JPH0532841A - Fluororesin composition cross-linkable with metal - Google Patents
Fluororesin composition cross-linkable with metalInfo
- Publication number
- JPH0532841A JPH0532841A JP20988591A JP20988591A JPH0532841A JP H0532841 A JPH0532841 A JP H0532841A JP 20988591 A JP20988591 A JP 20988591A JP 20988591 A JP20988591 A JP 20988591A JP H0532841 A JPH0532841 A JP H0532841A
- Authority
- JP
- Japan
- Prior art keywords
- polyvalent metal
- vinyl ether
- fluoropolymer
- metal
- parts
- 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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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は金属架橋性フッ素樹脂組
成物に関するものである。FIELD OF THE INVENTION The present invention relates to a metal crosslinkable fluororesin composition.
【0002】[0002]
【従来の技術】従来、水不溶性乳化重合体、ワックス及
び分散剤を含有するところの多くの床の艶出し組成物
は、水性アルカリ媒体を適用することにより除去するこ
とができる。それは、この様にして除去することができ
るようにわざわざしたもので、使用者が希望すれば(特
に長期間使用した後で汚れたり傷ついたりしたとき)容
易に以前に適用した艶出し剤を除去することができるよ
うにしたものである。これは床艶出し組成物が元来アル
カリ性であり、そのアルカリ性のため以前に適用された
艶出し剤が一部再分散されるためである。BACKGROUND OF THE INVENTION Many floor polish compositions, which conventionally contain water-insoluble emulsion polymers, waxes and dispersants, can be removed by applying an aqueous alkaline medium. It is purposely designed to be removed in this way, so that if the user so wishes (especially when it becomes dirty or scratches after long-term use), it can easily remove previously applied polishes. It is something that can be done. This is because the floor polish composition is alkaline in nature and because of its alkalinity, the previously applied polish is partly redispersed.
【0003】この再分散の際、艶出し組成物の粘度或は
濃度が変化し、新しい艶出しの適用は困難或は不規則に
なるという欠点があり、この欠点の解消を目的として、
特公昭47-15597号公報、特公昭49-1458 号公報の、艶出
し組成物へ多価金属化合物を含有させることが知られて
いる。しかし、これらの方法で得られた被覆膜には耐油
性がなく、有機溶剤、オイルなどが付着した場合、溶解
及び失沢、或いは、汚染してしまうので絶えず補修をし
なければならないという欠点を有していた。During this redispersion, there is a drawback that the viscosity or concentration of the glazing composition changes, and the application of new glazing becomes difficult or irregular. For the purpose of eliminating this drawback,
It is known that Japanese Patent Publication No. 47-15597 and Japanese Patent Publication No. 49-1458 include a polyvalent metal compound in a polishing composition. However, the coating films obtained by these methods do not have oil resistance, and when organic solvents, oils, etc. adhere to them, they dissolve and lose, or become contaminated, so they have to be constantly repaired. Had.
【0004】[0004]
【発明が解決しようとする課題】本発明は、従来にない
耐油性、耐水性及び耐候性をもつ艶出し用金属架橋性水
性組成物を提供することを目的とするものである。SUMMARY OF THE INVENTION It is an object of the present invention to provide a metal crosslinkable aqueous composition for polishing, which has oil resistance, water resistance and weather resistance which have not been found in the past.
【0005】[0005]
【課題を解決するための手段】本発明は、上記目的を達
成すべくなされたものであり、酸価が5〜50mgKO
H/gである含フッ素重合体、および金属架橋形成可能
な多価金属化合物を必須成分とすることを特徴とする金
属架橋性フッ素樹脂組成物を提供するものである。The present invention has been made to achieve the above object and has an acid value of 5 to 50 mg KO.
It is intended to provide a metal-crosslinkable fluororesin composition, which comprises a fluorine-containing polymer of H / g and a polyvalent metal compound capable of forming a metal crosslink as essential components.
【0006】本発明の含フッ素重合体とは、例えばフル
オロオレフィン系共重合体のうち、特にヒドロキシアル
キルビニルエーテルなどの水酸基含有単量体を共重合し
て得られる、水酸基含有含フッ素重合体に、二塩基性酸
無水物を反応せしめてカルボキシル基を導入したもの
(特開昭58−136605号公報参照)などが挙げら
れる。The fluorine-containing polymer of the present invention means, for example, a fluorine-containing polymer having a hydroxyl group obtained by copolymerizing a monomer having a hydroxyl group such as hydroxyalkyl vinyl ether among fluoroolefin copolymers. Examples thereof include those obtained by reacting a dibasic acid anhydride to introduce a carboxyl group (see JP-A-58-136605).
【0007】このような含フッ素重合体は、通常のポリ
カルボン酸樹脂とは異なり、低酸価領域において水に分
散し易く安定であるという特徴を有し、本発明では酸価
5〜50mgKOH/g、好ましくは7〜40mgKO
H/gの範囲の含フッ素重合体を水性組成物として使用
する。これは、酸価が5未満では水に十分に分散できず
たとえ分散できたとしても不安定であり、一方、酸価が
50mgKOH/gを超えると、形成された被覆の耐水
性が劣る。Unlike the usual polycarboxylic acid resin, such a fluorine-containing polymer is characterized in that it is easily dispersed in water in the low acid value region and is stable. In the present invention, the acid value is 5 to 50 mgKOH / g, preferably 7-40 mg KO
A fluoropolymer in the range of H / g is used as the aqueous composition. When the acid value is less than 5, it cannot be sufficiently dispersed in water and is unstable even if it can be dispersed. On the other hand, when the acid value exceeds 50 mgKOH / g, the water resistance of the coating formed is poor.
【0008】また、本発明における多価金属化合物とし
ては、金属錯体又は金属キレートも含まれる。多価金属
化合物は、水中に少なくとも1重量%のような顕著な溶
解性を有する酸化物、水酸化物又は塩基性塩、酸性塩又
は中性塩の形態で組成物に加えることができる。ベリリ
ウム、カドミウム、銅、カルシウム、マグネシウム、亜
鉛、ジルコニウム、バリウム、ストロンチウム、アルミ
ニウム、ビスマス、アンチモン、鉛、コバルト、鉄、ニ
ッケル又は他の多価金属が採用することができる。多価
金属化合物として、これらの金属のアンモニア及びアミ
ン錯体が特に有用である。The polyvalent metal compound in the present invention also includes a metal complex or a metal chelate. The polyvalent metal compound can be added to the composition in the form of oxides, hydroxides or basic salts, acid salts or neutral salts having a pronounced solubility in water such as at least 1% by weight. Beryllium, cadmium, copper, calcium, magnesium, zinc, zirconium, barium, strontium, aluminum, bismuth, antimony, lead, cobalt, iron, nickel or other polyvalent metals can be employed. As polyvalent metal compounds, ammonia and amine complexes of these metals are particularly useful.
【0009】錯体形成が可能なアミンには、モルホリ
ン、モノエタノールアミン、ジエチルアミノエタノー
ル、エチレンジアミン等がある。アルカリ性pH範囲で
可溶可能な有機酸の多価金属錯体もまた使用できる。酢
酸イオン、ダルタミン酸イオン、蟻酸イオン、炭酸イオ
ン、サリチル酸イオン、グリコール酸イオン等の陰イオ
ンが満足される。配位子がグリシナト又はアラニナトの
ような二座配位子である多価金属キレートもまた使用で
きる。Examples of amines capable of forming a complex include morpholine, monoethanolamine, diethylaminoethanol and ethylenediamine. Polyvalent metal complexes of organic acids soluble in the alkaline pH range can also be used. Anions such as acetate ion, dultamate ion, formate ion, carbonate ion, salicylate ion and glycolate ion are satisfied. Polyvalent metal chelates where the ligand is a bidentate ligand such as glycinate or alaninato can also be used.
【0010】多価金属化合物は、その金属が解離して、
多価金属含有イオンを形成するものでなければならな
い。好ましい多価金属化合物には、酢酸亜鉛、酢酸カド
ミウム、亜鉛グリシネート、カドミウムグリシネート、
炭酸亜鉛、炭酸カドミウム、安息香酸亜鉛、亜鉛サリチ
レート、カドミウムサリチレート等が含まれる。多価金
属化合物は、粉末のような乾燥形態で用いることができ
るけれども、アンモニアのような逃げやすい配位子を用
いて多価金属化合物を最初に可溶化するのが好ましい。In the polyvalent metal compound, the metal is dissociated,
It must form polyvalent metal-containing ions. Preferred polyvalent metal compounds include zinc acetate, cadmium acetate, zinc glycinate, cadmium glycinate,
Zinc carbonate, cadmium carbonate, zinc benzoate, zinc salicylate, cadmium salicylate and the like are included. Although the polyvalent metal compound can be used in dry form, such as a powder, it is preferred to first solubilize the polyvalent metal compound with a fugitive ligand such as ammonia.
【0011】[0011]
【作用】本発明において、含フッ素重合体の水性組成物
への適用は、フッ素樹脂に特有の撥水撥油性及び強い結
合エネルギーによって、床、家具及び類似物の表面に艶
を出し、さらには、耐油性、耐水性及び耐候性に優れた
被覆組成物を形成せしめる如き効果を生ずるものと考え
られる。In the present invention, the application of the fluorine-containing polymer to the aqueous composition makes the surface of the floor, furniture and the like glossy due to the water and oil repellency and strong binding energy peculiar to the fluororesin, and further, It is believed that it produces effects such as forming a coating composition having excellent oil resistance, water resistance and weather resistance.
【0012】本組成物は、繊維・皮革・紙或はその他も
多孔性或は繊維質の材料を含潰するのに用いることがで
きる。これらはセロハン、ポリエチレン、ポリエチレン
グリコールテレフタレート、サラン等のプラスチックシ
ートに適用してもよい。鋼、アルミニウム、銅、真鍮、
黄銅、錫、クロム、鍛鉄のようなすべての金属、木、
石、石造建材、煉瓦、ガラス、石綿セメント建材、モザ
イク、床のようなセメント及びコンクリート面等を含む
剛い面にも適用できる。本組成物は、木、リノリウム、
ゴム、すべての種類のプラスチック(リノリウム、アス
ファルト、ビニル及びビニルアスベストのような)でで
きている床の艶出しに特に有効である。The composition can be used to impregnate fibers, leather, paper or other porous or fibrous materials. These may be applied to plastic sheets such as cellophane, polyethylene, polyethylene glycol terephthalate, and saran. Steel, aluminum, copper, brass,
All metals, wood, such as brass, tin, chrome, wrought iron,
It can also be applied to hard surfaces including stone, masonry, bricks, glass, asbestos-cement building materials, mosaics, cement and concrete surfaces such as floors, etc. The composition is wood, linoleum,
It is especially effective in polishing floors made of rubber, all kinds of plastics (like linoleum, asphalt, vinyl and vinyl asbestos).
【0013】[0013]
【実施例】以下に実施例を挙げて本発明をより具体的に
説明するが、かかる実施例により本発明は何ら限定され
るものではない。なお、以下の例において部とあるもの
は特に明記のない限り重量部を示す。The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. In the following examples, parts are parts by weight unless otherwise specified.
【0014】[原料含フッ素重合体の合成例1]内容積
200mlのステンレス製撹拌機付オートクレーブ(耐
圧50kg/cm2 )にクロロトリフルオロエチレン3
5部、シクロヘキシルビニルエーテル11部、エチルビ
ニルエーテル4.3部、ω−ヒドロキシブチルビニルエ
ーテル15部、キシレン98部、エタノール28部、ア
ゾビスイソブチロニトリル0.5部、無水炭酸カリウム
1.5部を仕込み、液体窒素にて冷却して固化脱気によ
り溶存空気を除去した後、45℃で16時間反応を行な
い、水酸基含有含フッ素重合体を得た。[Synthesis Example 1 of Raw Material Fluorine-Containing Polymer] Chlorotrifluoroethylene 3 was added to an autoclave (withstand pressure of 50 kg / cm 2 ) made of stainless steel and having an internal volume of 200 ml.
5 parts, cyclohexyl vinyl ether 11 parts, ethyl vinyl ether 4.3 parts, ω-hydroxybutyl vinyl ether 15 parts, xylene 98 parts, ethanol 28 parts, azobisisobutyronitrile 0.5 parts, anhydrous potassium carbonate 1.5 parts After charging, cooling with liquid nitrogen and solidification degassing to remove dissolved air, reaction was carried out at 45 ° C. for 16 hours to obtain a hydroxyl group-containing fluoropolymer.
【0015】得られた水酸基含有含フッ素重合体(水酸
基価は約120mgKOH/g)の約60%キシレン溶
液を90℃に加熱し、重合体100部に対して5.6部
の無水コハク酸を加え、さらに0.2部のトリエチルア
ミンを添加して、2時間反応させた。An approximately 60% xylene solution of the obtained fluorine-containing polymer having a hydroxyl group (having a hydroxyl value of approximately 120 mgKOH / g) is heated to 90 ° C., and 5.6 parts of succinic anhydride is added to 100 parts of the polymer. In addition, a further 0.2 part of triethylamine was added and the reaction was carried out for 2 hours.
【0016】反応液の赤外スペクトルを測定すると、反
応前に観測された無水酸の特性吸収(1850cm-1,
1780cm-1)が反応後では消失しており、カルボン
酸(1710cm-1)およびエステル(1735c
m-1)の吸収が観測された。かくしてカルボキシル基を
導入された含フッ素重合体の酸価は20mgKOH/
g、水酸基価は100mgKOH/gであった。なお、
得られた含フッ素重合体は、溶剤を蒸発させ、重合体固
形分を単離した。When the infrared spectrum of the reaction solution was measured, the characteristic absorption of anhydrous anhydride observed before the reaction (1850 cm -1 ,
1780 cm −1 ) has disappeared after the reaction, and the carboxylic acid (1710 cm −1 ) and ester (1735c
m −1 ) absorption was observed. Thus, the acid value of the fluoropolymer having a carboxyl group introduced is 20 mgKOH /
g, and the hydroxyl value was 100 mgKOH / g. In addition,
In the obtained fluoropolymer, the solvent was evaporated and the polymer solid content was isolated.
【0017】[実施例1]合成例1の含フッ素重合体1
00部にジエチルアミン4.5部、蒸留水130部、多
価金属錯体10部を加え、通常の撹拌機を用いて撹拌混
合し、水性フッ素樹脂を得る。Example 1 Fluoropolymer 1 of Synthesis Example 1
4.5 parts of diethylamine, 130 parts of distilled water, and 10 parts of polyvalent metal complex are added to 00 parts, and the mixture is stirred and mixed using a usual stirrer to obtain an aqueous fluororesin.
【0018】この樹脂の塗膜物性を表1に示す。比較と
して該多価金属錯体を含有しないもの(比較例2)の塗
膜物性を示す。常温で架橋した透明、強靭な塗膜であ
る。The coating properties of this resin are shown in Table 1. For comparison, the physical properties of the coating film containing no polyvalent metal complex (Comparative Example 2) are shown. It is a transparent and tough coating film that is crosslinked at room temperature.
【0019】[比較例1]実施例1と同様な方法で、た
だし多価金属錯体は添加せず、水性フッ素樹脂を得る。
この樹脂の塗膜物性を表1に示す(耐溶剤性はキシレン
に対するものである)。Comparative Example 1 An aqueous fluororesin is obtained in the same manner as in Example 1 except that the polyvalent metal complex is not added.
The coating film physical properties of this resin are shown in Table 1 (solvent resistance is against xylene).
【0020】[0020]
【表1】 [Table 1]
【0021】[実施例2]実施例1で得られた水性フッ
素樹脂を用いて、ビニル床タイル用被覆材(以下フロア
ーポリッシュと呼ぶ)を調合して、性能を測定した。比
較として市販フロアーポリッシュ(アクリル樹脂ベー
ス)の性能も測定した。その結果を表2に示す。Example 2 Using the aqueous fluororesin obtained in Example 1, a vinyl floor tile coating material (hereinafter referred to as floor polish) was prepared and its performance was measured. For comparison, the performance of a commercial floor polish (acrylic resin base) was also measured. The results are shown in Table 2.
【0022】 [0022]
【0023】1.光沢度 半硬質ビニルタイルを用い、塗布量を1回当たり20±
2ml/m2 とし、2回塗布した後の光沢度(60°)
を通常の光沢計を使用し、測定した。1. Glossiness Use semi-hard vinyl tile and apply the amount of 20 ±
2 ml / m 2 and gloss after applying twice (60 °)
Was measured using a normal gloss meter.
【0024】2.撥水性 光沢度と同様な方法でタイルを準備し、室温で1日間保
持した後、タイル表面を水で濡らす。この状態で1時間
放置する。1時間後、水をふき取り、表面の状態を観察
する。 ○:試験前と変わらない ×:白化する2. Water repellency: Tile is prepared in the same manner as gloss, kept at room temperature for 1 day, and then the tile surface is wetted with water. Leave in this state for 1 hour. After 1 hour, the water is wiped off and the surface condition is observed. ◯: No change from before the test ×: Whitening
【0025】3.撥油性 光沢度と同様な方法でタイルを準備する。油性汚染物質
2gを予め洗浄乾燥した砂250gに均一に付着させ、
試験片(4×4cmに切断)とともに60分間撹拌、接
触させた。取り出した後、表面の汚染度合を観察する。 ○:乾拭きすると、元の状態にもどる △:水拭きすると、元の状態にもどる ×:乾拭き、水拭きしても、元の状態にもどらない3. Oil Repellent Prepare tiles in the same way as gloss. 2 g of oily pollutants are evenly attached to 250 g of sand that has been washed and dried in advance,
The test piece (cut into 4 × 4 cm) was stirred and contacted for 60 minutes. After taking out, the degree of contamination on the surface is observed. ◯: When wiped dry, it returns to its original condition. Δ: When wiped with water, it returns to its original condition. X: It does not return to its original state even after being wiped dry and with water.
【0026】4.耐摩耗性 歩行量800〜1200回/日の場所に光沢度と同様な
方法で塗布したタイルを置き、1ケ月後の表面の状態を
観察する。 ○:汚れ、光沢低下等が少ない △:汚れ、光沢低下等がある ×:汚れ、光沢低下等が激しい4. Abrasion resistance A tile applied by the same method as the glossiness is placed at a place where the walking amount is 800 to 1200 times / day, and the surface condition after one month is observed. ◯: Little stain, decrease in gloss etc. △: Stain, decrease in gloss etc. ×: Severe stain, decrease in gloss etc.
【0027】[0027]
【表2】 [Table 2]
【0028】実施例では、フロアーポリッシュに利用し
たときの性能について説明したが、本発明によって得ら
れた常温架橋型水性フッ素樹脂は上記以外の広範な被覆
材としての用途が考えられる。In the examples, the performance when used for floor polishing was explained, but the room temperature crosslinkable aqueous fluororesin obtained by the present invention can be used as a wide range of coating materials other than the above.
【0029】[0029]
【発明の効果】本発明の組成物は、光沢、撥水性、耐油
性、硬度等に優れた塗膜を与えるため、床の艶出し剤と
して極めて有用である。The composition of the present invention provides a coating film excellent in gloss, water repellency, oil resistance, hardness and the like, and is therefore extremely useful as a floor polish.
Claims (1)
ッ素重合体、および金属架橋形成可能な多価金属化合物
を必須成分とする金属架橋性フッ素樹脂組成物。Claim: What is claimed is: 1. A fluorine-containing polymer having an acid value of 5 to 50 mgKOH / g, and a metal-crosslinkable fluororesin composition containing a polyvalent metal compound capable of forming a metal crosslink as an essential component.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20988591A JPH0532841A (en) | 1991-07-26 | 1991-07-26 | Fluororesin composition cross-linkable with metal |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20988591A JPH0532841A (en) | 1991-07-26 | 1991-07-26 | Fluororesin composition cross-linkable with metal |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0532841A true JPH0532841A (en) | 1993-02-09 |
Family
ID=16580263
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP20988591A Withdrawn JPH0532841A (en) | 1991-07-26 | 1991-07-26 | Fluororesin composition cross-linkable with metal |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0532841A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999021920A1 (en) * | 1997-10-24 | 1999-05-06 | Daikin Industries, Ltd. | Aqueous dispersion composition of crosslinkable fluororesin |
WO2014057858A1 (en) * | 2012-10-12 | 2014-04-17 | シーシーエス株式会社 | Sealant composition for electrical and electronic parts, coating material for electrical and electronic parts, and led device |
US11040708B2 (en) | 2016-10-14 | 2021-06-22 | Trevor Michael Mennie | Brake control system |
-
1991
- 1991-07-26 JP JP20988591A patent/JPH0532841A/en not_active Withdrawn
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999021920A1 (en) * | 1997-10-24 | 1999-05-06 | Daikin Industries, Ltd. | Aqueous dispersion composition of crosslinkable fluororesin |
US6326437B1 (en) | 1997-10-24 | 2001-12-04 | Daikin Industries, Ltd. | Aqueous-dispersing composition of crosslinkable fluorine-containing resin |
EP1026201A4 (en) * | 1997-10-24 | 2004-12-29 | Daikin Ind Ltd | Aqueous dispersion composition of crosslinkable fluororesin |
WO2014057858A1 (en) * | 2012-10-12 | 2014-04-17 | シーシーエス株式会社 | Sealant composition for electrical and electronic parts, coating material for electrical and electronic parts, and led device |
US11040708B2 (en) | 2016-10-14 | 2021-06-22 | Trevor Michael Mennie | Brake control system |
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Date | Code | Title | Description |
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A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19981008 |