of dissolving a methacrylate monomer having a fluoroalkyl group with water to increase the solubility of the monomer in the aqueous phase. Is to do. However, this method cannot solve the problem of safety to the environment and human body because a relatively large amount of hydrophilic organic solvent is required. In addition, because the stability of the emulsion remains a problem because it contains a hydrophilic organic solvent, if a special fluorine-based surfactant is used to improve the stability or the amount of surfactant used is increased, the emulsion There is a large tendency that the foamability of the film is generated or the water resistance of the obtained film is deteriorated. As described above, it was difficult to obtain a resin emulsion containing a fluoroalkyl group by emulsion polymerization using only water as a medium.
In the invention described in No. 01, water is added to an organic solvent solution of a resin containing a fluoroalkyl group radical-polymerized in an organic solvent to cause self-dispersion, and then the organic medium is distilled off to contain a fluoroalkyl group. Is obtained.
【0007】[0007]
【発明が解決しようとする課題】水に難溶性のフルオロ
アルキル基を有するアクリレート系単量体を水相で直接
ラジカル重合させ、安定性の良いフルオロアルキル基を
含有する樹脂エマルジョンを得る良い方法は従来なかっ
た。A good method for obtaining a stable resin emulsion containing a fluoroalkyl group by directly radically polymerizing an acrylate-based monomer having a water-insoluble fluoroalkyl group in the water phase is described. It has never been before.
【0008】[0008]
【課題を解決するための手段】本発明者らは鋭意研究を
重ねた結果、炭素数6〜12のアルキル基を有するパー
フルオロアルキルアクリレート系単量体を含む単量体組
成物を水中に分散して単量体プレエマルジョンを作成し
た後、さらに、超音波照射あるいは高圧ホモジナイザー
処理等により該プレエマルジョンの粒子径を0.3μm
以下にしてからラジカル重合を行うと安定なフルオロア
ルキル基を含有する樹脂エマルジョンを得られることを
見いだした。Means for Solving the Problems As a result of intensive studies by the present inventors, a monomer composition containing a perfluoroalkyl acrylate monomer having an alkyl group having 6 to 12 carbon atoms was dispersed in water. To prepare a monomer pre-emulsion, and then the particle size of the pre-emulsion is 0.3 μm by ultrasonic irradiation or high-pressure homogenizer treatment.
It was found that a stable resin emulsion containing a fluoroalkyl group can be obtained by radical polymerization after the following.
【0009】つまり、本発明は、 「(1) (A)炭素数6〜12のアルキル基を有するパーフルオロアルキルア クリレート系単量体 2〜40m ol% (B)上記(A)と共重合可能なカルボキシル基を有するα、β−エチレン性 不飽和単量体 0.1〜15mol% (C)上記(A)、(B)と共重合可能なヒドロキシル基を有するα、β−エ チレン性不飽和単量体 0〜25mol% (D)上記(A)、(B)、(C)と共重合可能な上記以外のα、β−エチレ ン性不飽和単量体 97.9〜45mol% を界面活性剤を用い超音波照射または高圧ホモジナイザ
ーにより水中に乳化分散させ、分散粒子の粒径を0.3
μm以下の微粒となしてからラジカル重合することを特
徴とする粒径0.3μm〜0.05μmの分散粒子から
なる含フッ素アクリル系共重合体水性エマルジョンの製
造方法 (2) 単量体を界面活性剤を用いて水中に乳化分散さ
せた後、超音波照射または高圧ホモジナイザー処理によ
り分散粒子の粒径を0.3μm以下とする請求項1に記
載された、含フッ素アクリル系共重合体水性エマルジョ
ンの製造方法。 (3) (A)炭素数6〜12のアルキル基を有するパ
ーフルオロアルキルアクリレート系単量体がβー(パー
フルオロオクチル)エチルアクリレートである請求項1
または2に記載された含フッ素アクリル系共重合体水性
エマルジョンの製造力法 (4) 炭素数6〜12のアルキル基を有するパーフル
オロアルキルアクリレート系単量体と共重合可能なカル
ボキシル基を有するα、β−エチレン性不飽和単量体が
アクリル酸である請求項1ないし3のいずれか1項に記
載された含フッ素アクリル系共重合体水性エマルジョン
の製造方法 (5)請求項1ないし4のいずれか1項に記載された方
法により製造された粒径0.3μm〜0.05μmの分
散粒子からなる含フッ素アクリル系共重合体微粒子の水
性エマルジョン。 (6) 請求項5項に記載された含フッ素アクリル系共
重合体微粒子の水性エマルジョンと、ブロック化ポリイ
ソシアネートとを主要成分とする水性組成物。 (7) 請求項5または6に記載された含フッ素アクリ
ル系共重合体微粒子の水性エマルジョンと、分散粒子の
粒径が0.1〜10μmである合成樹脂水性エマルジョ
ンとを主要成分とする水性組成物。」 に関する。That is, the present invention provides "(1) (A) a perfluoroalkyl acrylate-based monomer having an alkyl group having 6 to 12 carbon atoms: 2 to 40 mol% (B) copolymerized with (A). Α, β-ethylenically unsaturated monomer having a possible carboxyl group 0.1 to 15 mol% (C) α, β-ethylene having a hydroxyl group copolymerizable with the above (A) and (B) Unsaturated monomer 0 to 25 mol% (D) α, β-ethylenically unsaturated monomer other than the above copolymerizable with (A), (B) and (C) 97.9 to 45 mol% Ultrasonic irradiation or high pressure homogenizer using surfactant
Emulsify and disperse in water by
From dispersed particles having a particle size of 0.3 μm to 0.05 μm, which is characterized by being radically polymerized after being made into fine particles of μm or less
Composed after the method of manufacturing fluorine containing acrylic copolymer aqueous emulsion (2) monomer was emulsified and dispersed in water using a surfactant, the particle size of the dispersed particles by ultrasonic irradiation or high-pressure auxiliary motor Jinaiza process The method for producing a fluorine-containing acrylic copolymer aqueous emulsion according to claim 1, wherein the diameter is 0.3 μm or less. (3) The perfluoroalkyl acrylate-based monomer having an alkyl group having 6 to 12 carbon atoms (A) is β- (perfluorooctyl) ethyl acrylate.
Or a method for producing an aqueous fluorinated acrylic copolymer aqueous emulsion described in (4) α having a carboxyl group copolymerizable with a perfluoroalkyl acrylate monomer having an alkyl group having 6 to 12 carbon atoms The method for producing the fluorinated acrylic copolymer aqueous emulsion according to any one of claims 1 to 3, wherein the β-ethylenically unsaturated monomer is acrylic acid (5). An aqueous emulsion of fluorine-containing acrylic copolymer fine particles, comprising dispersed particles having a particle diameter of 0.3 μm to 0.05 μm produced by the method described in any one of items. (6) An aqueous emulsion of the fluorine-containing acrylic copolymer fine particles according to claim 5, and a blocked poly
An aqueous composition containing a cyanate as a main component. (7) an aqueous emulsion of fluorine-containing acrylic copolymer particles according to claim 5 or 6, an aqueous composition the particle size of the dispersed particles and the synthetic resin aqueous emulsion and the principal ingredient is 0.1~10μm object. Regarding
【0010】通常の乳化重合のように単に水中に乳化さ
せると、パーフルオロアルキル基を有する単量体は疎水
性が大きいのでミセルの中に入り難く、モノマーのエマ
ルジョンが形成出来ない。それ故本発明は、パーフルオ
ロアルキル基を有する単量体を他のモノマーに溶解して
この混合物を界面活性剤を用いて水に分散する。しかし
これではまた分散粒子の粒径が大きすぎるので、更に小
さい粒子に分散させなければならない。微少滴状に分散
させないと重合中にゲル化物が多量に発生し、安定な乳
化重合が行われないばかりか、ゲル化物を除いた、エマ
ルジョン部分にはほとんど含フッ素アクリル系共重合体
の特徴は認められない。少なくとも0.3μm以下にす
る必要がある。微少滴に分散させるために、超音波を照
射するか高圧ホモジナイザーにより分散を行う。勿論両
方法を適宜併用し、例えば高圧ホモジナイザー処理して
更に超音波照射してもよい。[0010] When simply emulsified in water like ordinary emulsion polymerization, the monomer having a perfluoroalkyl group has a large hydrophobicity, so that it is difficult to enter the micelle and an emulsion of the monomer cannot be formed. Therefore, in the present invention, a monomer having a perfluoroalkyl group is dissolved in another monomer, and this mixture is dispersed in water using a surfactant. However, in this case, the particle size of the dispersed particles is too large, so that the particles must be dispersed in smaller particles. If not dispersed in the form of microdroplets, a large amount of gelled product will be generated during polymerization, stable emulsion polymerization will not be performed, and most of the features of the fluorinated acrylic copolymer will be found in the emulsion part excluding the gelled product. unacceptable. It must be at least 0.3 μm or less. In order to disperse into minute droplets, ultrasonic waves are irradiated or dispersion is performed by a high pressure homogenizer. Of course, both methods may be appropriately used in combination, for example, high-pressure homogenizer treatment may be performed, and further ultrasonic irradiation may be performed.
【0011】こうして得た単量体プレエマルジョンを直
接粒子内でラジカル重合させる方法はミニエマルジョン
重合法として知られ、単量体プレエマルジョンの粒子径
が0.5μm以下の細粒子であること、その粒子が安定
で重合中に壊れないことが必要とされている。この様に
安定なミニエマルジョン重合を行うには、乳化安定剤と
して高級アルコールやヘキサデカンが有効であることが
知られており、高級アルコールを使用しないと重合中に
乳化系が崩壊してしまうとされて来た。これがミニエマ
ルジョン重合の常識であった。A method of directly radically polymerizing the thus obtained monomer pre-emulsion in a particle is known as a mini-emulsion polymerization method, in which the particle size of the monomer pre-emulsion is fine particles having a particle size of 0.5 μm or less. It is required that the particles be stable and not break during polymerization. It is known that higher alcohols and hexadecane are effective as emulsion stabilizers for performing stable miniemulsion polymerization in this way, and it is said that the emulsion system will collapse during polymerization unless higher alcohols are used. Came. This was the common knowledge of miniemulsion polymerization.
【0012】ところが、本発明の方法は乳化安定助剤を
特に添加しなくともミニエマルジョン重合が安定に進行
し、−般的な乳化重合法で認められる様なパーフルオロ
アルキル基を有するアクリレート系単量体あるいは重合
体が析出したり、ゲル化物が多量に生成する様なことは
ない。本発明者はパーフルオロアルキル基を有するアク
リレート系単量体自体が単量体プレエマルジョンの安定
性に寄与しているものと考えている。However, according to the method of the present invention, miniemulsion polymerization proceeds stably without adding an emulsion stabilizing aid, and an acrylate-based monomer having a perfluoroalkyl group as is found in general emulsion polymerization methods is used. No polymer or polymer is deposited, or a large amount of gelled product is not formed. The present inventor believes that the acrylate-based monomer itself having a perfluoroalkyl group contributes to the stability of the monomer pre-emulsion.
【0013】本発明に用いられる(A)炭素数6〜12
のアルキル基を有するパーフルオロアルキルアクリレー
ト系単量体としては、例えば CH2=CHCO2C2H4C6F13、 CH2=CHCO2C2H4C8F17 CH2=C(CH3)CO2C2H4C6F13、 CH2=C(CH3)CO2C2H4C8F17 CH2=CHCO2C2H4C10F21、 CH2=CHCO2C2H4C12F25 CH2=C(CH3)CO2C2H4C10F21、 CH2=C(CH3)CO2C2H4C12F25 などが挙げられる。特に、CH2=CHCO2C2H4
C8F17(β−(パーフルオロオクチル)エチルアク
リレート)が好ましい。(A) C6-12 used in the present invention
Examples of the perfluoroalkyl acrylate-based monomer having an alkyl group include CH 2 ═CHCO 2 C 2 H 4 C 6 F 13 , CH 2 ═CHCO 2 C 2 H 4 C 8 F 17 CH 2 ═C (CH 3) CO2C2H4C6F13, CH 2 = C (CH 3) CO 2 C 2 H 4 C 8 F 17 CH 2 = CHCO 2 C 2 H 4 C 10 F 21, CH 2 = CHCO 2 C 2 H 4 C 12 F 25 CH 2 = C (CH 3) CO 2 C 2 H 4 C 10 F 21, CH 2 = C (CH 3) such as CO 2 C 2 H 4 C 12 F 25 and the like. In particular, CH 2 = CHCO 2 C 2 H 4
C 8 F 17 (β- (perfluorooctyl) ethyl acrylate) is preferred.
【0014】炭素数6〜12のアルキル基を有するパー
フルオロアルキルアクリレート系単量体の使用量は、2
〜40mol%であり、好ましくは5〜20mol%で
ある。2mol%未満では、パーフルオロアルキル基の
効果がなく、▲撥▼水性が得られない。また、40mo
l%を越えると、フッ素系界面活性剤を多量に用いない
と、粒子径の細かいプレエマルジョンを作成できなくな
り、この様にして得たエマルジョンは耐水性が悪く、発
泡し易いエマルジョンとなって好ましくない、などの欠
点がある。The amount of the perfluoroalkyl acrylate-based monomer having an alkyl group having 6 to 12 carbon atoms is 2
It is -40 mol%, preferably 5-20 mol%. If it is less than 2 mol%, the effect of the perfluoroalkyl group is not exerted, and water repellency cannot be obtained. Also, 40mo
If it exceeds 1%, a pre-emulsion having a small particle size cannot be prepared unless a large amount of a fluorosurfactant is used. The emulsion thus obtained has poor water resistance and easily foams. There are drawbacks such as not being.
【0015】本発明に用いられる炭素数6〜12のアル
キル基を有するパーフルオロアルキルアクリレート系単
量体と共重合可能なカルボキシル基を有するα、β−エ
チレン性不飽和単量体としては、アクリル酸、メタクリ
ル酸、クロトン酸、マレイン酸、マレイン酸ハーフエス
テル、フマール酸、フマール酸ハーフエステル、イタコ
ン酸ハーフエステル等が挙げられる。カルボキシル基を
有するα、β−エチレン性不飽和単量体を使用すること
により、乳化重合が安定に行われるばかりでなく、パー
フルオロアルキル基の効果もより発揮され優れた▲撥▼
水性が得られる。The α, β-ethylenically unsaturated monomer having a carboxyl group copolymerizable with the perfluoroalkyl acrylate monomer having an alkyl group having 6 to 12 carbon atoms used in the present invention is acrylic. Examples thereof include acid, methacrylic acid, crotonic acid, maleic acid, maleic acid half ester, fumaric acid, fumaric acid half ester, and itaconic acid half ester. By using the α, β-ethylenically unsaturated monomer having a carboxyl group, not only the emulsion polymerization is stably carried out, but also the effect of the perfluoroalkyl group is exerted more effectively.
Aqueous is obtained.
【0016】(B)カルボキシル基を有するα、β−エ
チレン性不飽和単量体の使用量は、0.1〜15mol
%であり、好ましくは2.5〜10mol%である。
0.1mol%未満では、得られたエマルジョンの安定
性が不十分であり、塗料化したり、保存中にゲル化物が
発生するので好ましくない。また、15mol%を越え
ると、皮膜の耐水性が低下する、などの欠点がある。The amount of the (B) α, β-ethylenically unsaturated monomer having a carboxyl group used is 0.1 to 15 mol.
%, And preferably 2.5 to 10 mol%.
If it is less than 0.1 mol%, the stability of the obtained emulsion is insufficient, and it is not preferable because it becomes a paint or a gel is generated during storage. On the other hand, if it exceeds 15 mol%, the water resistance of the coating film may be deteriorated.
【0017】(C)本発明に用いられる前記(A)炭素
数6〜12のアルキル基を有するパーフルオロアルキル
アクリレート単量体と(B)カルボキシル基を有する
α、β−エチレン性不飽和単量体と共重合可能なヒドロ
キシル基を有するα、β−エチレン性不飽和単量体とし
ては、2−ヒドロキシエチルアクリレート、2−ヒドロ
キシエチルメタクリレート、ヒドロキシプロピルアクリ
レート、ヒドロキシプロピルメタクリレート、2−ヒド
ロキシ−3−クロロプロピルアクリレート、β−ヒドロ
キシエチル−β′−アクリロイルオキシエチルフタレー
ト、1.4−ブチレングリコールモノアクリレート、ヒ
ドロキシスチレン、2−ヒドロキシブチルメタクリレー
ト、2−ヒドロキシ−3−フェノキシプロピルアクリレ
ートなどが挙げられる。(C) The above-mentioned (A) perfluoroalkyl acrylate monomer having an alkyl group having 6 to 12 carbon atoms and (B) a carboxyl group-containing α, β-ethylenically unsaturated monomer. As the α, β-ethylenically unsaturated monomer having a hydroxyl group capable of copolymerizing with the polymer, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 2-hydroxy-3- Examples thereof include chloropropyl acrylate, β-hydroxyethyl-β′-acryloyloxyethyl phthalate, 1.4-butylene glycol monoacrylate, hydroxystyrene, 2-hydroxybutyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate.
【0018】特殊な単量体として例えばアセトアセトキ
シエチルメタクリレート、アセトアセトキシエチルアク
リレートの様な互換異性体は、そのエノール型でもケト
型でも使用出来る。ヒドロキシル基を有するα、β−エ
チレン性不飽和単量体は、特に使用しなくてもよいが、
ヒドロキシル基を有するα、β−エチレン性不飽和単量
体を使用するとより▲撥▼水性が向上し、とくに硬化反
応化合物を併用した組成物においてヒドロキシル基が反
応基となり、硬化反応が充分に行われる。ヒドロキシル
基を有するα、β−エチレン性不飽和単量体の使用量
は、0〜25mol%であり、好ましくは5〜15mo
l%である。25mol%を越えると、硬化後の皮膜が
もろくなり好ましくない。本発明に用いられる前記
(A)、(B)、(C)単量体と共重合可能な前記以外
のα、β−エチレン性不飽和単量体としては、酢酸ビニ
ル、酪酸ビニル、プロピオン酸ビニル、α−位で分岐し
たカルボン酸のビニルエステル、などのビニルエステ
ル;アクリル酸メチル、アクリル酸エチル、アクリル酸
ブチル、アクリル酸2エチルヘキシルなどのアクリル酸
エステル;メタクリル酸メチル、メタクリル酸エチル、
メタクリル酸ブチル、メタクリル酸2エチルヘキシルな
どのメタクリル酸エステル;マレイン酸ジブチル、フマ
ル酸ジブチルなどの不飽和酸エステル;スチレン、アク
リロニトリル;などが挙げられる。As the special monomer, compatible isomers such as acetoacetoxyethyl methacrylate and acetoacetoxyethyl acrylate can be used in their enol form or keto form. The α, β-ethylenically unsaturated monomer having a hydroxyl group need not be particularly used,
When an α, β-ethylenically unsaturated monomer having a hydroxyl group is used, the water repellency is further improved, and the hydroxyl group becomes a reactive group particularly in the composition in which the curing reaction compound is used in combination, and the curing reaction is sufficiently performed. Be seen. The amount of the α, β-ethylenically unsaturated monomer having a hydroxyl group used is 0 to 25 mol%, preferably 5 to 15 mo.
1%. If it exceeds 25 mol%, the film after curing becomes brittle, which is not preferable. Examples of the α, β-ethylenically unsaturated monomers other than the above that are copolymerizable with the (A), (B), and (C) monomers used in the present invention include vinyl acetate, vinyl butyrate, and propionic acid. Vinyl, vinyl esters of carboxylic acids branched at the α-position, etc .; acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate,
Examples thereof include methacrylic acid esters such as butyl methacrylate and 2-ethylhexyl methacrylate; unsaturated acid esters such as dibutyl maleate and dibutyl fumarate; styrene and acrylonitrile.
【0019】また、これらの単量体の一部を官能性また
は架橋性単量体に置き換えて使用することもできる。官
能性または架橋性単量体としては、アクリルアミド、N
−メチロールアクリルアミド、グリシジルメタクリレー
ト、ジビニルベンゼン、トリアリルイソシアヌレート、
テトラアリルオキシエタンなどが挙げられる。また、
1,4−ジビニルパーフルオロn−ブタン、1,6−ジ
ビニルパーフルオロn−ヘキサンなどのフッ素含有ジビ
ニル化合物を架橋剤に用いることもできる。Further, a part of these monomers may be replaced with a functional or crosslinkable monomer for use. Examples of functional or crosslinkable monomers include acrylamide and N
-Methylol acrylamide, glycidyl methacrylate, divinylbenzene, triallyl isocyanurate,
Examples include tetraallyloxyethane and the like. Also,
A fluorine-containing divinyl compound such as 1,4-divinylperfluoro n-butane or 1,6-divinylperfluoro n-hexane can also be used as the crosslinking agent.
【0020】(A)、(B)、(C)単量体と共重合可
能な前記以外のα、β−エチレン性不飽和単量体の使用
量は、単量体全量より(A)、(B)、(C)単量体の
使用量を除いた残りの量であり、97.9〜45mol
%の範囲である。本発明により含フッ素アクリル系共重
合体を溶剤を使用せず、水系で直接に水性エマルジョン
の製造することが可能となった。The amount of the α, β-ethylenically unsaturated monomer other than the above copolymerizable with the monomers (A), (B) and (C) is (A), It is the remaining amount excluding the used amount of (B) and (C) monomers, and is 97.9 to 45 mol.
% Range. According to the present invention, it is possible to directly produce an aqueous emulsion of a fluorine-containing acrylic copolymer in an aqueous system without using a solvent.
【0021】本発明によって得られた含フッ素アクリル
系共重合体水性エマルジョン組成物は、乾燥することに
より、▲撥▼水性、▲撥▼油性に優れた皮膜が形成さ
れ、耐熱性、耐候性、耐光性、耐薬品性、離型性、滑り
性などにも優れている。従って、合成樹脂水性エマルジ
ョンが一般に応用されている塗料用バインダー、繊維処
理剤、紙加工剤、セメント混和剤、接着剤などに有用に
使用することができる。特に、皮膜の▲撥▼水性、▲撥
▼油性を利用した表面コーティング剤が有用であり、被
コーティング基材としては、繊維物質、不織布、紙、皮
革、ゴム、木材、金属、コンクリート、石膏、ALC
板、アスファルト、ガラス、ガラス繊維、陶磁器、プラ
スチックなど広い範囲の物に使用出来、特に限定される
ことはない。The fluorine-containing acrylic copolymer aqueous emulsion composition obtained according to the present invention is dried to form a film having excellent water repellency and oil repellency, heat resistance, weather resistance, and It is also excellent in light resistance, chemical resistance, releasability, and slipperiness. Therefore, the synthetic resin aqueous emulsion can be effectively used as a binder for paints, a fiber treating agent, a paper processing agent, a cement admixture, an adhesive agent, etc. to which the synthetic resin aqueous emulsion is generally applied. In particular, surface coating agents that utilize the water repellency and oil repellency of the film are useful, and as the substrate to be coated, fibrous materials, non-woven fabric, paper, leather, rubber, wood, metal, concrete, plaster, ALC
It can be used for a wide range of materials such as boards, asphalt, glass, glass fibers, ceramics, and plastics, and is not particularly limited.
【0022】本発明によって得られた含フッ素アクリル
系共重合体水性エマルジョン組成物として、特に、耐溶
剤性が更に求められる場合は、本発明によって得られた
含フッ素アクリル系共重合体水性エマルジョンに硬化反
応化合物を配合することが好ましい。特に好ましくはブ
ロック化ポリイソシアネートを用いて熱硬化させる方法
で、この様にして得られたフイルムは耐溶剤性が著しく
向上する。硬化反応化合物と併用する場合の含フッ素ア
クリル系共重合体水性エマルジョンを製造するための単
量体組成物としては、特に、ヒドロキシル基を有する
α、β−エチレン性不飽和単量体を使用することが好ま
しい。このヒドロキシル基と硬化化合物が反応する。勿
論他の官能基例えばカルボキシル基、アミノ基等を含有
させれば同様に硬化される。硬化反応化合物としては、
ヒドロキシル基と反応する、ブロック化ポリイソシアネ
ートが使用される。ブロック化ポリイソシアネートの使
用量は、特に限定されないが、含フッ素アクリル系共重
合体水性エマルジョンの固形分100重量部に対して、
1〜20重量部である。As the fluorine-containing acrylic copolymer aqueous emulsion composition obtained by the present invention, particularly when solvent resistance is further required, the fluorine-containing acrylic copolymer aqueous emulsion obtained by the present invention is used. It is preferable to add a curing reaction compound. Especially preferably the method for thermally cured using blocked polyisocyanates, film obtained in this manner is solvent resistance is remarkably improved. As the monomer composition for producing the fluorine-containing acrylic copolymer aqueous emulsion when used in combination with the curing reaction compound, in particular, an α, β-ethylenically unsaturated monomer having a hydroxyl group is used. It is preferable. This hydroxyl group reacts with the curing compound. Needless to say, if other functional groups such as a carboxyl group and an amino group are contained, the curing is similarly performed. As the curing reaction compound,
Reacts with the hydroxyl group, blocked poly isocyanate <br/> over preparative is used. The amount of the blocked polyisocyanate used is not particularly limited, but with respect to 100 parts by weight of the solid content of the fluorine-containing acrylic copolymer aqueous emulsion,
It is 1 to 20 parts by weight.
【0023】また、本発明の含フッ素アクリル系共重合
体水性エマルジョンは、合成樹脂水性エマルジョンと混
合して使用することが出来る。配合する水性合成樹脂エ
マルジョンとしては、従来より塗料用バインダー、繊維
処理剤、紙塗工用バインダー、接着剤などに用いられる
水性合成樹脂エマルジョンであればよく、合成ゴムエマ
ルジョンも含まれる。具体的には、酢酸ビニル系樹脂水
性エマルジョン、スチレン系樹脂水性エマルジョン、ア
クリル系樹脂水性エマルジョン、エチレン・酢酸ビニル
系樹脂水性エマルジョン、エチレン・塩化ビニル系樹脂
水性エマルジョン、酢酸ビニル・アクリル系樹脂水性エ
マルジョン、酢酸ビニル・ベオバ(シェル化学社;登録
商標)系樹脂水性エマルジョン、スチレン・アクリル系
樹脂水性エマルジョン、などの熱可塑性樹脂水性エマル
ジョンやスチレン・ブタジエンゴムラテックス、スチレ
ン・ブタジエン・アクリロニトリルゴムラテックス、イ
ソプレンゴムラテックスなどのゴムラッテクスがあげら
れるが、この他適宜のエマルジョンが使用出来る。これ
らの水性エマルジョンは、界面活性剤や保護コロイドを
用いて通常の乳化重合により製造されるもので、粒子径
は0.1〜10μmである。配合する割合は、目的によ
り異なり、限定されるものではないが、含フッ素アクリ
ル系共重合体水性エマルジョン10〜99重量部(固形
分換算)に通常の水性エマルジョン90〜1重量部(固
形分換算)で用いられる。含フッ素アクリル系共重合体
水性エマルジョンが10重量部以下では皮膜に▲撥▼水
性を与える効果が少なく、99重量部以上では100重
量部と変わりなく、通常の水性エマルジョンを加える効
果が得られない。皮膜の▲撥▼水性を充分に維持し、皮
膜の基材ヘの密着性や皮膜の強度・伸度などの機械的物
性を向上させるためには含フッ素アクリル系共重合体水
性エマルジョン50〜99重量部(固形分換算)と通常
の水性エマルジョン50〜1重量部(固形分換算)が好
ましく、皮膜に▲撥▼水性が得られない水性エマルジョ
ンの皮膜に多少の▲撥▼水性を付与する目的であれば、
含フッ素アクリル系共重合体水性エマルジョン10〜5
0重量部に通常の水性エマルジョン90〜50重量部
(固形分換算)で充分目的は達せられる。The fluorine-containing acrylic copolymer aqueous emulsion of the present invention can be used as a mixture with a synthetic resin aqueous emulsion. The water-based synthetic resin emulsion to be blended may be any water-based synthetic resin emulsion conventionally used as a binder for paints, a fiber treating agent, a binder for paper coating, an adhesive, etc., and also includes a synthetic rubber emulsion. Specifically, vinyl acetate resin aqueous emulsion, styrene resin aqueous emulsion, acrylic resin aqueous emulsion, ethylene / vinyl acetate resin aqueous emulsion, ethylene / vinyl chloride resin aqueous emulsion, vinyl acetate / acrylic resin aqueous emulsion. , Vinyl acetate / Veova (Shell Chemical Co., Ltd.) resin aqueous emulsion, styrene / acrylic resin aqueous emulsion, etc., thermoplastic resin aqueous emulsion, styrene / butadiene rubber latex, styrene / butadiene / acrylonitrile rubber latex, isoprene rubber Examples include rubber latex such as latex, but other appropriate emulsions can be used. These aqueous emulsions are produced by ordinary emulsion polymerization using a surfactant or protective colloid, and have a particle size of 0.1 to 10 μm. The proportion to be blended varies depending on the purpose and is not limited, but 10 to 99 parts by weight of the fluorine-containing acrylic copolymer aqueous emulsion (solid content conversion) to 90 to 1 parts by weight of the normal aqueous emulsion (solid content conversion). ) Used in. When the amount of the fluorinated acrylic copolymer aqueous emulsion is 10 parts by weight or less, the effect of imparting water repellency to the film is small, and when it is 99 parts by weight or more, the effect is the same as 100 parts by weight, and the effect of adding a normal aqueous emulsion cannot be obtained. . In order to maintain sufficient water repellency of the film and to improve the mechanical properties such as the adhesion of the film to the substrate and the strength and elongation of the film, fluorine-containing acrylic copolymer aqueous emulsion 50-99 It is preferable to add 50 parts by weight (as solid content) and 50 to 1 parts by weight of normal aqueous emulsion (as solid content), and to impart some water repellency to the film of an aqueous emulsion that does not give water repellency to the film. If,
Fluorine-containing acrylic copolymer aqueous emulsion 10-5
The purpose can be sufficiently achieved with 0 to 50 parts by weight of an ordinary aqueous emulsion of 90 to 50 parts by weight (solid content conversion).
【0024】本発明の水性組成物には、目的に応じて増
粘剤、可塑剤、消泡剤、顔料、着色剤、充填剤、香料、
防腐剤、蛍光増白剤、酸化防止剤、紫外線吸収剤、補強
剤、帯電防止剤、抗ブロッキング剤、難燃剤、滑剤、粘
着性付与剤などを配合することができる。とくに水性組
成物の粘度を高めるためにはポリビニルアルコール、ポ
リアクリル酸塩、水溶性でんぷん、水溶性セルロース誘
導体などの水溶性高分子化合物を増粘剤として配合する
ことが好ましい。The aqueous composition of the present invention contains a thickener, a plasticizer, an antifoaming agent, a pigment, a coloring agent, a filler, a fragrance, and
Preservatives, optical brighteners, antioxidants, ultraviolet absorbers, reinforcing agents, antistatic agents, antiblocking agents, flame retardants, lubricants, tackifiers and the like can be added. In particular, in order to increase the viscosity of the aqueous composition, it is preferable to add a water-soluble polymer compound such as polyvinyl alcohol, polyacrylic acid salt, water-soluble starch or water-soluble cellulose derivative as a thickener.
【0025】[0025]
【実施例】次に、実施例をあげて本発明を具体的に説明
する。EXAMPLES Next, the present invention will be specifically described with reference to examples.
【0026】実施例1 β−(パーフルオロオクチル)エチルアクリレート8.
3g(5mol%)、n−ブチルメタクリレート40.
6g(90mol%)、80%アクリル酸1.5g(5
mol%)を三角フラスコに秤量し均一な単量体混合液
とした。単量体混合液に(ポリオキシエチレンアルキル
フェニルエーテル硫酸ナトリウム)2.5g、リン酸二
ナトリウム・12水塩0.25g脱イオン水48gから
成る界面活性剤水溶液を加え、マグネットスターラーで
撹拌して、平均粒子径約1μmの単量体プレエマルジョ
ンを得た。続いて、周波数40KHZの超音波発信機
(W−210R 本多電子株式会社)を用いて、単量体
プレエマルジョンをチッ素ガスでバブリングしながら6
0分間超音波照射を行ったところ、平均粒子径は約0.
2μmに低下した。別な容器に、触媒溶液と還元剤溶液
を次の通り作成した。 触媒溶液 パーブチルH69(日本油脂株式会社製) 0.73g エマルゲン911(花王株式会社製) 0.25g 脱イオン水 9.3g 還元剤溶液 スーパーライトC(三菱ガス化学株式会社製)0.5g 脱イオン水 9.5g 撹拌機、還流冷却器、滴下ロート、温度計、チッ素ガス
導入管を備えた反応器を55℃に昇温させた後、蒸気の
超音波照射を行った単量体プレエマルジョンを20%を
仕込み、触媒溶液の10%及び還元剤溶液10%を加え
た。10分経過後にさらに触媒溶液の10%と還元剤溶
液10%を追加してから残りの単量体プレエマルジョン
を約3時間かけて、滴下ロートより連続的に滴下した。
この間、反応器内の温度は55〜60℃に保持し、また
触媒溶液の60%と還元剤溶液60%を15分ごとに分
割して加えた。滴下終了後、さらに触媒溶液の10%と
還元剤溶液10%を加え1時間撹拌して反応を終了させ
た。その結果、濃度43重量%、pH2.2の安定な含
フッ素アクリル系共重合体水性エマルジョンを得た。こ
の含フッ素アクリル系共重合体水性エマルジョンの平均
粒子径は0.2μmであり、この含フッ素アクリル系共
重合体水性エマルジョンをアルミニウム板に塗布乾燥し
て得られる被膜の▲撥▼水度はR9で良好な▲撥▼水性
を示した。 試験方法 エマルジョンの粒子径は、Nicomp Instru
ments Inc.製モデル370サブミクロン粒子
径アナライザーを用いて測定した。 ▲撥▼水度の測定 含フッ素アクリル系共重合体水性エマルジョンのpHを
10%水酸化ナトリウム水溶液で5〜7に調整後、#4
0のワイヤーロッドでアルミニウム板に塗工し、80℃
で乾燥して、さらにデシケーター内で約10日放置して
試料とした。JIS.P8137 に準じ、アルミニウ
ム板に塗工した試料の▲撥▼水度を試験長100mmで
評価した。▲撥▼水度の評価基準はJIS.P8137
により行った。評価は、R1からR10で数字の大きい
ほうがより▲撥▼水性が高い。Example 1 β- (perfluorooctyl) ethyl acrylate 8.
3 g (5 mol%), n-butyl methacrylate 40.
6 g (90 mol%), 80% acrylic acid 1.5 g (5
(mol%) was weighed in an Erlenmeyer flask to give a uniform monomer mixture. To the monomer mixture, 2.5 g of (sodium polyoxyethylene alkylphenyl ether sulfate), 0.25 g of disodium phosphate dodecahydrate and 48 g of deionized water was added, and the mixture was stirred with a magnetic stirrer. A monomer pre-emulsion having an average particle size of about 1 μm was obtained. Then, while bubbling the monomer pre-emulsion with nitrogen gas using an ultrasonic transmitter (W-210R Honda Electronics Co., Ltd.) having a frequency of 40 KHZ, 6
When ultrasonic irradiation was performed for 0 minutes, the average particle size was about 0.
It decreased to 2 μm. A catalyst solution and a reducing agent solution were prepared in separate containers as follows. Catalyst solution Perbutyl H69 (manufactured by NOF CORPORATION) 0.73 g Emulgen 911 (manufactured by Kao Corporation) 0.25 g Deionized water 9.3 g Reducing agent solution Super Light C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 0.5 g Deionized Water 9.5 g Monomer pre-emulsion that was heated to 55 ° C. in a reactor equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen gas introduction tube, and then subjected to ultrasonic irradiation of steam. 20% was charged, and 10% of the catalyst solution and 10% of the reducing agent solution were added. After 10 minutes, 10% of the catalyst solution and 10% of the reducing agent solution were further added, and the remaining monomer pre-emulsion was continuously added dropwise from the dropping funnel over about 3 hours.
During this period, the temperature in the reactor was maintained at 55 to 60 ° C., and 60% of the catalyst solution and 60% of the reducing agent solution were added in 15 minute portions. After completion of the dropping, 10% of the catalyst solution and 10% of the reducing agent solution were further added and stirred for 1 hour to complete the reaction. As a result, a stable fluorine-containing acrylic copolymer aqueous emulsion having a concentration of 43% by weight and a pH of 2.2 was obtained. The average particle diameter of this fluorine-containing acrylic copolymer aqueous emulsion was 0.2 μm, and the water-repellency of the coating obtained by coating and drying this fluorine-containing acrylic copolymer aqueous emulsion on an aluminum plate was R9. And showed good water repellency. Test method The particle size of the emulsion is Nicomp Instru
mens Inc. It was measured using a Model 370 submicron particle size analyzer manufactured by KK. ▲ Measurement of water repellency After adjusting the pH of the fluorine-containing acrylic copolymer aqueous emulsion to 5 to 7 with a 10% aqueous sodium hydroxide solution, # 4
Coated on aluminum plate with 0 wire rod, 80 ℃
Then, the sample was left to stand in a desiccator for about 10 days to obtain a sample. JIS. According to P8137, the water repellency of the sample coated on the aluminum plate was evaluated at a test length of 100 mm. ▲ The water repellency evaluation standard is JIS. P8137
Went by. In the evaluation, the larger the number from R1 to R10, the higher the water repellency.
【0027】実施例2 実施例1と同様な手法で表1の単量体組成のプレエマル
ジョンをマグネットスターラーで撹拌して得た後、高圧
ホモジナイザー(GAULIN INC. 製MANT
ON GAOLIN LABORATORY HOMO
GENIZER型式15M−6TA)を用いて圧力8,
000P.S.I.で1回処理した。この処理によって
単量体プレエマルジョンの平均粒子径は約0.2μmと
なり、その後は実施例1と同様の操作を行った。Example 2 In the same manner as in Example 1, a pre-emulsion having the monomer composition shown in Table 1 was obtained by stirring with a magnetic stirrer, and then a high pressure homogenizer (MANT manufactured by GAULIN INC.) Was used.
ON GAOLIN LABORATORY HOMO
GENIZER model 15M-6TA) and pressure 8,
000P. S. I. Treated once. By this treatment, the average particle size of the monomer pre-emulsion became about 0.2 μm, and thereafter the same operation as in Example 1 was performed.
【0028】実施例3 表1の単量体組成を用いて実施例1と同様の操作によっ
てラジカル乳化重合を行って含フッ素アクリル系共重合
体水性エマルジョンを得た。Example 3 Using the monomer compositions shown in Table 1, radical emulsion polymerization was carried out in the same manner as in Example 1 to obtain a fluorine-containing acrylic copolymer aqueous emulsion.
【0029】実施例4 実施例3で得た含フッ素アクリル系共重合体水性エマル
ジョンに5%水酸化ナトリウムでpHを5〜7に調整し
てから有効成分23重量%のジフェニルメタン−ビス−
4、4′−N、N′−ジエチレン尿素水性分散液(明成
化学工業株式会社製)を10phr加え、均一に混合し
た後、アルミ板に塗工し、80℃で乾燥した。さらに1
50℃×30分間の条件で熱処埋を行い、遊離イソシア
ネート基による硬化を行い、室温にまで冷却した。硬化
塗膜の耐溶剤性試験をトルエンによるラビングテストに
より実施したところ、100回に耐え、耐溶剤性が向上
しており、熱硬化反応が確認された。Example 4 The pH of the fluorine-containing acrylic copolymer aqueous emulsion obtained in Example 3 was adjusted to 5 to 7 with 5% sodium hydroxide, and then 23% by weight of the active ingredient, diphenylmethane-bis- was used.
10 phr of 4,4'-N, N'-diethylene urea aqueous dispersion (manufactured by Meisei Chemical Industry Co., Ltd.) was added and uniformly mixed, and then coated on an aluminum plate and dried at 80 ° C. 1 more
Heat treatment was performed under the condition of 50 ° C. for 30 minutes to cure with free isocyanate groups, and then cooled to room temperature. When the solvent resistance test of the cured coating film was conducted by a rubbing test with toluene, it was able to withstand 100 times and the solvent resistance was improved, and a thermosetting reaction was confirmed.
【0030】実施例5 表1の単量体組成を用い、超音波照射を120分間行な
い、単量体プレエマルジョンの平均粒子径を約0.1μ
mとした以外は、実施例1と同様の操作によってラジカ
ル乳化重合を行なって含フッ素アクリル系共重合体水性
エマルジョンを得た。Example 5 Using the monomer composition shown in Table 1, ultrasonic irradiation was carried out for 120 minutes, and the average particle size of the monomer pre-emulsion was about 0.1 μm.
Radical emulsion polymerization was performed in the same manner as in Example 1 except that m was changed to obtain a fluorine-containing acrylic copolymer aqueous emulsion.
【0031】実施例6 実施例5で得た含フッ素アクリル系共重合体水性エマル
ジョンに5%水酸化ナトリウムでpHを5〜7に調整し
てから有効成分23重量%のジフェニルメタン−ビス−
4、4′−N、N′−ジエチレン尿素水性分散液(明成
化学工業株式会社製)を10phr加え、均一に混合し
た後、アルミ板に塗工し、80℃で乾燥した。さらに1
50℃×30分間の条件で熱処理を行い、遊離イソシア
ネート基による硬化を行い、室温にまで冷却した。硬化
塗膜の耐溶剤性試験をトルエンによるラビングテストに
より実施したところ、100回に耐え、耐溶剤性が向上
しており、熱硬化反応が確認された。Example 6 The pH of the fluorine-containing acrylic copolymer aqueous emulsion obtained in Example 5 was adjusted to 5 to 7 with 5% sodium hydroxide, and 23% by weight of the active ingredient, diphenylmethane-bis-, was added.
10 phr of 4,4'-N, N'-diethylene urea aqueous dispersion (manufactured by Meisei Chemical Industry Co., Ltd.) was added and uniformly mixed, and then coated on an aluminum plate and dried at 80 ° C. 1 more
Heat treatment was performed under the conditions of 50 ° C. for 30 minutes to cure with free isocyanate groups, and then cooled to room temperature. When the solvent resistance test of the cured coating film was conducted by a rubbing test with toluene, it was able to withstand 100 times and the solvent resistance was improved, and a thermosetting reaction was confirmed.
【0032】実施例7 実施例3で得た含フッ素アクリル系共重合体水性エマル
ジョン80重量部(固形分換算)に、ポリビニルアルコ
ールを保護コロイドとして通常の乳化重合により得られ
た平均粒子径1μmの酢酸ビニル(80)・ジブチルマ
レート(20)共重合体水性エマルジョン20重量部
(固形分換算)を加えて均一に撹拌混合して水性組成物
を得た。得られた水性組成物について実施例1と同様な
手法により▲撥▼水性を調べたところ▲撥▼水度はR
10で実施例3と同様であった。また、水性組成物をガ
ラス板に塗布・乾燥して皮膜を形成し、密着力を調べた
ところ、実施例3で得た含フッ素アクリル系共重合体エ
マルジョン単独に比較して著しく向上していた。Example 7 80 parts by weight (in terms of solid content) of the fluorine-containing acrylic copolymer aqueous emulsion obtained in Example 3 was obtained by ordinary emulsion polymerization using polyvinyl alcohol as a protective colloid and had an average particle diameter of 1 μm. 20 parts by weight (in terms of solid content) of a vinyl acetate (80) / dibutyl maleate (20) copolymer aqueous emulsion were added and uniformly mixed with stirring to obtain an aqueous composition. When the obtained aqueous composition was examined for water repellency by the same method as in Example 1, the water repellency was R.
10 was the same as in Example 3. Further, when the aqueous composition was applied to a glass plate and dried to form a film and the adhesion was examined, it was remarkably improved as compared with the fluorine-containing acrylic copolymer emulsion alone obtained in Example 3. .
【0033】実施例8 界面活性剤を乳化剤として通常の乳化重合により得られ
た平均粒子径0.5μmのエチルアクリレート重合体水
性エマルジョン70重量部(固形分換算)に実施例3で
得た含フッ素アクリル系共重合体水性エマルジョン30
重量部(固形分換算)を加えて、均一に撹拌混合して水
性組成物を得た。得られた水性組成物について実施例1
と同様な手法で▲撥▼水性を調べたところ▲撥▼水度は
R10で実施例3と同様であった。また、水性組成物を
ガラス板に塗布・乾燥して皮膜を形成し、密着力を調べ
たところ、実施例3で得た含フッ素アクリル系共重合体
エマルジョン単独に比較して著しく向上していた。Example 8 70 parts by weight (in terms of solid content) of an aqueous emulsion of an ethyl acrylate polymer having an average particle diameter of 0.5 μm obtained by ordinary emulsion polymerization using a surfactant as an emulsifier was used to obtain the fluorine-containing compound obtained in Example 3. Acrylic copolymer aqueous emulsion 30
By weight (in terms of solid content), the mixture was stirred and mixed uniformly to obtain an aqueous composition. Example 1 of the obtained aqueous composition
When the water repellency was examined by the same method as above, the water repellency was R 10 and was the same as in Example 3. Further, when the aqueous composition was applied to a glass plate and dried to form a film and the adhesion was examined, it was remarkably improved as compared with the fluorine-containing acrylic copolymer emulsion alone obtained in Example 3. .
【0034】[0034]
【表1】 [Table 1]
【0035】比較例1 実施例1において超音波処理を行わない以外は、実施例
1と全く同様にラジカル重合を行ったところ、重合中に
ゲル化物が多量に発生した。重合終了後、ゲル化物を含
むエマルジョンを瀘過して、実施例1と同様な手法によ
り▲撥▼水度を調べたところ▲撥▼水性は認められなか
った。Comparative Example 1 When radical polymerization was carried out in the same manner as in Example 1 except that ultrasonic treatment was not carried out in Example 1, a large amount of gelled product was generated during the polymerization. After the polymerization was completed, the emulsion containing the gelled product was filtered and the water repellency was examined by the same method as in Example 1. No water repellency was observed.
【0036】比較例2 表2の単量体組成を用いてβ−(パーフルオロオクチ
ル)エチルアクリレートを使用せずに、超音波処理を行
わず比較例1と同様の操作によって通常のラジカル乳化
重合を行って、(メタ)アクリル系共重合体水性エマル
ジョンを得た。重合終了後、得られた(メタ)アクリル
系共重合体水性エマルジョンについて、実施例1と同様
な手法により▲撥▼水度を調べたところ▲撥▼水性は認
められなかった。Comparative Example 2 Using the monomer composition shown in Table 2, without using β- (perfluorooctyl) ethyl acrylate, and without ultrasonic treatment, the same procedure as in Comparative Example 1 was carried out to carry out the usual radical emulsion polymerization. Then, a (meth) acrylic copolymer aqueous emulsion was obtained. After the completion of the polymerization, the obtained water-soluble (meth) acrylic copolymer was examined for water repellency by the same method as in Example 1. No water repellency was observed.
【0037】比較例3 実施例1において使用した単量体混合液を β−(パーフルオロオクチル)エチルアクリレート 1mol% n−ブチルメタクリレート 94mol% アクリル酸 5mol% とした以外は実施例1と同様にしてアクリル系共重合体
水性エマルジョンを得た。得られたアクリル系共重合体
水性エマルジョンについて実施例1と同様な手法によ
り、▲撥▼水度を調べたところ▲撥▼水性は認められな
かった。Comparative Example 3 The same procedure as in Example 1 was repeated except that the monomer mixture used in Example 1 was β- (perfluorooctyl) ethyl acrylate 1 mol% n-butyl methacrylate 94 mol% acrylic acid 5 mol%. An aqueous acrylic copolymer emulsion was obtained. The obtained acrylic copolymer aqueous emulsion was examined for water repellency by the same method as in Example 1. No water repellency was observed.
【0038】比較例4 表2の単量体組成を用いてβ−(パーフルオロオクチ
ル)エチルアクリレートの代わりにトリフルオロエチル
メタクリレートを使用した以外は実施例1と同様にして
ラジカル乳化重合を行なって、アクリル系共重合体水性
エマルジョンを得た。重合終了後、得られたアクリル系
共重合体水性エマルジョンについて実施例1と同様な手
法により▲撥▼水度を調べたところ、▲撥▼水性は認め
られなかった。Comparative Example 4 Radical emulsion polymerization was carried out in the same manner as in Example 1 except that trifluoroethyl methacrylate was used instead of β- (perfluorooctyl) ethyl acrylate using the monomer composition shown in Table 2. An aqueous acrylic copolymer emulsion was obtained. After the completion of the polymerization, the water-repellency of the obtained acrylic copolymer aqueous emulsion was examined by the same method as in Example 1. No water-repellency was observed.
【0039】比較例5 実施例1において使用したβ−(パーフルオロオクチ
ル)エチルアクリレートの代わりに、β−(パーフルオ
ロステアリル)エチルアクリレートを用いた。β−(パ
ーフルオロステアリル)エチルアクリレートはn−ブチ
ルメタクリレートには溶解せず、超音波照射を行なって
も、均一な単量体プレエマルジョンを得ることができな
かった。さらに、ラジカル乳化重合を行なっても水性エ
マルジョンを得ることができなかった。Comparative Example 5 In place of β- (perfluorooctyl) ethyl acrylate used in Example 1, β- (perfluorostearyl) ethyl acrylate was used. β- (Perfluorostearyl) ethyl acrylate was not soluble in n-butyl methacrylate, and even if ultrasonic irradiation was performed, a uniform monomer pre-emulsion could not be obtained. Furthermore, even if radical emulsion polymerization was performed, an aqueous emulsion could not be obtained.
【0040】[0040]
【表2】 [Table 2]
【0041】[0041]
【発明の効果】安定性と▲撥▼水性と▲撥▼油性に優れ
た微粒状のフッ素含有アクリル水性エマルジョンを重合
成分をモノマーに溶解し水中に微粒状に分散して重合す
ることにより製造することが出来る。そして、このエマ
ルジョン組成物を単独で使用し、または他の物質と併用
することにより▲撥▼水性と▲撥▼油性を必要とする各
種用途に使用することが出来る。EFFECT OF THE INVENTION It is produced by dissolving a finely divided fluorine-containing acrylic aqueous emulsion having excellent stability, water repellency and oil repellency in a monomer in which a polymerization component is dissolved, and finely dispersed in water for polymerization. You can The emulsion composition can be used alone or in combination with other substances for various uses requiring water repellency and oil repellency.
Claims (7)
ーにより水中に乳化分散させ、分散粒子の粒径を0.3
μm以下の微粒となしてからラジカル重合することを特
徴とする、粒径0.3μm〜0.05μmの分散粒子か
らなる含フッ素アクリル系共重合体水性エマルジョンの
製造方法1. (A) 2 to 40 mol% of a perfluoroalkyl acrylate-based monomer having an alkyl group having 6 to 12 carbon atoms (B) α, β-ethylene having a carboxyl group copolymerizable with the above (A) Unsaturated monomer 0.1 to 15 mol% (C) α, β-ethylenically unsaturated monomer having a hydroxyl group copolymerizable with the above (A) and (B) 0 to 25 mol% (D ) 97.9 to 45 mol% of an α, β-ethylenically unsaturated monomer other than the above copolymerizable with (A), (B) and (C) is ultrasonically irradiated with a surfactant or under high pressure. Homogenizer
Emulsify and disperse in water by
Dispersed particles having a particle size of 0.3 μm to 0.05 μm, characterized by being radically polymerized after forming fine particles of μm or less
Of producing fluorine-containing acrylic copolymer aqueous emulsion comprising
分散させた後、超音波照射または高圧ホモジナイザー処
理により分散粒子の粒径を0.3μm以下とする請求項
1に記載された、含フッ素アクリル系共重合体水性エマ
ルジョンの製造方法。2. After the monomer is emulsified and dispersed in water using a surfactant, wherein the particle size of the dispersed particles by ultrasonic irradiation or high-pressure auxiliary motor Jinaiza process in claim 1, 0.3μm or less And a method for producing a water-based emulsion of a fluorine-containing acrylic copolymer.
するパーフルオロアルキルアクリレート系単量体がβ−
(パーフルオロオクチル)エチルアクリレートである請
求項1または2に記載された含フッ素アクリル系共重合
体水性エマルジョンの製造方法3. A (A) perfluoroalkyl acrylate-based monomer having an alkyl group having 6 to 12 carbon atoms is β-
(Perfluorooctyl) ethyl acrylate, The method for producing the fluorinated acrylic copolymer aqueous emulsion according to claim 1 or 2.
−フルオロアルキルアクリレート系単量体と共重合可能
なカルボキシル基を有するα、β−エチレン性不飽和単
量体がアクリル酸である請求項1ないし3のいずれか1
項に記載された含フッ素アクリル系共重合体水性エマル
ジョンの製造方法4. An α, β-ethylenically unsaturated monomer having a carboxyl group copolymerizable with a perfluoroalkyl acrylate monomer having an alkyl group having 6 to 12 carbon atoms is acrylic acid. Any one of items 1 to 3
Of producing fluorine-containing acrylic copolymer aqueous emulsion described in paragraph
された方法により製造された粒径0.3μm〜0.05
μmの分散粒子からなる含フッ素アクリル系共重合体微
粒子の水性エマルジョン。5. A particle size of 0.3 μm to 0.05 produced by the method according to any one of claims 1 to 4.
Aqueous emulsion of fluorine-containing acrylic copolymer fine particles composed of dispersed particles of μm.
ル系共重合体微粒子の水性エマルジョンと、ブロック化
ポリイソシアネートとを主要成分とする水性組成物。6. An aqueous emulsion of the fluorine-containing acrylic copolymer fine particles according to claim 5, and blocking
An aqueous composition containing a polyisocyanate as a main component.
アクリル系共重合体微粒子の水性エマルジョンと、分散
粒子の粒径が0.1〜10μmである合成樹脂水性エマ
ルジョンとを主要成分とする水性組成物。7. A aqueous emulsion of fluorine-containing acrylic copolymer particles according to claim 5 or 6, the particle size of the dispersed particles and the synthetic resin aqueous emulsion and the principal ingredient is 0.1~10μm Aqueous composition.
Priority Applications (1)
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JP3264266A JPH0778154B2 (en) | 1991-07-11 | 1991-07-11 | Method for producing aqueous fluorinated acrylic copolymer emulsion and composition thereof |
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Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3264266A JPH0778154B2 (en) | 1991-07-11 | 1991-07-11 | Method for producing aqueous fluorinated acrylic copolymer emulsion and composition thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0517538A JPH0517538A (en) | 1993-01-26 |
JPH0778154B2 true JPH0778154B2 (en) | 1995-08-23 |
Family
ID=17400784
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JP3264266A Expired - Fee Related JPH0778154B2 (en) | 1991-07-11 | 1991-07-11 | Method for producing aqueous fluorinated acrylic copolymer emulsion and composition thereof |
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JP2660312B2 (en) * | 1992-05-29 | 1997-10-08 | ヘキスト合成株式会社 | Fluorine-containing water- and oil-repellent composition |
US5965659A (en) * | 1993-12-29 | 1999-10-12 | Daikin Industries Ltd. | Fluorine-containing-oil-in-water emulsion and surface treatment composition |
FR2725721B1 (en) * | 1994-10-18 | 1998-12-04 | Atochem Elf Sa | LATEX AND MIXTURES OF FLUORINATED ACRYLIC AND METHACYL LATEX, THEIR MANUFACTURING PROCESSES AND THEIR APPLICATIONS IN THE FIELD OF HYDROPHOBIC COATINGS |
ATE313605T1 (en) * | 1997-07-08 | 2006-01-15 | Arkema | COATING MATERIAL |
JP3876495B2 (en) * | 1997-09-12 | 2007-01-31 | ユニマテック株式会社 | Water and oil repellent and method for producing the same |
US6121372A (en) * | 1998-03-06 | 2000-09-19 | Nippon Mektron Limited | Aqueous emulsion component for a water- and oil-repellant agent |
WO2002024828A1 (en) | 2000-09-21 | 2002-03-28 | Daikin Industries, Ltd. | Aqueous dispersion of water- and oil-repellent and process for the production thereof |
US6861489B2 (en) * | 2001-12-06 | 2005-03-01 | Gore Enterprise Holdings, Inc. | Low equivalent weight ionomer |
JP3972824B2 (en) * | 2003-01-28 | 2007-09-05 | ユニマテック株式会社 | Manufacturing method of aqueous dispersion |
JP4329559B2 (en) * | 2003-05-02 | 2009-09-09 | ダイキン工業株式会社 | Surface treatment agent comprising fluorine-containing polymer |
WO2004108779A1 (en) * | 2003-06-09 | 2004-12-16 | Daikin Industries, Ltd. | Masonry-treating agnet |
JP4984889B2 (en) * | 2004-03-12 | 2012-07-25 | ダイキン工業株式会社 | Polymers and treatments for the treatment of leather and protein fibers |
US20070197717A1 (en) * | 2004-04-09 | 2007-08-23 | Akihiko Ueda | Polymer for masonry treatment and treating agent |
CN1942541B (en) | 2004-04-20 | 2010-12-01 | 大金工业株式会社 | Water- and oil-repellent composition and process for production thereof |
US8394887B2 (en) | 2005-04-27 | 2013-03-12 | Daikin Industries, Ltd. | Fluoropolymer having S-sulfate group and water/oil repellent composition containing the polymer |
CA2607627C (en) * | 2005-05-09 | 2010-12-14 | Daikin Industries, Ltd. | Fluorosilicones and fluorine- and silicon-containing surface treatment agent |
JP5567334B2 (en) * | 2006-10-20 | 2014-08-06 | ダイキン工業株式会社 | Treatment with water and oil repellent |
US7964657B2 (en) | 2007-03-23 | 2011-06-21 | Peach State Labs, Inc. | Polymeric dispersions and applications thereof |
KR101554114B1 (en) * | 2007-05-15 | 2015-09-17 | 다이킨 고교 가부시키가이샤 | Water-repellent oil-repellent antifouling agent having good solubility in solvent |
KR20100087143A (en) | 2007-11-01 | 2010-08-03 | 아사히 가라스 가부시키가이샤 | Fluorinated copolymer, water-proof and oil-proof agent composition, and their production methods |
JPWO2009110091A1 (en) * | 2008-03-07 | 2011-07-14 | 綜研化学株式会社 | Light diffusing resin composition and light diffusing sheet using the same |
JP5605034B2 (en) * | 2010-07-09 | 2014-10-15 | 株式会社野田スクリーン | Fluorine copolymer, method for producing fluorine copolymer, and coating agent |
JP2013245314A (en) * | 2012-05-28 | 2013-12-09 | Noda Screen:Kk | Coating agent |
JP7231915B1 (en) * | 2022-11-04 | 2023-03-02 | サイデン化学株式会社 | Fluorine-containing aqueous resin particle dispersion and method for producing the same |
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JPS58185606A (en) * | 1982-04-26 | 1983-10-29 | Showa Denko Kk | Acrylic resin emulsion |
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LAPS | Cancellation because of no payment of annual fees |