JPH09296134A - Water-repellent and oil-repellent powder and its production - Google Patents
Water-repellent and oil-repellent powder and its productionInfo
- Publication number
- JPH09296134A JPH09296134A JP8131171A JP13117196A JPH09296134A JP H09296134 A JPH09296134 A JP H09296134A JP 8131171 A JP8131171 A JP 8131171A JP 13117196 A JP13117196 A JP 13117196A JP H09296134 A JPH09296134 A JP H09296134A
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- JP
- Japan
- Prior art keywords
- powder
- group
- fluorine
- water
- carbon atoms
- 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.)
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Landscapes
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Polyethers (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【0001】[0001]
【発明が属する技術の分野】本発明は塗料及び化粧料等
に用いられる顔料等の粉体に関し、特に、撥水撥油性を
有する粉体及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to powders such as pigments used in paints and cosmetics, and more particularly to powders having water and oil repellency and a method for producing the same.
【0002】[0002]
【従来の技術】従来、塗料及び化粧料等に適用されてい
る顔料等の粉体は、通常無機粉体と有機粉体に大別する
ことができる。これらのうち、無機粉体は、通常複合酸
化物であり、それらは表面に水酸基を有し、また、その
水酸基の量は粉体の種類により異なっている。このた
め、粉体の種類によって表面の親水化度や親油化度に相
違が見られ、また表面活性度の異なる各種粉体が存在す
る。2. Description of the Related Art Conventionally, powders such as pigments applied to paints and cosmetics can be roughly classified into inorganic powders and organic powders. Of these, inorganic powders are usually complex oxides, which have hydroxyl groups on the surface, and the amount of the hydroxyl groups differs depending on the type of powder. For this reason, there are differences in the degree of hydrophilicity and lipophilicity of the surface depending on the type of powder, and there are various powders with different surface activities.
【0003】更に、それらの微細表面の機械的衝撃力に
よる粒子サイズ及び形状の変化、あるいは新生表面の発
現(産生)等による表面活性度の相違等からくる水又は
有機物に対する濡れ方の違い等から、塗料においては、
塗膜のムラや浮き、化粧料においては化粧膜のくずれや
密着感の不足の原因となっていた。Further, due to a difference in particle size and shape due to mechanical impact force of the fine surface, or a difference in surface activity due to expression (production) of a new surface, a difference in wettability with water or an organic substance. , In paint,
This caused unevenness and floating of the coating film, and in cosmetics, it was the cause of collapse of the cosmetic film and lack of adhesion.
【0004】これらの欠点を解決する手段としては、以
下の如く種々の方法が提案されていた。 イ.金属石鹸、界面活性剤で粉体を表面処理する方法 ロ.粉体表面に≡SiH基を有するポリシロキサン等で
焼付け処理する方法(例えば、特公昭41−9890号
公報) ハ.アルコール化合物等で粉体表面を処理する方法 しかしながら、上述のいずれの方法も、密着性や撥水撥
油性が充分でない等の欠点があった。As means for solving these drawbacks, various methods have been proposed as follows. I. Method of surface treatment of powder with metallic soap and surfactant b. Method of baking treatment on the powder surface with polysiloxane or the like having ≡SiH group (for example, Japanese Patent Publication No. 41-9890) c. However, all of the above methods have drawbacks such as insufficient adhesion and insufficient water / oil repellency.
【0005】これらの欠点を克服するために、無機粉体
基剤を、加熱下でガス状の撥水撥油性剤と接触反応さ
せ、該基剤表面の活性点に撥水撥油剤を反応結合させて
気相析着被覆層を基剤表面に形成させる方法(特開平1
−318070号公報)が提案された。しかしながら、
この方法では黄色の酸化鉄や紺青のような熱に弱いもの
を処理することができない。また、焼付け温度を下げる
ために触媒を用いる方法もあるが(例えば、特公昭45
−18999号公報)、焼付け後に残留した触媒が、表
面処理した物質や共存する他の成分の分解を促進するの
で、塗料や化粧料等においては使用することができなか
った。In order to overcome these drawbacks, an inorganic powder base is reacted with a gaseous water-repellent and oil-repellent agent by heating, and the water- and oil-repellent agent is reactively bonded to an active site on the surface of the base. To form a vapor-deposition coating layer on the surface of the base (Japanese Patent Application Laid-Open No. HEI-1)
-318070 publication) was proposed. However,
This method cannot handle heat-sensitive materials such as yellow iron oxide and dark blue. There is also a method of using a catalyst to lower the baking temperature (see, for example, Japanese Patent Publication No.
No. 18899), the catalyst remaining after baking accelerates the decomposition of the surface-treated substance and other coexisting components, and therefore cannot be used in paints and cosmetics.
【0006】[0006]
【発明が解決しようとする課題】そこで、本発明者等
は、上記の欠点を解決するために鋭意検討した結果、粉
体の表面に低温で含フッ素基変性(メタ)アクリルモノ
マー共重合体を処理することにより、無機粉体のみなら
ず有機粉体の表面に均一な処理被膜を形成させ、撥水及
び撥油性を付与することができることを見いだし、本発
明に到達した。The inventors of the present invention have made extensive studies in order to solve the above-mentioned drawbacks. As a result, the fluorine-containing group-modified (meth) acrylic monomer copolymer was formed on the surface of the powder at a low temperature. It was found that the treatment makes it possible to form a uniform treated film not only on the surface of the inorganic powder but also on the surface of the organic powder, and imparts water repellency and oil repellency to the present invention.
【0007】従って、本発明の第一の目的は、塗料及び
化粧料等の顔料に好適な、撥水撥油性を有する粉体を提
供することにある。本発明の第二の目的は、塗料及び化
粧料等の顔料に好適な、撥水撥油性を有する粉体の製造
方法を提供することにある。Therefore, a first object of the present invention is to provide a powder having water and oil repellency, which is suitable for pigments such as paints and cosmetics. A second object of the present invention is to provide a method for producing a powder having water / oil repellency, which is suitable for pigments such as paints and cosmetics.
【0008】[0008]
【課題を解決するための手段】本発明の上記の諸目的
は、無機又は有機の粉体の表面を、含フッ素(メタ)ア
クリル酸エステルを必須成分とする含フッ素共重合体で
処理してなる、撥水撥油性を有する粉体及びその製造方
法によって達成された。The above-mentioned various objects of the present invention are achieved by treating the surface of an inorganic or organic powder with a fluorine-containing copolymer having a fluorine-containing (meth) acrylic ester as an essential component. And a powder having water and oil repellency and a method for producing the same.
【0009】本発明で使用することのできる無機粉体と
しては、例えば、酸化チタン、酸化亜鉛、酸化鉄、黄酸
化鉄、酸化クロム、群青、紺青、タルク、マイカ、セリ
サイト、珪そう土、アルミニウムパウダー、炭酸カルシ
ウム、ハイドロキシアパタイト、シリカ、カーボン粉末
等を挙げることができる。また、有機粉体としては、例
えば、ポリスチレン・ポリエチレン等の樹脂パウダー、
赤色201号、黄色202号等の有機顔料、クロロフィ
ル、β−カロチンなどの天然色素、ウレタン、ネオプレ
ン、シリコーン等のゴムパウダー、シリコーンゲル、シ
ルセスキオキサン等のシリコーン製品等を挙げることが
できる。Examples of the inorganic powder which can be used in the present invention include titanium oxide, zinc oxide, iron oxide, iron oxide yellow, chromium oxide, ultramarine blue, dark blue, talc, mica, sericite, diatomaceous earth, Examples thereof include aluminum powder, calcium carbonate, hydroxyapatite, silica and carbon powder. As the organic powder, for example, resin powder such as polystyrene and polyethylene,
Examples thereof include organic pigments such as Red No. 201 and Yellow No. 202, natural pigments such as chlorophyll and β-carotene, rubber powders such as urethane, neoprene and silicone, silicone gel, silicone products such as silsesquioxane.
【0010】本発明において、使用する含フッ素共重合
体は少なくとも、下記一般式(1)で表される含フッ素
アクリル酸エステル、または、含フッ素メタクリル酸エ
ステルを必須成分とするが、特に、後記する一般式
(2)で表される(メタ)アクリロキシ基含有シランを
も含有することが好ましい。 一般式(1):CH2 =CR1 COORf 但し、式中のR1 は水素原子又はメチル基、Rf は炭素
数1〜20のアルキル又は炭素数6〜22のアルキエー
テルの水素原子の一部又は全部をフッ素原子で置換した
ポリフルオロアルキル基又はポリフルオロエーテル基で
ある。In the present invention, the fluorine-containing copolymer to be used contains at least a fluorine-containing acrylic acid ester or a fluorine-containing methacrylic acid ester represented by the following general formula (1) as an essential component. It is also preferable to contain a (meth) acryloxy group-containing silane represented by the general formula (2). Formula (1): CH 2 = CR 1 COOR f where, R 1 in the formula is a hydrogen atom or a methyl group, R f is a hydrogen atom alkylene ethers having 6 to 22 alkyl carbon atoms or 1 to 20 carbon atoms It is a polyfluoroalkyl group or a polyfluoroether group in which some or all are substituted with fluorine atoms.
【0011】上記一般式(1)中のRfの具体例として
は下記化1で表される基が挙げられる。Specific examples of Rf in the above general formula (1) include groups represented by the following chemical formula 1.
【化1】 また、撥水撥油性効果を有効に付与させる観点から、前
記一般式(1)で表される化合物の使用量は、共重合体
中の50〜99.9重量%であることが好ましい。Embedded image From the viewpoint of effectively imparting the water and oil repellency effect, the amount of the compound represented by the general formula (1) used is preferably 50 to 99.9% by weight in the copolymer.
【0012】本発明においては、粉体表面への含フッ素
共重合体の密着性を向上させるために、前記一般式
(1)で表される含フッ素(メタ)アクリル酸エステル
と共に、下記一般式(2)で表される、ビニルシラン、
及び、(メタ)アクリロキシ基含有シランの中から選択
される少なくとも一種のシランをも、必須成分として加
えて製造した含フッ素共重合体を用いて、粉体の表面に
被膜処理を行うことが好ましい。In the present invention, in order to improve the adhesion of the fluorine-containing copolymer to the powder surface, the following general formula is used together with the fluorine-containing (meth) acrylic acid ester represented by the above general formula (1). Vinylsilane represented by (2),
Also, it is preferable to perform a coating treatment on the surface of the powder by using the fluorine-containing copolymer produced by adding at least one silane selected from the (meth) acryloxy group-containing silanes as an essential component. .
【0013】一般式(2): CH2=CR1(COOCH2CH2CH2) m -SiR2 3-c(OR3) c 但し、R1 は水素原子又はメチル基、R2 は炭素数1〜
8のアルキル基、R3 は炭素数1〜4のアルキル基、ア
ルコキシ置換アルキル基、又はアルケニル基、mは0又
は1、Cは1、2又は3である。General formula (2): CH 2 = CR 1 (COOCH 2 CH 2 CH 2 ) m -SiR 2 3-c (OR 3 ) c where R 1 is a hydrogen atom or a methyl group and R 2 is a carbon number. 1 to
8 is an alkyl group, R 3 is an alkyl group having 1 to 4 carbon atoms, an alkoxy-substituted alkyl group, or an alkenyl group, m is 0 or 1, and C is 1, 2 or 3.
【0014】上記一般式(2)で表されたシランの具体
例としては下記化2で表される化合物が挙げられる。Specific examples of the silane represented by the general formula (2) include compounds represented by the following chemical formula 2.
【化2】 又、共重合体の密着性を向上する観点から、前記一般式
(2)で表された化合物の使用量は、共重合体中の0.
1〜10.0重量%であることが好ましい。Embedded image From the viewpoint of improving the adhesiveness of the copolymer, the amount of the compound represented by the general formula (2) used is 0.
It is preferably from 1 to 10.0% by weight.
【0015】本発明において設ける粉体の皮膜の強度、
硬度、基材への密着性、及び耐汚染性等を調節するため
に、本発明においては、前記一般式(1)及び(2)で
表された化合物と共重合可能なビニル系単量体を、更に
適宜用いることができる。上記ビニル系単量体の具体例
としては、メチル(メタ)アクリレート、エチル(メ
タ)アクリレート、n−ブチル(メタ)アクリレート等
の、アクリレート若しくはメタクリレート類、スチレン
及びビニルトルエン等の芳香族系ビニル化合物、マレイ
ン酸、フマル酸等の不飽和ジカルボン酸と炭素数1〜1
8の1価アルコールとのジエステル類、n−ブチルビニ
ルエーテル、シクロヘキシルビニルエーテル等のビニル
エーテル類等が挙げられる。The strength of the powder coating provided in the present invention,
In the present invention, a vinyl-based monomer copolymerizable with the compounds represented by the general formulas (1) and (2) in order to adjust hardness, adhesion to a substrate, stain resistance and the like. Can be used as appropriate. Specific examples of the vinyl-based monomer include acrylates or methacrylates such as methyl (meth) acrylate, ethyl (meth) acrylate and n-butyl (meth) acrylate, aromatic vinyl compounds such as styrene and vinyltoluene. Dicarboxylic acids such as carboxylic acid, maleic acid, and fumaric acid, and 1 to 1 carbon atoms
And diethers with monohydric alcohols, vinyl ethers such as n-butyl vinyl ether and cyclohexyl vinyl ether.
【0016】本発明における、含フッ素共重合体を用い
た被膜処理方法としては、まず、該共重合体の溶剤溶液
を調製し、あるいは、乳化剤の存在下乳化共重合するこ
とによって水性乳化物を作製し、これらを粉体にスプレ
ー等によって塗布したり、粉体をこれらの液体中に分散
させて該粉体表面に共重合体を付着させた後、水又は有
機溶剤を蒸発させることによって、皮膜を形成させる方
法を挙げることができる。As a coating treatment method using a fluorine-containing copolymer in the present invention, first, a solvent solution of the copolymer is prepared, or an aqueous emulsion is prepared by emulsion copolymerization in the presence of an emulsifier. By making them, applying them to the powder by spraying or the like, or by dispersing the powder in these liquids and attaching the copolymer to the surface of the powder, by evaporating water or an organic solvent, The method of forming a film can be mentioned.
【0017】共重合体溶液をつくるための有機溶剤は、
該共重合体を容易に溶解することができると共に蒸発し
易いものであれば特に制限されず、その具体例としては
メチルエチルケトン、メチルイソブチルケトンのような
ケトン類、及びm−キシレンヘキサフロライド、トリフ
ルオロメチルベンゼンのような含フッ素炭化水素類が挙
げられる。The organic solvent for preparing the copolymer solution is
The copolymer is not particularly limited as long as it can be easily dissolved and easily evaporated, and specific examples thereof include ketones such as methyl ethyl ketone and methyl isobutyl ketone, and m-xylene hexafluoride and tri Fluorine-containing hydrocarbons such as fluoromethylbenzene may be mentioned.
【0018】また、粉体に共重合体を付着させた後水又
は有機溶剤を蒸発させる温度は、溶剤の種類によって変
化するが、その範囲は20℃〜150℃であることが好
ましく、また、減圧下で水又は有機溶剤を蒸発させるこ
ともできる。このようにして得られた本発明の粉体は塗
料や化粧料の顔料等として使用することができる。The temperature at which the water or organic solvent is evaporated after the copolymer is attached to the powder varies depending on the type of solvent, but the range is preferably 20 ° C to 150 ° C. It is also possible to evaporate the water or organic solvent under reduced pressure. The powder of the present invention thus obtained can be used as a pigment for paints and cosmetics.
【0019】[0019]
【発明の実施の形態】本発明の粉体は、前記一般式
(1)で表される含フッ素(メタ)アクリル酸エステル
を必須成分とする含フッ素共重合体の溶剤溶液又は水性
乳化物を調製し、適宜選択した粉体を前記溶剤溶液又は
水性乳化物中に分散させ、粉体表面に共重合体を付着さ
せた後、水又は有機溶剤を蒸発させることによって得る
ことができる。BEST MODE FOR CARRYING OUT THE INVENTION The powder of the present invention comprises a solvent solution or an aqueous emulsion of a fluorine-containing copolymer containing the fluorine-containing (meth) acrylic acid ester represented by the general formula (1) as an essential component. It can be obtained by dispersing powder prepared and appropriately selected in the solvent solution or the aqueous emulsion, adhering the copolymer on the powder surface, and then evaporating water or an organic solvent.
【0020】[0020]
【発明の効果】本発明の撥水性、及び、撥油性を有する
粉体は、均一の被膜が形成されている上、皮膜が粉体の
表面に密着している。また、その被膜処理は粉体の表面
に塗布する、若しくは、付着させる等の極めて簡単な手
法で足りる。しかも、その過程においては触媒を用いず
に、低温で行うことができるため、熱に弱い粉体にも処
理することができ、触媒の残留による影響もない。INDUSTRIAL APPLICABILITY The powder having water repellency and oil repellency according to the present invention has a uniform coating formed thereon and the coating adheres to the surface of the powder. Further, the coating treatment may be carried out by an extremely simple method such as coating or adhering on the surface of the powder. Moreover, in that process, since it can be carried out at a low temperature without using a catalyst, it is possible to process even a powder which is weak against heat, and there is no influence due to the catalyst remaining.
【0021】[0021]
【実施例】以下、本発明を実施例によって更に詳述する
が、本発明はこれによって限定されるものではない。
又、特に断らない限り、以下に記載する「部」及び
「%」は、それぞれ「重量部」及び「重量%」を意味す
る。EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.
Unless otherwise specified, “parts” and “%” described below mean “parts by weight” and “% by weight”, respectively.
【0022】合成例1.200ミリリットルのフラスコ
中にマレイン酸1.1部、及び、メチルイソブチルケト
ン(MIBK)23.8部を仕込み、窒素気流下で60
℃まで加熱し、アゾビスイソブチロニトリル(AIB
N)0.06部を投入した後、下記化3及び化4で表さ
れる化合物をそれぞれ13.5部、7.9部、そして更
に、AIBN0.06部、及び、MIBK3.8部を加
え、60〜65℃で16時間反応させた。Synthetic Example 1. A 200 ml flask was charged with 1.1 parts of maleic acid and 23.8 parts of methyl isobutyl ketone (MIBK), and the mixture was placed under a nitrogen stream at 60.
Heat to ℃, azobisisobutyronitrile (AIB
N) After adding 0.06 part, 13.5 parts and 7.9 parts of the compounds represented by the following chemical formulas 3 and 4, respectively, and further, AIBN 0.06 part and MIBK 3.8 parts are added. The reaction was carried out at 60 to 65 ° C for 16 hours.
【0023】[0023]
【化3】 Embedded image
【化4】 反応終了後室温まで冷却し、MIBK100部を加えて
反応液を希釈し、含フッ素メタクリル酸エステル共重合
体溶液を得た。得られた溶液の不揮発分は14.8%で
あった。Embedded image After completion of the reaction, the mixture was cooled to room temperature and 100 parts of MIBK was added to dilute the reaction solution to obtain a fluorinated methacrylic acid ester copolymer solution. The nonvolatile content of the obtained solution was 14.8%.
【0024】合成例2.攪拌装置を装着した200ミリ
リットルのフラスコ中に、下記化5で表される化合物を
28.0部、ポリオキシエチレンラウリルエーテル0.
8部、トリメチルオクタデシルアンモニウムクロライド
0.8部、ラウリルメルカプタン0.28部、アセトン
14.0部、及び、脱酸素した純水56.4部を入れ、
窒素気流下で約1時間、60℃に保ちながら充分に攪拌
したのち、2,2−アゾビス(2−アミジノプロパン)
二塩酸塩0.28部を添加し、更に、60℃下で5時間
攪拌して不揮発分30.0%のエマルジョンを作製し
た。Synthesis Example 2. In a 200 ml flask equipped with a stirrer, 28.0 parts of a compound represented by the following chemical formula 5 and polyoxyethylene lauryl ether
8 parts, 0.8 parts of trimethyloctadecyl ammonium chloride, 0.28 parts of lauryl mercaptan, 14.0 parts of acetone, and 56.4 parts of deoxygenated pure water,
After thoroughly stirring under a nitrogen stream for about 1 hour at 60 ° C, 2,2-azobis (2-amidinopropane)
0.28 parts of dihydrochloride was added, and the mixture was further stirred at 60 ° C. for 5 hours to prepare an emulsion having a nonvolatile content of 30.0%.
【化5】 Embedded image
【0025】合成例3.上記化5で表された化合物2
8.0部の代わりに、下記化6で表される化合物19.
6部を使用すると共に、ラウリルメルカプタン0.28
部の代わりに、ステアリルアクリレート8.1部を使用
した他は、合成例2と全く同様にして不揮発分29.1
%のエマルジョンを作製した。Synthesis Example 3. Compound 2 represented by the above chemical formula 5
Instead of 8.0 parts, compound 19.
Using 6 parts, lauryl mercaptan 0.28
In the same manner as in Synthesis Example 2 except that 8.1 parts of stearyl acrylate was used in place of parts, the nonvolatile content was 29.1.
% Emulsion was made.
【化6】 [Chemical 6]
【0026】合成例4.攪拌装置を装着した1リットル
のフラスコの中に、前記化5で表される化合物を60.
0部、下記化7で表される化合物を1.0部、メタクリ
ル酸ラウリル35部、メタクリル酸−2−ヒドロキシエ
チル5部、脱酸素した純水290部、アセトン100
部、トリメチルオクタデシルアンモニウムクロライド
2.5部、及び、ポリオキシエチレンラウリルエーテル
2.5部を入れ、窒素気流下で約1時間60℃に保ちな
がら充分に攪拌した後、脱酸素した純水4部にアゾビス
イソブチルアミジン塩酸塩0.4部を溶解させた液を添
加し、更に、60℃で5時間加熱攪拌して、不揮発分2
1.0%のエマルジョンを作製した。Synthesis Example 4. In a 1 liter flask equipped with a stirrer, the compound represented by the above chemical formula 5 was added to a 60.
0 part, 1.0 part of the compound represented by the following chemical formula 7, 35 parts of lauryl methacrylate, 5 parts of 2-hydroxyethyl methacrylate, 290 parts of deoxygenated pure water, and 100 parts of acetone.
Parts, 2.5 parts of trimethyloctadecyl ammonium chloride, and 2.5 parts of polyoxyethylene lauryl ether were added, and thoroughly stirred under a nitrogen stream for about 1 hour while maintaining at 60 ° C., then deoxidized pure water 4 parts. A solution in which 0.4 part of azobisisobutylamidine hydrochloride was dissolved was added to the above, and the mixture was further heated and stirred at 60 ° C. for 5 hours to give a nonvolatile content of 2
A 1.0% emulsion was made.
【化7】 [Chemical 7]
【0027】合成例5.合成例2で使用した化5で表さ
れた化合物28.0部の代わりに、ステアリルアクリレ
ート28.0部を用いると共に、ラウリルメルカプタン
を用いなかった他は、合成例2と全く同様にして不揮発
分29.3%のエマルジョンを作製した。Synthesis Example 5. The nonvolatile content was the same as in Synthesis Example 2 except that 28.0 parts of stearyl acrylate was used instead of 28.0 parts of the compound represented by Chemical formula 5 used in Synthesis Example 2 and lauryl mercaptan was not used. A 29.3% emulsion was made.
【0028】実施例1〜4.上記合成例1〜4で得られ
た各処理液の固型分濃度を20%に調整した後、その5
0部を攪拌装置を装着した300ミリリットルのフラス
コ中に入れた後、粉体として酸化チタン粉末100部を
加えて、60℃で1時間攪拌した。80℃/2mmHg
で溶媒を留去して、減圧乾燥させ、処理粉体1〜4を得
た。Examples 1 to 4. After adjusting the solid content concentration of each treatment liquid obtained in Synthesis Examples 1 to 4 to 20%,
0 part was placed in a 300 ml flask equipped with a stirrer, 100 parts of titanium oxide powder was added as powder, and the mixture was stirred at 60 ° C. for 1 hour. 80 ° C / 2mmHg
The solvent was distilled off with and dried under reduced pressure to obtain treated powders 1 to 4.
【0029】実施例5.合成例1で得られた処理液の固
形分濃度を20%に調整した後、その50部を攪拌装置
を装着した300ミリミットルのフラスコ中に入れた
後、粉体として紺青粉末100部を加えて、25℃で1
時間攪拌した。25℃/2mmHgで溶媒を溜去して、
減圧乾燥させ、処理粉体5を得た。Embodiment 5 FIG. After adjusting the solid content concentration of the treatment liquid obtained in Synthesis Example 1 to 20%, 50 parts of the solution was put into a 300 mi limitle flask equipped with a stirrer, and 100 parts of dark blue powder was added as powder. , At 25 ℃ 1
Stir for hours. The solvent is distilled off at 25 ° C / 2 mmHg,
It was dried under reduced pressure to obtain a treated powder 5.
【0030】得られた処理粉体を、それぞれアルミニウ
ムシャーレ(直径60mm、高さ9mm)の中に敷き詰
めた状態で、純水又はスクワランを滴下し、撥水性及び
撥油性の試験を行った。The treated powders thus obtained were spread in aluminum petri dishes (diameter: 60 mm, height: 9 mm), and pure water or squalane was added dropwise to the water and oil repellency tests.
【0031】この試験結果を以下の基準で判断した結果
は表1に示した通りである。 液滴の形状を保持し、染み込みは全くない..............◎ 液滴の形状は保持しているが、僅かに染み込みがある.........○ 液滴が広がってしまい、かなり染み込んでいる............△ 液滴が残っておらず、全て染み込んでいる..............×Table 1 shows the results of judgment of the test results based on the following criteria. It retains the shape of the droplets and has no penetration. . . . . . . . . . . . . . ◎ The shape of the droplet is retained, but it is slightly soaked. . . . . . . . . ○ The liquid droplets have spread and are soaking in. . . . . . . . . . . . △ There are no liquid droplets remaining, and they are all infiltrated. . . . . . . . . . . . . . ×
【0032】[0032]
【表1】 ──────────────────────── 試験 試験粉体 撥水性 撥油性 ──────────────────────── 実施例1 処理粉体1 ◎ ○ 実施例2 処理粉体2 ◎ ○ 実施例3 処理粉体3 ◎ ◎ 実施例4 処理粉体4 ◎ ◎ 実施例5 処理粉体5 ○ ○ 比較例1 処理粉体6 △ △ 比較例2 分解したため測定不能 比較例3 未処理粉体 × × ────────────────────────[Table 1] ──────────────────────── Test test powder Water repellency Oil repellency ─────────────── ────────── Example 1 treated powder 1 ◎ ○ Example 2 treated powder 2 ◎ ○ Example 3 treated powder 3 ◎ ◎ Example 4 treated powder 4 ◎ ◎ ◎ Example 5 treated Powder 5 ○ ○ Comparative example 1 Treated powder 6 △ △ Comparative example 2 Impossible to measure due to decomposition Comparative example 3 Untreated powder × × ───────────────────── ────
【0033】比較例1.合成例5で得られた処理液を用
いて、実施例1〜4と全く同様にして処理粉体6を作製
し、全く同様にして粉体の撥水性及び撥油性の試験を行
い、評価した結果は表1に示した通りである。Comparative Example 1 Using the treatment liquid obtained in Synthesis Example 5, treated powder 6 was prepared in exactly the same manner as in Examples 1 to 4, and the water repellency and oil repellency of the powder were tested and evaluated in exactly the same manner. The results are as shown in Table 1.
【0034】比較例2.メチルハイドロジェンポリシロ
キサンの10%トルエン溶液100部を攪拌装置を装着
した300ミリリットルのフラスコ中に入れた後、粉体
として紺青粉体100部と亜鉛オクトエート0.1部を
加え、150℃で加熱したところ、除々に変色し分解ガ
スを発生した。Comparative Example 2. 100 parts of a 10% solution of methyl hydrogen polysiloxane in toluene was placed in a 300 ml flask equipped with a stirrer, 100 parts of navy blue powder as powder and 0.1 part of zinc octoate were added, and heated at 150 ° C. Then, the color gradually changed and a decomposition gas was generated.
【0035】比較例3.処理前の粉体の基体となる酸化
チタン粉末を用いて、実施例1〜4と全く同様にして撥
水性及び撥油性の試験を行い、評価した結果は表1に示
した通りである。Comparative Example 3 Using the titanium oxide powder which is the base of the powder before treatment, water repellency and oil repellency tests were conducted in the same manner as in Examples 1 to 4, and the evaluation results are shown in Table 1.
───────────────────────────────────────────────────── 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 C09K 3/18 104 C09K 3/18 104 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location C09K 3/18 104 C09K 3/18 104
Claims (3)
も一般式(1)CH2 =CR1 COORf で表される含
フッ素(メタ)アクリル酸エステルを必須成分とする含
フッ素共重合体を用いて処理してなる撥水撥油性を有す
る粉体;但し、式中のR1 は水素原子又はメチル基、R
f は炭素原子数1〜20のアルキル基又は炭素原子数6
〜22のアルキルエーテルの水素原子の一部又は全部を
フッ素原子で置換したポリフルオロアルキル基又はポリ
フルオロエーテル基である。1. A fluorine-containing copolymer having, as an essential component, at least the surface of an inorganic or organic powder, the fluorine-containing (meth) acrylic acid ester represented by the general formula (1) CH 2 ═CR 1 COOR f. A water- and oil-repellent powder obtained by treating with R; wherein R 1 is a hydrogen atom or a methyl group, and R is
f is an alkyl group having 1 to 20 carbon atoms or 6 carbon atoms
22 is a polyfluoroalkyl group or a polyfluoroether group in which some or all of the hydrogen atoms of the alkyl ether of 22 are substituted with fluorine atoms.
(2)CH2 =CR1 −(COOCH2 CH2 CH2)m
−SiR2 3-C( OR3)C で表されるビニルシラン及び
(メタ)アクリロキシ基含有シランから選択される少な
くとも一種のシランを必須成分とする含フッ素共重合体
である、請求項1に記載された撥水撥油性を有する粉
体;但し、式中のR1 は水素原子又はメチル基、R2 は
炭素原子数1〜8のアルキル基、R3 は炭素原子数1〜
4のアルキル基、アルコキシ置換基、又はアルケニル
基、mは0又は1、Cは1、2または3である。2. The fluorine-containing copolymer further has the formula (2) CH 2 ═CR 1 — (COOCH 2 CH 2 CH 2 ) m.
The fluorine-containing copolymer containing at least one silane selected from vinylsilane represented by —SiR 2 3-C (OR 3 ) C and silane containing a (meth) acryloxy group as an essential component. R 1 is a hydrogen atom or a methyl group, R 2 is an alkyl group having 1 to 8 carbon atoms, and R 3 is 1 to 1 carbon atoms.
4, an alkyl group, an alkoxy substituent, or an alkenyl group, m is 0 or 1, and C is 1, 2 or 3.
般式(1)CH2 =CR1 COORf で表される含フッ
素共重合体の溶剤溶液、又は、乳化剤を含有する前記含
フッ素共重合体の水性乳化物を均一に塗布・付着させた
後、水又は有機溶剤を蒸発させることを特徴とする、撥
水撥油性を有する粉体の製造方法;但し、式中のR1 は
水素原子又はメチル基、Rf は炭素原子数1〜20のア
ルキル基又は炭素原子数6〜22のアルキエーテルの水
素原子の一部又は全部をフッ素原子で置換したポリフル
オロアルキル基又はポリフルオロエーテル基である。3. A solution of a fluorine-containing copolymer represented by the general formula (1) CH 2 ═CR 1 COOR f on the surface of an inorganic and / or organic powder, or a solution containing the emulsifier. A method for producing a powder having water and oil repellency, which comprises uniformly applying and adhering an aqueous emulsion of a fluorocopolymer and then evaporating water or an organic solvent; provided that R 1 in the formula Is a hydrogen atom or a methyl group, and R f is a polyfluoroalkyl group or a polyfluoroalkyl group in which part or all of the hydrogen atoms of an alkyl group having 1 to 20 carbon atoms or an alkyl ether having 6 to 22 carbon atoms are substituted with fluorine atoms. It is an ether group.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8131171A JPH09296134A (en) | 1996-04-26 | 1996-04-26 | Water-repellent and oil-repellent powder and its production |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8131171A JPH09296134A (en) | 1996-04-26 | 1996-04-26 | Water-repellent and oil-repellent powder and its production |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH09296134A true JPH09296134A (en) | 1997-11-18 |
Family
ID=15051676
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8131171A Pending JPH09296134A (en) | 1996-04-26 | 1996-04-26 | Water-repellent and oil-repellent powder and its production |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH09296134A (en) |
Cited By (8)
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---|---|---|---|---|
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JP2006169393A (en) * | 2004-12-16 | 2006-06-29 | Toyo Aluminium Kk | Metallic pigment and coating material containing the same |
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WO2014057712A1 (en) * | 2012-10-13 | 2014-04-17 | 東洋アルミニウム株式会社 | Water- and oil-repellent coating film and article containing same |
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1996
- 1996-04-26 JP JP8131171A patent/JPH09296134A/en active Pending
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2005007755A1 (en) * | 2003-07-18 | 2005-01-27 | Toyo Aluminium Kabushiki Kaisha | Flake pigment, coating material and powder coating composition each containing the same, and surface-treating agent for flaky particle for use therein |
JPWO2005007755A1 (en) * | 2003-07-18 | 2007-04-12 | 東洋アルミニウム株式会社 | Flake pigment, paint and powder paint containing the same, and surface treatment agent for flake particles used therefor |
JP4553844B2 (en) * | 2003-07-18 | 2010-09-29 | 東洋アルミニウム株式会社 | Flake pigment, paint and powder paint containing the same, and surface treatment agent for flake particles used therefor |
JP2006169393A (en) * | 2004-12-16 | 2006-06-29 | Toyo Aluminium Kk | Metallic pigment and coating material containing the same |
US8314037B2 (en) | 2007-12-07 | 2012-11-20 | E. I. Du Pont De Nemours And Company | Fluoropolymer emulsions |
JP2010215746A (en) * | 2009-03-16 | 2010-09-30 | Toray Ind Inc | Coating material composition, method for manufacturing antireflection film, and image display device |
US8329822B2 (en) | 2009-11-09 | 2012-12-11 | E.I. Du Pont De Nemours And Company | Fluoropolymer emulsions |
US8507601B2 (en) | 2009-11-09 | 2013-08-13 | E. I. Du Pont De Nemours And Company | Method using fluoropolymer emulsions |
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US10494554B2 (en) | 2012-10-13 | 2019-12-03 | Toyo Aluminium Kabushiki Kaisha | Water- and oil-repellent coating film and articles having this coating film |
WO2019026816A1 (en) * | 2017-07-31 | 2019-02-07 | 東洋アルミニウム株式会社 | Fluorine-containing composite particles |
JPWO2019026816A1 (en) * | 2017-07-31 | 2020-06-11 | 東洋アルミニウム株式会社 | Fluorine-containing composite particles |
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