JPH0432873B2 - - Google Patents
Info
- Publication number
- JPH0432873B2 JPH0432873B2 JP58148807A JP14880783A JPH0432873B2 JP H0432873 B2 JPH0432873 B2 JP H0432873B2 JP 58148807 A JP58148807 A JP 58148807A JP 14880783 A JP14880783 A JP 14880783A JP H0432873 B2 JPH0432873 B2 JP H0432873B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- oil repellent
- group
- polyhydric alcohol
- 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.)
- Expired - Lifetime
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Paper (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、飽和多価アルコール水溶液中で乳化
重合して得られる、高引火点を有するフツ素系撥
水撥油剤に関する。
ポリフルオロアルキル基を有する重合可能な化
合物（以下PFA化合物という）を含有する共重
合体からなる撥水撥油剤は従来より種々知られて
いる。これらの共重合体は乳化重合、溶液重合、
又は塊状重合で得られ、水性分散液、有機溶液、
あるいは有機分散液として使用されるが、火災や
作業環境汚染の問題から水性分散液として使用す
ることが望ましい。乳化重合においては、水性乳
濁液が直接得られるが、この水性分散液は安定性
が低く、一般に分散を助長する目的で有機溶媒が
使用される。従来、かかる有機溶媒には重合体と
の相溶性の問題から、アセトンのような比較的低
沸点の溶媒を使わざるを得ず、引火の恐れや環境
汚染の心配があつた。本発明者等の検討によれ
ば、必ずしも低沸点溶媒でなくとも、飽和多価ア
ルコールのような溶媒を使用すれば、乳化重合も
可能であり、しかも安定な水性分散液が得られる
ことがわかつた。これにより、引火の恐れや環境
汚染の心配がない水性分散液型の撥水撥油剤を得
ることができる。すなわち、本発明はポリフルオ
ロアルキル基を有する重合可能な化合物と、他の
共重合可能な化合物を飽和多価アルコール水溶液
中で乳化重合してなることを特徴とする高引火点
を有する撥水撥油剤に関するものである。
本発明におけるPFA化合物としては、特に限
定されるものではなく、例えば、
CF3（CF2）8（CH2）2OCOCH＝CH2、
CF3（CF2）7（CH2）11OCOCH＝CH2、
CF3（CF2）8（CH2）2OCOC（CH3）＝CH2、
CF3（CF2）4CH2OCOC（CH3）＝CH2、
CF3（CF2）6（CH2）2OCOC（CH3）＝CH2、
CF3（CF2）7SO2N（C3H7）（CH2）2OCOCH＝
CH2、
CF3（CF2）7SO2N（CH3）（CH2）2OCOC（CH3）
＝CH2、
CF3（CF2）7（CH2）3OCOCH＝CH2、
等の炭素数３〜20個、好ましくは４〜16個のパー
フルオロアルキル基を有するアクリレート又はメ
タクリレートで代表される不飽和エステル類であ
る。特に、一般式RfR1OCOCR2＝CH2（但し、式
中のRfは炭素数４〜16個の直鎖状又は分岐状の
パーフルオロアルキル基、R1は炭素数１〜10個
の直鎖状又は分岐状の二価のアルキレン基、R2
は水素原子又はメチル基を示す。）で表される不
飽和エステルが好適な具体例として例示され得
る。
PFA化合物と共重合可能な化合物としてはＮ
―メチロールアクリルアミド、Ｎ―メチロールメ
タクリルアミド、ダリシジルアクリレート、グリ
シジルメタクリレート、アジリジニルアクリレー
ト、アジリジニルメタクリレート、ジアセトンア
クリルアミド、ジアセトンメタクリルアミド、メ
チロール化ジアセトンアクリルアミド、エチレン
ジアクリテート、エチレンジメタクリレート、ヒ
ドロキシアルキルアクリレート、ヒドロキシアル
キルメタクリレート、３―フロロ―２―ヒドロキ
シプロピルメタクリレートの如き架橋性単量体の
他、塩化ビニル、エチレン、酢酸ビニル、弗化ビ
ニル、アクリルアミド、メタクリルアミド、スチ
レン、ａ―メチルスチレン、ｐ―メチルスチレ
ン、アクリル酸又はメタクリル酸のアルキルエス
テル、ベンジルアクリレート、又はメタクリレー
ト、ビニルアルキルエーテル、ハロゲン化アルキ
ルビニルエーテル、ビニルアルキルケトン、シク
ロヘキシルアクリレート又はメタクリレート、無
水マレイン酸、ブタジエン、イソプレン、クロロ
プレン等を例示できるが、これらの一種又は二種
以上とPFA化合物とで共重合体を形成し得る。
本発明の撥水撥油剤は、前記化合物を飽和多価
アルコール水溶液中で乳化重合することにより得
ることができる。飽和多価アルコールの具体例
は、エチレングリコール、１，２―プロパンジオ
ール、１，３―プロパンジオール、ジエチレング
リコール、トリエチレングリコール、ジプロピレ
ングリコール、トリプロピレングリコール、１，
４―ブタンジオール、１，３―ブタンジオール、
２，３―ブタンジオール、１，５―ペンタンジオ
ール、１，６―ヘキサンジオールの如きグリコー
ル類、その他グリセリン、ソルビトールの如きも
のである。特に溶解度係数８〜16、好ましくは９
〜12.5の飽和脂肪族ジオールであり、ジプロピレ
ングリコール、１，６―ヘキサンジオール、１，
５−ペンタンジオール、１，４―ペンタンジオー
ルが好適である。これらの多価アルコールは、単
独もしくは混合して用いることができる。さらに
水溶性ケトン、エステル、あるいはエーテル類を
併用してもよいが、かかる場合には多価アルコー
ルの割合を70重量％以上とすることが好ましい。
本発明における共重合体においてPFA化合物
の共重合体割合は少なくとも40重量％、特に50〜
80重量％程度が適当である。架橋性単量体の共重
合割合は少量でよく、通常は１〜10重量％、特に
２〜５重量％程度が適当である。多価アルコール
の使用量については乳化重合時に使用する全単量
体に対して10〜200重量％、特に60〜100重量％が
適当である。使用する界面活性剤、重合開始源に
ついては特に制限はなく、界面活性剤として陰イ
オン性、陽イオン性、あるいは非イオン性の各種
乳化剤のほとんどすべてを使用でき、重合開始剤
として有機過酸化物、アゾ化合物、過硫酸塩の如
き各種重合開始剤、更にはｒ線の如き電離性放射
線などが採用できる。
本発明の撥水撥油剤は被処理物品の種類により
任意の方法で適用され得る。例えば、浸漬塗布等
の如き被覆加工の既知の方法により、被処理物の
表面に付着させ乾燥する方法が採用され得る。
又、必要ならば適当なる架橋剤と共に適用し、キ
ユアリングを行なつても良い。更に本発明の撥水
撥油剤は、他の重合体ブレンダーを混合しても良
く、他の撥水剤や撥油剤あるいは防虫剤、難燃
剤、帯電防止剤、染料安定剤、防シワ剤など添加
剤を適宜添加して併用することも勿論可能であ
る。
本発明の撥水撥油剤で処理され得る物品は、特
に限定なく種々の例をあげることができる。例え
ば、繊維織物、ガラス、紙、木、皮革、毛皮、石
綿、レンガ、セメント、金属及び酸化物、窯業製
品、プラスチツク、塗面およびプラスターなどが
ある。而して、繊維織物としては、綿、麻、羊
毛、絹などの動植物性天然繊維、ポリアミド、ポ
リエステル、ポリビニルアルコール、ポリアクリ
ロニトリル、ポリ塩化ビニル、ポリプロピレンの
如き種々の合成繊維、レーヨン、アセテートの如
き半合成繊維、ガラス繊維、炭素繊維、アスベス
ト繊維の如き無機繊維、或いはこれらの混合繊維
の織物があげられる。
次に、本発明の実施例について長に具体的に説
明するが、この説明が本発明を限定するものでな
いことは勿論である。以下の実施例中に示す撥水
性、撥油性については、次の様な尺度で示してあ
る。即ち、撥水性はJISL―1005のスプレー法に
よる撥水性No.（下記第１表参照）をもつて表わ
し、撥油性は下記第２表に示された試験溶液を試
料布の上、二ケ所に数滴（径約４mm）置き、30秒
後の浸透状態により判定する（AATCC―
TM118―1966）。
The present invention relates to a fluorine-based water and oil repellent having a high flash point and obtained by emulsion polymerization in an aqueous saturated polyhydric alcohol solution. BACKGROUND ART Various water and oil repellents made of copolymers containing a polymerizable compound having a polyfluoroalkyl group (hereinafter referred to as a PFA compound) have been conventionally known. These copolymers can be processed by emulsion polymerization, solution polymerization,
Or obtained by bulk polymerization, aqueous dispersion, organic solution,
Alternatively, it is used as an organic dispersion, but it is preferable to use it as an aqueous dispersion due to the problems of fire and work environment pollution. In emulsion polymerization, an aqueous emulsion is directly obtained, but this aqueous dispersion has low stability, and an organic solvent is generally used to promote dispersion. Conventionally, such organic solvents have been forced to use solvents with relatively low boiling points, such as acetone, due to compatibility with polymers, and there have been concerns about ignition and environmental pollution. According to studies conducted by the present inventors, it has been found that emulsion polymerization is possible and a stable aqueous dispersion can be obtained by using a solvent such as a saturated polyhydric alcohol, even if it is not necessarily a low boiling point solvent. Ta. This makes it possible to obtain an aqueous dispersion type water and oil repellent that is free from the fear of ignition and environmental pollution. That is, the present invention provides a water repellent having a high flash point, which is obtained by emulsion polymerizing a polymerizable compound having a polyfluoroalkyl group and another copolymerizable compound in an aqueous saturated polyhydric alcohol solution. It concerns oil agents. The PFA compound in the present invention is not particularly limited, and for example, CF 3 (CF 2 ) 8 (CH 2 ) 2 OCOCH=CH 2 , CF 3 (CF 2 ) 7 (CH 2 ) 11 OCOCH=CH 2 , CF 3 (CF 2 ) 8 (CH 2 ) 2 OCOC (CH 3 ) = CH 2 , CF 3 (CF 2 ) 4 CH 2 OCOC (CH 3 ) = CH 2 , CF 3 (CF 2 ) 6 (CH 2 ) 2 OCOC (CH 3 )=CH 2 , CF 3 (CF 2 ) 7 SO 2 N (C 3 H 7 ) (CH 2 ) 2 OCOCH=
CH 2 , CF 3 (CF 2 ) 7 SO 2 N (CH 3 ) (CH 2 ) 2 OCOC (CH 3 )
＝CH 2 , CF 3 (CF 2 ) 7 (CH 2 ) 3 OCOCH＝CH 2 , These are unsaturated esters represented by acrylates or methacrylates having a perfluoroalkyl group having 3 to 20 carbon atoms, preferably 4 to 16 carbon atoms. In particular, the general formula RfR 1 OCOCR 2 = CH 2 (wherein, Rf is a linear or branched perfluoroalkyl group having 4 to 16 carbon atoms, and R 1 is a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms. or branched divalent alkylene group, R 2
represents a hydrogen atom or a methyl group. ) Unsaturated esters represented by the following can be exemplified as preferred specific examples. N is a compound that can be copolymerized with PFA compounds.
- Methylolacrylamide, N-methylolmethacrylamide, dalicidyl acrylate, glycidyl methacrylate, aziridinyl acrylate, aziridinyl methacrylate, diacetone acrylamide, diacetone methacrylamide, methylolated diacetone acrylamide, ethylene diacrylate, ethylene dimethacrylate , hydroxyalkyl acrylate, hydroxyalkyl methacrylate, 3-fluoro-2-hydroxypropyl methacrylate, as well as vinyl chloride, ethylene, vinyl acetate, vinyl fluoride, acrylamide, methacrylamide, styrene, a-methyl Styrene, p-methylstyrene, alkyl esters of acrylic acid or methacrylic acid, benzyl acrylate or methacrylate, vinyl alkyl ethers, halogenated alkyl vinyl ethers, vinyl alkyl ketones, cyclohexyl acrylates or methacrylates, maleic anhydride, butadiene, isoprene, chloroprene, etc. For example, one or more of these and a PFA compound can form a copolymer. The water and oil repellent of the present invention can be obtained by emulsion polymerization of the above compound in an aqueous saturated polyhydric alcohol solution. Specific examples of saturated polyhydric alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 1,
4-butanediol, 1,3-butanediol,
These include glycols such as 2,3-butanediol, 1,5-pentanediol, and 1,6-hexanediol, and others such as glycerin and sorbitol. Especially solubility coefficient 8-16, preferably 9
~12.5 saturated aliphatic diols, including dipropylene glycol, 1,6-hexanediol, 1,
5-pentanediol and 1,4-pentanediol are preferred. These polyhydric alcohols can be used alone or in combination. Further, a water-soluble ketone, ester, or ether may be used in combination, but in such a case, the proportion of polyhydric alcohol is preferably 70% by weight or more. In the copolymer of the present invention, the proportion of the PFA compound in the copolymer is at least 40% by weight, especially from 50% to 50% by weight.
Approximately 80% by weight is appropriate. The copolymerization ratio of the crosslinkable monomer may be small, and is usually about 1 to 10% by weight, particularly about 2 to 5% by weight. The appropriate amount of polyhydric alcohol to be used is 10 to 200% by weight, particularly 60 to 100% by weight, based on the total monomers used during emulsion polymerization. There are no particular restrictions on the surfactant or polymerization initiator, and almost all anionic, cationic, or nonionic emulsifiers can be used as the surfactant, and organic peroxides can be used as the polymerization initiator. Various polymerization initiators such as , azo compounds, persulfates, and ionizing radiation such as r-rays can be used. The water and oil repellent of the present invention can be applied by any method depending on the type of article to be treated. For example, a method may be employed in which the coating material is adhered to the surface of the object to be treated by a known coating method such as dip coating, and then dried.
Further, if necessary, curing may be performed by applying a suitable crosslinking agent. Furthermore, the water and oil repellent of the present invention may be mixed with other polymer blenders, and other water and oil repellents, insect repellents, flame retardants, antistatic agents, dye stabilizers, anti-wrinkle agents, etc. may be added. Of course, it is also possible to add appropriate agents and use them together. There are various examples of articles that can be treated with the water and oil repellent of the present invention without particular limitation. Examples include textiles, glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces and plasters. The fiber fabrics include natural fibers of animal and plant origin such as cotton, linen, wool, and silk, various synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, and rayon and acetate. Examples include semi-synthetic fibers, glass fibers, carbon fibers, inorganic fibers such as asbestos fibers, and woven fabrics of mixed fibers thereof. Next, embodiments of the present invention will be specifically explained in detail, but it goes without saying that this explanation does not limit the present invention. The water repellency and oil repellency shown in the following examples are shown on the following scale. That is, water repellency is expressed by the water repellency number (see Table 1 below) determined by the JISL-1005 spray method, and oil repellency is expressed by applying the test solution shown in Table 2 below to two locations on the sample cloth. Place several drops (approximately 4 mm in diameter) and judge by the penetration state after 30 seconds (AATCC-
TM118―1966).
【表】【table】
【表】
尚、撥水性No.、撥油性に十印を付したものは、
それぞれの性能がわずかに良好なものを示す。
合成例 １
この例では、多価アルコール水溶液中での乳化
重合の典型的な方法を、多価アルコールとしてジ
プロピレングリコールを用いPFA化合物、塩化
ビニル、ステアリルメタクリレート、Ｎ―メチロ
ールアクリルアミドの四元共重合体の具体例にて
説明する。
撹拌機を装着したガラス製オートクレーブ（内
容積１）中にCH2＝CHCOOCH2CH2CnF2o+1
（ｎ＝６〜12、平均９）112ｇ、ステアリルメタク
リレート44ｇ、Ｎ―メチロールアクリルアミド４
ｇ、脱酸素した純水260ｇ、ジプロピレングリコ
ール140ｇ、アゾビスイソブチルアミジン―２塩
酸塩3.2ｇ、C18H33 [Table] Water repellency No. and oil repellency marked with a 10 are as follows:
Each shows slightly better performance. Synthesis Example 1 In this example, a typical method of emulsion polymerization in an aqueous polyhydric alcohol solution is described using dipropylene glycol as the polyhydric alcohol and a quaternary copolymerization of a PFA compound, vinyl chloride, stearyl methacrylate, and N-methylolacrylamide. This will be explained using a specific example of merging. CH 2 =CHCOOCH 2 CH 2 CnF 2o+ 1 in a glass autoclave (inner volume 1) equipped with a stirrer
(n=6-12, average 9) 112g, stearyl methacrylate 44g, N-methylolacrylamide 4
g, 260 g of deoxygenated pure water, 140 g of dipropylene glycol, 3.2 g of azobisisobutyramidine dihydrochloride, C 18 H 33
【式】（CH2CH2O）20H16ｇ、
CnH2o+1Ｎ
（CH3）2・CH3COO
（ｎ＝８〜
16、平均13）２ｇを入れ、窒素気流下に撹拌する
ことによつて充分乳化分散させる。次に塩化ビニ
ル40ｇを圧入充填し、反応容器の温度を徐々に上
げていき、撹拌下に50℃で20時間共重合反応せし
める。固形分濃度34.5％の半透明なラテツクスが
得られた。引火点を測定したところ100℃以上で
あつた。
実施例１〜４及び比較例１〜４
ポリエステル布を試験布として使用する。本発
明による撥水撥油剤及び本発明品以外の撥水撥油
剤を水で希釈して濃度0.075重量％の乳濁液を調
整した後、各試験布を該乳濁液に２秒間浸漬し、
２本のゴムローラーの間で布を絞つて、ウエツト
ピツクアツプを90％とした。次いで100℃で３分
間乾燥、更に175℃で１分間熱処理することによ
り撥水撥油処理した。
第３表に性能を示す。尚第３表においては、
FAはCH2＝CHCOOCH2（CF2）oCF3（ｎ＝５〜11、
平均８）、FMAはCH2＝Ｃ（CH3）COOCH2CH2
（CF2）oCF3（ｎ＝５〜11、平均８）、STMAは
CH2＝Ｃ（CH3）COOC18H37、DOMはジオクチ
ルマレート、VC1は塩化ビニル、Ｎ―MAMはＮ
―メチロールアクリルアミドを示している。OR
は撥油性、WRは撥水性、DC―３はJISL―1092
―322法によるドライクリーニング３回後の結果、
HL―３はJISL―0217―103法による洗濯３回後
の結果を示している。[Formula] (CH 2 CH 2 O) 20 H16g, CnH 2o+1 N (CH 3 ) 2・CH 3 COO (n=8~
16, average 13) 2g was added and thoroughly emulsified and dispersed by stirring under a nitrogen stream. Next, 40 g of vinyl chloride was press-fitted, the temperature of the reaction vessel was gradually raised, and a copolymerization reaction was carried out at 50°C for 20 hours with stirring. A translucent latex with a solids concentration of 34.5% was obtained. When the flash point was measured, it was over 100℃. Examples 1-4 and Comparative Examples 1-4 Polyester fabrics are used as test fabrics. After diluting the water and oil repellent according to the present invention and the water and oil repellent other than the products of the present invention with water to prepare an emulsion with a concentration of 0.075% by weight, each test cloth was immersed in the emulsion for 2 seconds,
The cloth was squeezed between two rubber rollers to obtain a wet pick-up of 90%. The film was then dried at 100°C for 3 minutes and further heat-treated at 175°C for 1 minute to make it water and oil repellent. Table 3 shows the performance. In Table 3,
FA is CH 2 = CHCOOCH 2 (CF 2 ) o CF 3 (n = 5 to 11,
Average 8), FMA is CH 2 = C(CH 3 ) COOCH 2 CH 2
(CF 2 ) o CF 3 (n=5-11, average 8), STMA is
CH 2 =C(CH 3 )COOC 18 H 37 , DOM is dioctyl malate, VC1 is vinyl chloride, N-MAM is N
- Indicates methylol acrylamide. OR
is oil repellent, WR is water repellent, DC-3 is JISL-1092
-Results after 3 dry cleanings using the 322 method.
HL-3 shows the results after washing three times according to JISL-0217-103 method.
Claims (1)
化合物と他の共重合可能の化合物を飽和多価アル
コール水溶液中で乳化重合してなることを特徴と
する高引火点を有する撥水撥油剤。 ２ ポリフルオロアルキル基を有する重合可能な
化合物が、一般式RfR1OCOCR2＝CH2（但し、式
中のRfは炭素数４〜16個の直鎖状又は分岐状の
パーフルオロアルキル基、R1は炭素数１〜10個
の直鎖状又は分岐状の二価のアルキレン基、R2
は水素原子又はメチル基を示す。）で表わされる
不飽和エステルである特許請求の範囲第１項記載
の撥水撥油剤。 ３ 飽和多価アルコールが溶解度係数９〜12.5の
飽和脂肪族ジオールである特許請求の範囲第１項
記載の撥水撥油剤。[Scope of Claims] 1. A water repellent having a high flash point, which is obtained by emulsion polymerizing a polymerizable compound having a polyfluoroalkyl group and another copolymerizable compound in an aqueous saturated polyhydric alcohol solution. Oil repellent. 2 A polymerizable compound having a polyfluoroalkyl group has the general formula R f R 1 OCOCR 2 =CH 2 (wherein R f is a linear or branched perfluoroalkyl having 4 to 16 carbon atoms). group, R 1 is a linear or branched divalent alkylene group having 1 to 10 carbon atoms, R 2
represents a hydrogen atom or a methyl group. ) The water and oil repellent according to claim 1, which is an unsaturated ester represented by: 3. The water and oil repellent according to claim 1, wherein the saturated polyhydric alcohol is a saturated aliphatic diol having a solubility coefficient of 9 to 12.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14880783A JPS6040182A (en) | 1983-08-16 | 1983-08-16 | Water- and oil-repellent having high ignition point |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14880783A JPS6040182A (en) | 1983-08-16 | 1983-08-16 | Water- and oil-repellent having high ignition point |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6040182A JPS6040182A (en) | 1985-03-02 |
| JPH0432873B2 true JPH0432873B2 (en) | 1992-06-01 |
Family
ID=15461145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14880783A Granted JPS6040182A (en) | 1983-08-16 | 1983-08-16 | Water- and oil-repellent having high ignition point |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6040182A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120061230A (en) * | 2010-12-03 | 2012-06-13 | 서울시립대학교 산학협력단 | Solar cell and method of the manufacturing of the same |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0674409B2 (en) * | 1985-05-31 | 1994-09-21 | ダイキン工業株式会社 | Water and oil repellent aqueous dispersion |
| FR2722791B1 (en) | 1994-07-22 | 1996-09-06 | Atochem Elf Sa | PROCESS FOR THE MANUFACTURE OF AQUEOUS EMULSIONS OF FLUORINATED COPOLYMERS |
| US6197878B1 (en) | 1997-08-28 | 2001-03-06 | Eastman Chemical Company | Diol latex compositions and modified condensation polymers |
| WO2000037583A1 (en) | 1998-12-22 | 2000-06-29 | Daikin Industries, Ltd. | Aqueous dispersion of repellant for water and oil |
| WO2000052083A1 (en) | 1999-03-03 | 2000-09-08 | Eastman Chemical Company | Silicone polymer diol compositions and condensation polymer/silicone polymer blends |
| EP1161497B1 (en) | 1999-03-03 | 2003-05-07 | Eastman Chemical Company | Polyamide/emulsion polymer blends |
| CN101362935A (en) | 1999-04-07 | 2009-02-11 | 大金工业株式会社 | Water-based dispersion of water and oil repellent |
| EP1192206A1 (en) | 1999-06-18 | 2002-04-03 | Eastman Chemical Company | Amide-type polymer/silicone polymer blends and processes of making the same |
| EP1187870A1 (en) | 1999-06-18 | 2002-03-20 | Eastman Chemical Company | Nylon 6-silicone blends |
| US6479612B1 (en) | 1999-08-10 | 2002-11-12 | E. I. Du Pont De Nemours And Company | Fluorochemical water and oil repellents |
| US6462109B1 (en) | 1999-10-12 | 2002-10-08 | Eastman Chemical Company | Surfactantless latex compositions and methods of making polymer blends using these compositions |
| WO2001032800A1 (en) * | 1999-10-29 | 2001-05-10 | Asahi Glass Company, Limited | Aqueous dispersion for water-and-oil repellant and process for producing the same |
| JP2001233906A (en) * | 2000-02-22 | 2001-08-28 | Nicca Chemical Co Ltd | Method for manufacturing copolymer composition, and water/oil-repellent agent |
| US6699931B2 (en) | 2001-04-09 | 2004-03-02 | Eastman Chemical Company | Modified alkyd compositions comprising diol latex compositions and processes of making the same |
| US6844390B2 (en) | 2001-04-09 | 2005-01-18 | Eastman Chemical Company | Modified alkyd compositions comprising polyol latex compositions and processes of making them |
| US6479605B1 (en) | 2001-05-15 | 2002-11-12 | E. I. Du Pont De Nemours And Company | High-durability, low-yellowing repellent for textiles |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3403122A (en) * | 1967-12-22 | 1968-09-24 | Minnesota Mining & Mfg | Emulsion polymerization of water insoluble omega-(n-perfluoroalkanesulfonyl) aminoalkyl acrylates or methacrylates |
| JPS5734294B2 (en) * | 1973-05-15 | 1982-07-22 | ||
| US4426476A (en) * | 1982-02-03 | 1984-01-17 | Minnesota Mining And Manufacturing Company | Textile treatments |
-
1983
- 1983-08-16 JP JP14880783A patent/JPS6040182A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120061230A (en) * | 2010-12-03 | 2012-06-13 | 서울시립대학교 산학협력단 | Solar cell and method of the manufacturing of the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6040182A (en) | 1985-03-02 |
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