GB2218097A

GB2218097A - Perfluoroalkylsulphonamidoalkyl silanes; surface treatment agents

Info

Publication number: GB2218097A
Application number: GB8909086A
Authority: GB
Inventors: Motohiko Yoshizumi; Yukiya Yamashita; Akira Nishihara; Akihiro Nakamura; Toshiharu Hayashi; Midori Kaneko; Kazuyoshi Muraoka
Original assignee: Mitsubishi Metal Corp
Current assignee: Mitsubishi Metal Corp
Priority date: 1988-04-26
Filing date: 1989-04-21
Publication date: 1989-11-08
Also published as: FR2630443A1; DE3913485A1; GB8909086D0

Description

1 1

Title of the Invention

Novel fluorine-containing silane compounds, processes for preparing the same and uses thereof Field of the Invention

This invention relates to a class of novel N-alkyl-,N'-[3(substitutedsilyl)propyl]-perfluoroal.kylsulfonamide compounds, processes for preparing the same and uses thereof. The compounds of the present invention can be used as surface modifiers for various materials.

Background of the Invention

Silane compounds having a perfluoroalkyl group or groups are known and use thereof as mold release agents is being considered.

Recently, improvement of water-.repollency, oil-repellericy, nontackiness of" both resins and inorganic materials are desired.

Conventional silane compounds are not satisfactory in waterrepellency, o. I-repellency and non-tackiness when they are used as su.--.112ace property improver.

Silane compounds having a perfluoroalkyl group or groups have,good waterand o-il-repellency but are still unsatisfactory in adhesion to substrate materials and thermal and chemical stability. Some of them have disadvantage in that starting materials for the preparation decompose during the hydrosilylization reaction for the synthesis thereof resulting in low yield of the product.

We conducted an extensive study in order to overcome the above- described problems and have found that certain silane compounds having a perfluoroalkyl group and a sulfonamide group in a molecule overcome the above problems and are suitable for the purpose of the present invention. Summary of the Invention

This invention provides a class of novel N-alkyl-N-[3_(substituted-silyl)propyl]-perfluoroalkylsulfonamides represented by the formula C, F,,, I SO, NRI CH2CH., M SiR 2 3 - BAN J) wherein RI is a Cj_,; alkyl group, R2 is a CL-s alkyl group and A-is chlorine or bromine or a C, alkoxy group, n is an integer of 4 to 12, m is an integer of 1 to 3.

Preferably, RI is C, -, alkyl, R is C, - 3 alkyl, A is methoxy or ethoxy or chlorine, n is 6-10 and m is 3.

1 1 More preferably, R' is n-propyl, R2 is methyl or ethyl, A is methoxy or ethoxy, n is 8 and m is 3.

This invention also provides processes for preparing the N-alkylN-[3-(substituted-silyl)propyl]-perfluoroalkylsulfonamides recited above.

The compounds of the present invention can be prepared by a process comprising reacting an N-allyl-N-alkyl-perfluoroalkylsulfonbLmide represented by the formula Q Fz.. 1 SOz NRI. CH,. CH =CH (II) wherein R' and n are as defined above, with a halo-, alkoxy- or- haloalkoxysilane represented by the formula HSiR2,, A.

wherein R2, A and m are as defined above, in the presence of an addition catalyst; and further reacting the resulting addition product x,,ith a C-,-,s alcohol, if desired when A is chlorine or bromine.

The compounds of the formula JI) can be prepared by reacting a perfluoroalkylsulfonyl fluoride prepared by electrolytic fluorination with an N-alkylallylamine, or reacting perffluoroalkylsulfonyl fluoride with an N-alkylamine to form an N-alkylperfluoroalkyl sulfonamde and thereafter reacting it with an allyl halide in the presence of an alkali.

These compounds are produced by New Akita Chemical Co., Ltd.

(Shin-Akita Kasei Kabushiki Kaisha) and N-n-propyl-N--perfluorooctyl allyl-sulfonamide is marketed by said company.

i The compounds of the general formula -(III) are also commercially available, from Tokyo Kasei Kabushiki Kaisha for instance.

In.the process as recited above, the preferred addition catalysts are chloroplatinic acid, azo-bis-isobutyronitrile, benzoyl peroxide, an octacarbonyl complex of cobalt, platinum and rhodium.

In the process as recited above, the reaction of the addition product, of which A is chlorine or bromine, and a Ci-s alcohol can preferably be conducted by blowing dry air into the reaction mixture or under a reduced pressure. The evacuation should be enough to remove formed hydrogen halide but not to be excessive lest it should cause loss of the used alcohol.

The reaction of the addition product, of which A is chlorine or bromine, and said alcohol also can preferably be conducted in the presence of a base such as organic amine.

1 t1 t 3 The compounds of the present invention, of which A is C,-., alkoxy,also can be prepared by reacting the addition product of the -compound of the formula (II) and the compound of the formula (III) with a corresponding metal alkoxide.

The compounds of the present invention, of which A is C,-,, alkoxy,,also can be prepared by reacting the addition product of the compound of the formula (II) and the compound of the formuia (III) with an orthoformic acid ester of the corresponding alcohol.

The compounds of the present invention represented by the formula (I), wherein A is a Cj_r, alkoxy group, can be prepared by a process comprising reacting a compound represented by the formula Q, F2, L SO, Y (IV) wherein Y is fluol-ine, chlorine or bromine and n is as defined above, wh an aminosilane represented by the formula it NR'CH:,CHt-CH,SiR2., -, A, IV) k wherein R!, R2 and m are as defined above and A is as defined above.

In the compounds of the present invention represented by formula J), the alkyl group R! nay be straight-chained or branched.

A compound represented by formula (III) is used in an amount of 1 mole equivalent or more, preferably 1.3-1.5nol per mole of the compound (II). The reaction. of a compound of formula JI) and a compound of (III) is conducted at 30-1500-k., preferably 40-80C under agitation.

- 25 The amount of the catalyst to be used is usually 1x10-1 to 1x10-2%, preferably 1x10-1 to 5x10% by weight of the amount of the compound of formula (II).

The reaction of a compound of formula (I), wherein A is chlorine or bromine, and a Cl-s alcohol can be easily conducted by blowing a dry inert gas into the reaction mixture at 5-401C, preferably 10-20'r, -or by stirring the reaction mixture under a reduced pressure.

The gas should be inert to the compound of formula (I)-wherein A is chlorine or bromine and the Cl-s alcohol, specifically, dried N., He, Ar, etc. are preferred.

Blowing-in of the dry inert gas is made for removal of liberated HCl or HBr and evacuation has-the same effect. If the pressure is reduced excessively, loss of the used alcohol by vaporization will occur.

When the compounds of the present invention reprented by the At formula (I), wherein A is a C,-s alkoxy group, are prepared by the raction of a perfluoroalkylsulfonyl, chloride (compound of formula (IV) and an aminosilane (compound of formula (V)), it is preferred that the former is used in an amount of more than 1 mole equivalent, preferably 1. 05 or 1.2 moles, to the amount of the latter.

The reaction of the compound of formula (IV) and the compound of formula (V) is preferably conducted in the presence of an organic base such as pyridine, triethylamine, etc. in order to remove formed hydrogen halide.

Although it is not necessary to employ a solvent, a solventinert to the reaction not specifically limited can be used. Specific examples of such solvents are ether compounds such as tetrahyu'rofurane, isopropylether, etc. Although the reaction temperature is varied in accordance with the species of the solvent employed, it is usually between room temperature and 100T., preferably 20-50-C.

The sulfonamide moiety of the compounds of the present invention enhances the yield in the hydrosilylization in their synthesis and brings about better orientation of the perfluoroalkyl group more than carboxylic acid compounds or carboxylic amide compounds when used as a surface property modifier, and thus improves water-repellency, oilrepellency and nontackiness of the substrate.

Furl-her, the alkyl group bonded to the nitrogen atom promotes miscibilitv with organic solvents.- The compounds of this invention are useful as water- and oilrepellent, surface property modifier and for other various uses.

That is, this invention also provides filler powders or filler short fibers to the surface of which one of the above described silane compounds is bonded or adheres.

This invention also provides fluorine resin compositions containing an inorganic filler treated with one of the above recited silane compounds.

This invention also provides water- and oil-repellent paper and glass treated with or containing the above described silane compounds.

This invention also provides weathering-resistant construction materials the surface of which is treated with the above-described silane compounds.

This invention also provides water- and oil-repellent and non- i i i 35' solderable electroconductive metallic materials, the surface of which is treated with one of the above-described silane compounds.

This invention also provides inorganic pigments and fillers which are treated with tfie above-described silane compounds and have good dispersibility in organic solvents and gives less viscous coating materials (paints).

The water-repellency, oil-repellency and non-tackiness of the compounds of the present invention is exhibited by the perfluoroalkyl group thereof and the halogen or alkoxy groups thereof react with water to be converted to hydroxysilyl groups, which combines with -ing on the surface of inorganic materials by hydroxy groups exist dehydration condensation, hydrogen bond, etc.

Ihen the compound of the present invention is applied to the surface of a material or incorporated therein, it is usually used as -Jon and is a solution in an organic solvent. The manner of the applicat ly, the compound is mixing is not speciflcally LLMited. Preferabl dissolved in an anhydrous chlorinated solvent, a fluorinated solvent, acetone, tetrahydrofurane, hexane, an alcohol and the like or a P or those in which a small amount of an aqueous mixture thereoL solution of an amine or acid is added, and the solution is applied to - surface by a known method such as spraying, dipping, etc.

the objec'Ll Specific Description of the Invention

Now the invention t-jill be illustrated by way of workng examples. Example 1 In a 500ml three-necked flask equipped with a magnetic stirrer, a thermometer and a reflux cooler, 108.lg (0.200mol) of N-n-propyl_Nperfluorooctylsulfonamide ("EF-111" marketed by New Akita Chemical Co.), 15.4g of 85% potassium hydroxide (0.233mol) and 200ml of acetone were placed, and into this mixture,-30.71g (0.254mol) of allyl bromide wbLs added dropwise over a period of 10 minutes at room temperature. After stirring was continued further for 4 hours, the reaction mixture was filtered, the filtrate was concentrated by distillation until the volume thereof was reduced to 100ml and was poured into a 5% ammonium chloride aqueous solution. The organic layer was collected, the vacuum distillation of which gave N-n-propylN-allyl- perfluorooctylsulfonamide.

Then, in a 100ml three-necked flask equipped with a magnetic stirrer, a thermometer and a reflux cooler, 96.9g (0.167mol) of the 46 above N-n-propyl-N-allyl-perfluorooctylsulfonamide and 5mg of a 0.11M isopropanol solution of chloroplatinic acid hexahydrate (9.67x 10- 3 MM01) were placed and 25.3m1 (0.250mol) of trichlorosilane was added dropwise over a period of 30min.

Stirring'was further continued for 2 hours after the addition of trichlorosilane was finished, and then the vacuum distillation of the reaction mixture gave 110.3g (0.1539mol) of N-n-propyl-N[3(trichlorosilyl)propyl]-perfluorooctylsulfonamide. Yield: 92.3%; B. P. 153V2. Omm Hg. The compound was identified. as: W 2 CE? 2 CH11 1 Ca'Fl 7 SO2IN-CH! -- CHL 2 CW 2 SiCL by NNIR analysis, MS analysis and IR spectrophotonetric analysis.

Condlitions and results of tli-le n1R and IMS analyses were as f ollows.

1 ID IR ana.vs--Ls:

113(1,1,2-trichloro-2,2,1-triflucroethane), Solvent: Flon-j- i -andard: benzene Internal st 51.30(t, 3H, H-a), 81.6-2.z-)(m, 67HT,H-b, d, 4H, H1c, f) analysis: Ionization voltage: 70eV m/e, relative intensity and noiety are as follows in this order: 554, 60. 57d, M' -- CHz C11, SiCl,; 133, 1E. 0, 10, SiG13, 69, 100%, - CF,3 IR spectrophotometry Sample: neat 3350, 29ESO, 1390, 1260-1130 (cmExample 2 In a 300m1 four-necked flask equipped with a mechanical stirrer, a trap, a thermometer and a reflux cooler to which an aspirator was connected, 48. 1g (0. 0671mol) of N-n-propyl-N- [3- (trichlorosilyl) propyl]'-perfluorooctylsulfonamide was placed and SOmI, of methanol was added dropwise over a period of 2 hours at 15-201C under a reduced pressure. Thereafter, vacuum distillation gave 40. 1g (0. 057mol) of N- n-propyl-N- [3- (trimethoxysilyl) propyl] -perf luorooctylsulfonamide.

Yield: 85. Oloyo; B. P. 1341C/0. 25mmHg. The compound was identified as:

CH' 2 CW 2 CIP 3 Q F,.; SOR N-CH9 2 CHI -- CR2 2 Si (OCH4.1) 3 Q Q c 7 by NMR analysis, MS analysis and IR spectrophotometric analysis.

Conditions and results af analyses were as follows.

IHNMR analysis:

Solvent: Flon-113, Internal standard: benzene 80. 9 (t, 2H, H-e), 61. 25 (t, 3H. H-a), 61. 6-2. 5 (m, 6H, H-b, e, f), 63. 5-4. 0 (m, 4H, H-c, g), 83. 8 (s, 9H, H-d) MS analysis: Ionization voltage: 70eV nVe, relative intensity and moiety are-as followis in this order: 672, 22. 6%, 1P OCH3; 554, 1. 8%, M' - CH2CH2SiffiCH3).3, 121, 100%, ^Si(OCH,,)-,., 69, 21%, 'CF,, IR spectrophotometry:

SanpLe: neat 3350, 2950, 1390, 1260-1130, 1090 (cm is Example 3

In a 300m1 four-necked flask equipped with a magnet-ic stirrer, a thermometer, a reflux cooler, to which a trap was connected, and a of N-n-propyl-N-E3- nitrogen inlet tube, 50.2g (0.070mol) (trichlorosilyl)propylj'-per-. 4L'luorooet,isulfonanide was placed, and 50m1 of methanol was added thereto dropwise at 10-15T_ over a period of 5 hours as nitrogen gas was viaorousl,.y being blown into the bot 4- om C5 L of the flask. After the addition of the methanol was finished, the -ion mixture was further stirred fo.

react - 5 hours. Thereafter, by removing the excess methanol by vacuum distillation, 38.2g (0.054mol) of N-n-propyl-N-[3-(trimethoxysilyl)propylj-perfluorooetylsulfonamide was obtained. Yield: 7-1%. Example 4 In a 500m1 three-necked flask equipped with a mechanical stirrer, a thermometer, a reflux cooler and a dropping funnel, 143.3g (0.20mol) of pulverized N-n-propyl-N-[3(trichlorosilyl)propyl]perfluorooctylsulfonamide, 121.2g (1.2mol) of triethylamine was added and further 96g (3.Omol) of methanol was added dropwise over a period of 2 hours at 15-201C under stirring as the flask was cooled by ice water.

After the addition of methanol, the produced salt was separted by filtration, 130. 9g (0. 186mol) of N-n-propyl-N- [3- (trimethoxysilyl) propyl]-perfluorosulfonamide was obtained by vacuum distillation. Yield: 92. 0%. B. P. 1341C/0. 25mmEg.

i Example 5

In a 30On.1 three-necked flask equipped with a mechanical stirrer, a reflux cooler and a dropping funnel, 71.7g (0.10mol) of N n-propyl-N-[3-(trichlorosilyl)propyl]-perfluorooctylsulfonamide was placed and 75g of a 28% methanol solution of C1130Na was added dropwise at 15-201C over a period of 2 hours.

After the addition of the mettoxide, the produced salt was separated by filtration, 65.4g (0.093mol) of N-n-propyl-N-[3 (trinethoxysilyl)propyl]-perfluorooctylsulfonamide was obtained by vacuum distillation. Yield: 93.0%.

Example 6

In a 300nl four-necked flask equipped with a mechanical stirrer and a reflux cooler, 83.6g (0.10mol) of N-ethyl-N-[3-(tribromo silyl)propyl]-perfluoroocty'Lsul-fonamide and 133.2g (0.9mol) of ethyl orthoformate were placed. To this mixture, 3.Og of alu,-,ii.,num. chloride was added as a catalyst and the mixture was allowed to react at 800C for 12 hours.

After the reaction. was finished, 55.6g (0.076mol) of IN-ethyl-N [3-(triethoxysilyl)propyl]-perfluorooctylsulfonan,ide was obtained by vacuum distillation. Yield: 76.1%. B.P. 146C/0.18mn.Hg.

Example 7

In a 100m1 three-necked flask equipped with a magnetic stirrer, a-thermometer and a reflux cooler, 53.1g (0.10mol) of N-npropyl perfluoroheptylsulfonamid.e, which was supplied by New Akita Chemical Co., and 10mg (1.9x10-5mol) of chloroplatinic acid were placed, and 14.9g (0.11mol) of trichlorosilane was added dropwise through a dropping funnel over a period of 1 hour at 60T_ After further stirring for 1 hour, the excess trichlorosilane was removed by distillation, and thus 61.3g of N-n-propyl-N-[3(trichlorosilyl)- propyl]-perfluoroheptylsulfonamide was obtained. Yield: 92%. The compound was confirmed to be:

c"- H, C H, Ca % 1 C? H, s SO. NW Ha C H, C,' H, SiC13 by IHNMR analysis, MS analysis and IR spectrophotometric analysis. Conditions and results of the analyses were as follows. IMR analysis:

Solvent: Flon-113, Internal standard: benzene 61.25(t, 3H, H-a), 81.6-2. 5(m, 6H, H-b, d, e), 83.5-4.0(m, Q 1 1 1 4H, H-c, g), 6 (s, 9H, Hd) MS analysis: Ionization voltage: 70eV m/e, relative intensity and moiety are as follows in this order: 504, 68. 1%, M+ -+ CH2 CH, SiCl,; 133, 21. 1%,.1 SA13; 69, 100%, CF,3 IR photospectrometry: Sample: neat 3350, 2950, 1390, 1260-1130(cm-1) Example 8

In a 500m1 three-necked flask equipped with a magnetic stirrer, a thermometer and a reflux cooler, 133.3g (0.20mol) of Xl-n- 3- (t m-L propyl-N-[ tlrichlorosilyl)propyll-perfluoroheptylsulfona. de, which was supplied by New Akita Chemical Go., i,.;as placed, and 200m1 of is methanol was added dropwise through a dropping funnel over a period of 5 hours at 3ST- under a reduced pressure of 70mmHg. After the SJyj) 4 addition of methanol, 105.8g of N-n-propyl-N-C3(trimethoxy -L propyl]perfluoroheptylsulfonamide was obtained by vacuum distillation. Yield: 81%. The compound was confirmed to be: Cc Ha C H2 C, H, 1 C-, H, 5 SQ, NCI H, W Hz C" Hz Si (OCH!! 3),3 by 1 HN-MR analysis, MS analysis and IR spectrophotometric analysis.

Conditions and results of the analyses were as follows.

IHNMR analysis: Solvent: Flon-113, Internal standard: benzene 60.9(t, 2H, H-e), 51.25(t, 3H, H-c), 81.6-2.5(m, 6H, H-b, f) 83.5-4.0(m, 4H, H-c, g), 83.8(s, 9H, H-d) MS analysis: Ionization voltage: 70eV m/e, relative intensity and moiety are as follows in this order: 622, 24. 5%, W -4 OCH4,,; 504, 3. 4%, W 'I CHa CH, Si (OCH3).,; 121, 100%, 4 Si (OCH3) 3; 69s 100%, CF3 IR spectrophotometry: Sample: neat 3350, 2950, 1390, 1260-1130, 1090(cm- 1) Example 9 In a 300m1 three-necked flask-equipped with a magnetic stirrer, a thermometer and a reflux cooler, 73.4g (10.20mol) of N-ethyl1xallyl- perf luorobutylsulf onamide and 5m1 of 0. LM isopropanol solution of chloroplatic acid (9.67x10- 3mmol) were placed, and 27.6g (0.24mol) of methyldichlorosilane was added dropwise at WC over a period of 1 hour. After the addition was finished, the stirring was further continued for 1 hour at the - same temperature. The unreacted N-ethylN- allylperfluorobutylsulfonamide and methyldichlorosilane were distilled of f and thus 73. lg of - N-ethyl-IN- [3- (dichloromethylsilyl) propyl]- perfluorobutylsufonam-ide was obtained. Yield: 76%. The compound was confirmed to be:

CHz CH3 1 C4 F;, S02 N-CH2 CH2 CH2 Si (CH3) Cl' Z -1 -1 "rophotoretr-JLc ana-lysis.

by!HN2;4R analysl_s, MS ana_lysis and IR spectL.

Conditions and re.sullts of the analyses were as follows.

1\f "vsis:

tandard: benzene So.1Vent: Flon-113, Internal st 60. 10 (s, 3H), 61. 30 (t, 3H), 81. 6-50- 2. 5 (m, 411), 83. 5-4. 0 (m, 411) MS ana Lys-Ls: Ionization voltage: 7OeV n/e and relative intensity are as follows: 339, 56. 21,11); 113, 24. 6%; 69, 100% IP spectrophotometry: Sample: neat 3350, 2950, 1390, 1260-1130 (cr.i- Example 10

In a 300ml three-necked flask equipped with a magnetic stirrer, a thermometer and a reflux. cooler, 48.2g (0.10mol) of N-ethyl-N-[3 (dichloromethylsilyl)propyl]-perfluorobutylsulfonamide, 40.4g (0.40mol) of triethylamine and 150ml of isopropylether were placed and 30ml of ethanol was added dropwise over a period of 2 hours as the flask was being cooled by ice water. Thereafter, stirring was further continued for I hour at the same temperature. The produced salt was removed by filtration and the excess ethanol-and isopropylether and triethylamine were distilled away and thus 38. 6g of N-ethyl-N-[3-(diethoxymethylsilyl)propyl]-perfluorobutyl- sufonamide was obtained. Yield: 77%. The compound was confirmed to be:

11 CH2 CHa 1 C.t Fa SO N-CHa CH2 CH2 Si (CH3) (OCa Hr,),,. by IHNMR analysis, MS analysis and IR analysis.

Conditions and results of the analyses were as follows.

H1MR analysis:

Solvent: Flon-113, Internal standard: benzene 60. 10 (s, W), 61. 31 (t, 3H), 81. 42 (t, 6H), 61. 6-2. 5 (m, 4H) 63. 5-4. 1 (n,, 8H) MS analysis:

Ionization voltage: 70eV m/d and relative intensity are as follows in this order:

370, 58. 9%; 131, 100%; 69, 84. 1% IR spectrophotometry: Sample: neat 32)50, 2350, 11390, 1-960--11U Exanple 111.

Tn a 200rl three-necked Eask equipped w.ith a nagnetic Stirrer, L -L 11 L 1 a thermoneter and a reflux -cooler, 18.9g (0.20riol) of N-ethy]L-N[3(nonoethoxydimethylsilyl) propyl] -amine, 15. 8g (0. 20mol) Of pYridLne -her svere placed, and 30.2g (0.10n.ol) of and 100m1 of isopropyl-el. perfluorobutylsulfonyl fluoride was added dropwise through a dropping funnel over a period of 1 hour at 20'C. The reaction mixture wasstirred for 1 hour at that temperature and then further stirred for 2 hours at 40t. Thereafter, the produced salt was removed by filtration, the excess pyridine and isopropylether were distilled off and 18.4g of N-ethylN-C3-(monoethoxydimethylsilyl)propyl]- perfluorobutylsulfonamide was obtained. Yield: 39%. The compound was confirmed to be:

CHCH3 C4 H9 SOr. NCHl CH. CH,1 Si (OCH3) (CH,3) 2 by IMR analysis, MS analysis and IR spectrophotometric analysis.

Conditions and results of the analyses were as follows.

35- IMR analysis: Solvent: Flon-113, Internal standard: benzene 60.1(s, 6H), 60.9(t, 2H), 61.3d(t, 3H), 61.6-2.5(m, 2H), 63.5-4.1(m, 4H), 83.8(s, 3H) MS analysis:

Ionization voltage: 70eV 12.

We and relative-intensity are as follows: 426, 12.3%; 103, 62.2%; 69, 100% IR spectrophotometry: Sample: neat 3350, 2950, 1390, 1260-1130, 1090(cm1) Example 12 In a 50ml three-necked flask equipped with a magnetic stirrer, a thermometer and a reflux cooler,_ 20.4g (30mmol) of N-n-propylLNallylperfluorodec.ylsulfonamide, which was supplied by Net; Akita Chemical Co., and-5mg (LOUO-6=0 of chloroplatinic acid were placed; and 4.5g (33mmol) of trichlorosilane was added dropwise through-a dropping funnel over a period of 20min at 801" Thereafter, the reaction system t.-,;as stirred for 1 hour at the same temperature.

By distilling off the ex.cess trichlorosilane, 22. 8g of N-n-propyl--N [ " - (tr --chloros ily.',' pro pyl] - per flu or odecyl su 1 'L o namide was obtained.

Yield: 931%. Tj"iE-- compound was confirmed to be:

CH2 CH,- CH.3 I C,, H-z 1 SO-- NNCH- C"112 CH2 SiC13 -ric analysis.

by '-FLNVR analysis, IMS analysis and DR% spectrophotomet.

Conditions and results of the analyses were as follows. I MAR analysis:

Solvent: Flon-113, Internal standard: benzene 81.31(t, 3H), 81.7-29.6(n, 6H), S3.6-4.1(m, 4H) MS analysis:

Ionization voltage: 70eV m/e and relative intensity are as follows in this order:

654, 720.3%; 133, 24-6511; 69, 1001"o IR spectrophotometry: Sample: neat 3350, 2950, 1390, 1260-1130(cm-1) Example 13

In a 100m1 three-necked flask equipped with a magnetic stirrer, a thermometer and a teflux cooler, 16.3g (20mmol) of N-n-propyl-N-[3 [trichlorosilyl)propyl]-perfluorodecylsulfonamide was placed, and 20m1 of methanol was added dropwise at 401C under a reduced pressure -of 6OmmHg over a period of 1 hour. By distilling off the excess methanol, 12.1g of X-n-propyl-N-C3(trimethoxysilyl)propyl]- perfluorodecylsulfonamide was obtained. Yield: 75%. The compound 17 was confirmed to be: CHR CH, CR3 1 C, c Ha i S0a NCH2 CH2 CHI Si (OCH3) 3 by WIMR analysis, MS analysis and IR spectrophotometric analysis.

Conditions and results of the analyses were as follows.

Ifi NIR analysis:

Solvent: Flon-113, Internal standard: benzene 60.9(t, 2H), 611.24(t, 3H), 81.63-2.52(m, 6H), 63.4-3.9(m, 4H), 83.8(s, 9H) MS analysis:

Ionization voltage: 70eV n/e and relative intensity are as follows in this order:

77-9, 20.4%; 654-1, 5.6%; 121, 100%, 69, 89.1% IR spectrophotometry:

Sample: neat 3350, 2950, 1390, 1260-1130, 1090(cm---) T 1he fluorine-containing silane compounds of the present invention have excellent water- and oil-repellency.

Example 14:

An ordinary glass plate 24mmx75mm in dimension was immersed for 30sec-in a solution consisting of LOg of Ce Fj -, S02 N (C311.,) CH2 M, CHs Si (OCH.,).3 and 100g of ethanol and' 0.5g of a 100,', HC-1 aqueous solution. The glass plate was dried at room temperature and the contact angle of the plate was measured. It was 1100 for water and 75 for liquid paraffin.

Comoarative Example 1 The procedures of Example 14 was repeated except that 1.0g of CILSi(OCH3)3 was used instead of said fluorine-containing silane compound. The contact angle was 350 for water and 37 for liquid paraffin.

Comparative Example 2 The procedures of Example 14 wa-s repeated except that 1.0g of NH,CH,tCH,NHCH,CH,CH,,CH,Si(OCH3) was used instead of the fluorine containing silane compound was used. The contact angle was 270 for water and 34 for liquid paraffin.

Example 15

A 25nmx75mm plate of ordinary glass was immersed in a solution /v consisting of 1.0g of N-ethyl-,NT-[a-(triethoxylsilyl)propyl]perfluorohexylsufonamide, 200ml of ethanol and 0.5g of a 10% hydrochloric acid for 1min and dried at -room temperature.

The contact angle of the thus treated glass plate was 110 for water and 76for liquid paraffin.

Comparative Example 3 The procedures of Example 15 was repeated using 1.0g of trimetfioxymethylsilane instead of the fluorine containing silane compound. The contact angle was 35" for water and 37 for liquid paraffin.

Comparative Example 4 The procedures of Example 15 was repeated using 1.0g of 3- tr--..7,ek-hoxys--L.!-,y-'.'Lpropy','- perfluoroheptylearbonate instead of sa4Ld fluorine containing silane compound. The contact angle was 81 for water and 4'j for liquid paraf-.1 Example 16 Three grams of LN-n-propyl-N-[3- (trimethoxylsilyl)propyl]perfluorobutylsufonamid_e was admixed tiith 100g of epoxy resin paint S4_ base (melamine-hardenable epoxy re in supplied by Tokyo Paint Kabushiki Kaisha) and the mixture was applied to 50mnx1OOmnx1mm steel test panel (marketed by Nippon Test Panel Kabushiki Kaisha) to a thickness of O.1mn and cured at 120'C for 20min. The contact angle of the surface vjas measured as indices of viater-repellency and oilropellency. The angle was 11T for water and 850 for liquid paraffin. Comparative Example 5 The epoxy resin used in Example 16 was applied to 50mmx1OOr,,nx1mm - panel (marketed by Nippon Test Panel Kabushiki Kaisha) to steel tes&I a thickness of O.1mm without addition of the fluorine- containing silane compound-and cured at 120'C for 20min. The test for water- and oil-repellency was carried out in the same manner as in Example 16. The contact angle was 330 for water and 12' for liquid paraffin. Comparative Example 6 The procedures of Example 16 was repeated using 3g of 2trifluoromethyl-l- trimethoxysilylethane. The contact angle was 45, for water and 23" for liquid paraffin.

When inorganic fillers such as glass fiber, glass beads, alumina, graphite, carbon fiber, molybdenum disulfide, metal powders 1 1 r such as bronze powder, lead powder, etc. are treated with the fluorine-containing silane compound of the present invention, they -can be easily mixed with fluorine resins such as polytetrafluoroethylene, polychlorotrifluoroethylene, poly(vinylidene fluoride), poly(vinyl fluoride), hexafluoroethylene-hexafluoropropene copolymer, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-perfluoroalkylvinylether copolymer, chloro trifluoroethylene-ethylene copolymer, etc. with good affinity and the resulting resin composition has excellent compression resistance and abrasion resistance. Usually, 0.1-20% by weight of the fluorine-containing silane compound is

used on the basis of the weight of fillers. 17 Example.

Fifty (50) grams of glass fiber (about '61,1,m in diameter and about 500m' of an ethanol solution of 2.- 50gm, in length" t.,;a;z immersed in 5 - _L r, of C,a F., -, SOw. N (C, H,) CIA-14 CH,- CH Si (OCH,),, 1 % by weight of a 109 HC' -ion and the cont 10 L aqueous solut mixture was vigorously agitated by means of an electric shaker for --h the 10min at room temperature. The glass fiber thus treated wit J fluorine-containing silane compound was mixed vjjth polytetrafluoroethylene (Teflon'D) powder at a weight ratio of 50:150 and the -ed by a pressure of 400kg/cm' to a piece 172mm in mixture i.-)as compact L diameter and 10mm in thickness. The piece was bakedat 370C for 1 hour and a glass-fiber-reinforced TeflorP resin was obtained.

- on The compression strength (compression rate 3mm/min) and fricti properties and abrasion properties were measured. The compression strength was measured at a compression rate of 3mm/min, the friction and abrasion properties were measured using a Suzuki's abrasion -tester. The results are shown in Table 1 together with the results of the following comparative example. Comparative Example 7' The procedures of Example 17 were repeated using the same glass fiber which was not treated with said fluorine-.;containing silane compound, and thus a glass-fiber-reinforced Teflon" resin piece was obtained and the tests were carried out with this resin piece. The results are shown in Table 1.

1 1 14 Table 1

Compression strength Example 17 Comp.Ex. 7 Load required for 1% deformation (kg/cm2) 98 84 n 25% 346 305 Friction coefficient static 0.07 0.07 dynamic 0.24 0.24 Abrasion coefficient (kg/cm2) 1.1x10-5 1.1x10-5 Test conditions: Counter piece: SUS27 stainless steel piece, "156nnx20mn, x15mn Load: 4kg/cm2 Rate: 60m/min line: 16hrs after 30min of pre-operation Example 18

In a 1 liter three-necked flask equipped with a thermometer, a stirrer and a reflux cooler, '50g of graphite powder was placed and 100ml of a 10% by weight of solution of the same fluorine-containing silane compound as used in Example 17 was added dropwise over a period of 1 hour under stirring. Thereafter, the mixture was heated to 100T. to remove the solvent.. The thus obtained treated graphite -s were powder was mixed with the same TefloiP resin and the same test carried out. The results are shown in Table 2.

Comparative Example 8 The procedures and tests of Example 17 were repeated with untreated graphite powder and the results are shown in Table 2.

Table 2

Compression strength Load required for 1% deformation (kg/cml) 25% Friction coefficient static dynamic Abrasion coefficient (kg/CM2) Example 18 Comp.Ex. 8 391 0.05 0.23 6. 7x10- 5 76 355 0.06 0.23 6. 7x10- 1 f 3517 When inorganic fillers such as silicon oxide, tin oxide, titanium oxide, aluminum oxide, silicon nitride, graphite, zinc oxide, iron oxides, mica, glass fiber, carbon fiber, asbestos, etc. are treated with the fluorine- containing silane compound of the present invention, they are provided with excellent water- and oil repellency and non-tackiness.

of the fluorine-containing silane Usually, 0.1-20% by weight compound is used on the basis of the weight of the filler. Example 19 Fifty (50) grams of silica powder (about Igm in diameter) was.mixed with 50OmI of ethanol solutions respectively containing 0.1, 1, 5 and 10% by weight of C F S 3 -, N (C _ FP,) C 1111 -, CLI. - C Hs. S i (0 C 3 on the bas Ls of the -:eigh+L. of the fi'Lleú- and 1% by weight of a 10% HCl aqueous so-'u+,-'o,, and tho mixt-re was -Lgorously Led by means of an electric shaker for 10min at room temperature.

The mixtu.re was heated tc 1OWC, to remove the solvent by evaporation and thus silica pox,.,jders treated with the fluorine- containin; -L L L 11 g silane compound were obtaJned. Substant-ally all of the -aining silane compound adhered to the s-'lica added fluorine-cont J_ powder.

Lhe IR absorption spectra oJL' the thus treated silica powde -ion met e'y were measurc-%d by pot..,der reflect Lhod and it was obs r-ed that there were an absorption caused by the C-H bond at 2850-2950cm-1, an absorption caused by the sulfonamide bond at 1390cm-land an absorption caused by the C-F bond at 1100-1300cm-1. That is, it was revealed that the fluorine-containing silane compound exists on the surface of the silica powders.

The water repellency of the thus treated silica powders were measured. The powders were respectively mixed with 500m1 of water and vigorously agitated with an electric shaker for 15 minutes at room temperature. The water repellency was evaluated based on the observation by the naked eye. Comparative Example 9 The procedures of Example 19 was repeated using CH2CHp.CHa0CH2CH2CHa Si (OGR, \ 0 / -The results are summerised in Table 3 together with those of Example i 1 qv 19.

p Example 19 F-containing silane Water compound content repellecy by weight) 0.1 - 5.11%) Table 3

0 0 0 Comparative Example 9 Silane compound content (% by weight) 1 tlater repellency X X x: Silica powder completely disperses _in water.

0: Sil-Lca powder partly disperses in water and partly 'Lloats on 'Uhe t.-jater surface. the water surface.

0: Silica po,.,de.- completely floats on 4.

Example 20

En a 31- liter -three-neclked flask equipped a therMomete, a stirrer and a reflux cooler, BOg of alumina powder (about igm in diameter) was placed and 50ml of solutions ('57, 10, 20 and 25m. bv weight) of 'Che same fluorine-conta-ining silane compound were re - spectively added dropwise over a period of 1 hour under stirring. Thereafter each mixture was heated to 100'C to remove the solvent. Thus alumina powders treated with the same fluo-Aine-containing silane compound were obtained.

It was confirmed that the fluorine-containing silane compound.adhered to the surface of alumina powder with the IR absorption spectra by the powder reflection method in the same manner as in Example 19. Comparative Example 10 The procedures-and tests of Example 19 were repeated.using CRI CH2 C% CH2 Si (OCH,,),, as a silane compound. The results are shown in Table 4 together with those of Example 19.

14 Table 4

Example 19

F-containing silane Water compound content repellecy (% by weight) - 5 is Comparative Example 10 Silane compound content (% by weight) 5 0 Water repellency X @ 0) 20 - 0 @ Symbols have the same meanings-as in Table 3 Example 21

Fifty (50) grams of silica powder (about 1Ogm in diameter) was mixed WIth 50OmI of ethanol solutions respectively containing 0.1, 1, 5 and 10% by weight of Ce F - S02 N(C3H-.) CH, M CH Si (OCH, on the bas-Js of the weight cl.' the f_iller and 1% by weight of a 10% HCl aqueous solution and the mixture was vigorously agitated by means of an electric shaker for 20min at room temperature.

The mixture was heated to 100T to remove ethanol by evaporation and thus silica powders treated with said fluorine-containing silane compound was obtained. The IR absorption spectra of the thus treated silica powders were measured by the powder reflection method and it was observed that there were an absorption caused by the C-H bond at 2850:.-2950cm-1, an absorption caused by the S02N bond at 13-90cm-land an absorption caused by the C-F bond at 1100-1300cm-1. That is, it was confirmed that the fluorinecontaining silane compound exists on the surface of the silica powders.

The thus treated silica powders were respectively mixed with an epoxy resin paint base (melamine-hardenable epoxy resin supplied by Tokyo Paint Kabushiki Kaisha) in an amount of 50% by weight of the resin paint base and the mixture was applied on the surface of steel test panels to a thickness of 100pm. The coated test panels were cured at 1401C for 20min and tested for water resistance. That is, the panels were heated in an autoclave containing water under a pressure of 5atm for 2 hours. Thereafter, the water content of the i coating was measured. The results are shown in Table 5). Comparative Example 10 The procedures of Example 21 were repeated using CH3 Si (OC%) 3.

The results are shown in Table 5.

Exanple 21 'later F-containing silane 1.

compound content content (% by weight) 0.1 1 Example 22

50. 31% 0. 2 % 0. 2 %;5%'. 2% Table 5

Comparative Example 10 Silane compound Water content content (% by t..,jeight) 1 :3110 In a 1 liter three-necked flask equipped with a thermometel, a stirrer and a reflux cooler, 50g of alumina powder (about 10pm in diameter) was placed and 50m1 of solutions (5, 10, 20 and 2511% by weight) of the same fluorine-containing silane compound as that used in Example 21 was added dropwise over a period of 1 hour under stirring. Thereafter the mixture was heated to 1001C to remove the solvent. With respect to the thus treated silica powders, the presence of the fluorine-containing silane compound on the surface thereof was confirmed by the IR absorption spectra by the powder reflection method in the same manner as in Example 21. Further the same water resistance test as that carried out in Example 21 was conducted. The results are shown in Table 6.

Comparative Example 11 The procedures and tests of Example 22 were repeated using CESi(OG113),,, which was used in Comparative Example 10 as'a silane compound. The-results are shown in Table 6 for comparison with those of Example 22.

i Z# Table 6

Example 22

F-containing silane Water compound content content (% by weight) Comparative Example 11 Silane compound Water content content (% by weight) 50.2% 5 12% 0. 2% 20;50. 2% 20 a2% 25 Poor dispersion. No coating material formed.

Example 22

L, I The procedures of Example 22 was repeated using alumina powder (about Bgm in diameter). The results are shown in Table 7. Comparative Example 12 The procedures of Example 23 was repeated using - NHa (CH), Si (OCH.,), as a silane compound. The results are shown in Table 7 for the comparison with Example 23.

Table 7

Example 23

F-containing silane Water compound content content (% by weight) Comparative Example 12 Silane compound content (% by weight) Water content 0.1 - 50. 2% 1 kA 1 50.1% 5;so. 1% 10 10;so. 1% Example 24

The procedures of Example 22 was repeated using 50g of alumina powder (not larger than about SILm in diameter). The results are shown in Table 8.

21 Comparative Example 13 The procedures of Example 22 was repeated using NH2 (CHit) 3Si(OCH3)3 as a silane compound. The resu lts are shown in Table 8 for comparison with those of Example 24.

Table 8

Example 24

F-containing silane Water compound content content by weight) 2.5 Poor dispersion.

Comparative Example 13 Silane compound Water content content (% by weight) 0. 2% 50. 100 0. 1.

0 No coating composition formed.

_15 I at r,.A. ru !1% Example 25

Fifty (50) grams of glass fiber (about 3gm in diameter and about 5-Ogm in average length) was mixed with 500ml of acetone solut Ilions containing various amounts of C8 FL 7 S02 N' (C2Hr,) CH2CH2CH2 Si (CH3) 3 containing 1% by weight of a 10% HC1 aqueous solution, and the mixture was stirred for 20min at room temperature. The concentra- -tions of the fluorine-containing silane compound in these solutions were 0.1, 1, 5 and 10% by weight on the basis of the weight of glass fiber. After 30min, acetone was removed by heating to 100'C and the thus treated glass fibers were tested for the IR spectrum by the diffusion reflection method. Absorptions were observed at 28592950cm- I (C-H), - 1390cm- 11 (SOit N) and 1100-1300cm- I (C-F) and thus it was confirmed that-the fluorine-containing silane compound was. present on the surface of glass fiber. The thus treated glass fiber was mixed with an acryl resin paint base (self-curable acryl resin paint base supplied by Tokyo Paint Kabushiki Kaisha) in an amount of 50% by weight and the mixture was poured into a 10cmxlOcmxlOcm mold and cured at 150'C for 30min. The thus obtained acryl resin lump was - 35 ' 2.1 is subjected to a water resistance test with steam at Satm for 2 hours in the same manner as in Example 21. The water content was measured and the results are shown in Table 9. Comparative Example 14 The procedures of Example 25 was repeated using CH3SiffiCH3)3 as a silane compound and the results are shown in Table 9.

Table 9

Example_25

F-containing silane livater compound content content by weight) 0.1 1 50.8%:!o. sw, !50. 5% m ZW 50. 'D Comparative Example 14 Silane compound content by weight 1 Water content 15% ?W =3,j 1 When metallic materials such as copper, aluninum, iron, lead, zinc, tin, titanium, cobalt, nickel, chromium. etc.; alloys such as stainless steels, HastelloyO, InconelO, StelliteO, etc.; magnetic -1 t 1 the alloys such as Sm-Co alloy, Nd-Fe-B alLoy, etc. are treated wi.l. fluorine-containing silane compound of the present invention, they are provided with excellent water- and oil-repellency. The metallic materials can be in the forms of sheet, sphere, ribbon, etc.

Also, when organic resin materials such as phenol resin, furane resin, xylene-formaldehyde resin, ketone-formaldehyde resin, urea resin, melamine resin, aniline resin, epoxy-resin, poly(vinyl acetate) resin, polyacryl resin, polymethacryl resin, poly(vinyl chloride) resin, poly(vinylydene chloride) resin, polyacrylonitrile resin, polyvinylether resin, polycarbonate resin, polyamide resin, polyurethane resin, etc. including almost all hydrocarbon resins are treated with the fluorine- containing silane compound of this invention, they are provided with excellent waterand oilrepellency. The resin materials can be in the form of sheet, film, fiber or in any other form. Adherence and effect of the compounds of the present invention are not influenced by the shape of the Ilt substrate materials.

Also, when paper is treated with the fluorine-containing silane compound of the present invention, such paper is provided with ecxellent water- and oil-repellency. The paper encompasses machine made paper, hand-made paper, cardboard, corrugated cardboard, etc.

The fluorine-containing silane compound of the present invention is applicable to glass to provide it with excellent water- and oilrepellency.

The fluorine-containing silane compound of the present invention can be added to paper-making pulp slurry-when incorporation in paper is intended.

The fluorine-containing silane compound of the present invention can be applied to the surface of various materials by admixing with a resin coating composition.

is ExaMple 26

A 0. WOG acetone sollution of Ce F1 7 S07 N (C, H;) CH2 CH2 CH;. Si (OC2Hs), ' by weight of a 10% acetic acid aqueous solution was containing 0.5% applied to a 100mmx5Ommxlrn aluminum plate.

The contact angles of this plate for water and liquid paraffin were measured for evaluation of its water- and oil-repellency. The results are shown in Table 10. Comparative Examples 15 _ The same aluminum plate as used in Example 26 was coated with an acryl resin paint base (a self-curing type acryl resin supplied by Tokyo Paint Kabushiki Kaisha) o the coating weight of 3% by weight.

Water- and oil-repellency of this aluminum plate were measured and the results are shown in Table 10 together with the results of.Example 26.

Table 10

Contact Angle () Water Liquid paraffin Example 26 1430 1120 Comp. Ex. 15 960 280 Example 27 c 29 A 5% acetone solution of C4 F, 7 SO, N (C3 H,) CHx CH, CH, Si (OC%) 3 containing 1% by weight of a 10% HCl aqueous solution was applied to a 10Omnx50n.nxlm copper plate.

The plate was dried at 801C for 1 hour. The coated copper plate was checked by IR spetrophotometry and there was observed absorption of the C-F bond at 1100-1300cm71. That is, adhesion of the fluorine containing silane compound was confirmed.

The plate was immersed in a 5% c=non salt a-queous solution and weight loss was measured.

Comparative Example 16 The same copper plate as used in Example 27 which was not treated with the fluorine-containing silane compound was tested in the same manner. The results of Example 27 and Comparative Exampl 16 are shown in Table 11.

Table 11

No. of days Example 27 Comp. Ex. 16 1 0% 5% 2 10.1 8% 3 3% 12% 18% 8% 24% Example 28

A 5% by weight ethanol solution of C& FL 7 S02 N (Cz He) CH., CHIt CHx Si (OCjt He),3 containing 0.5% by weight of a 10% n-propylamine aqueous solution was applied to a 100mmx5Ommxlmm steel plate.- The plate was allowed to stand outdoors and staining of this surface was observed. Comparative Example 17 The procedures of Example 28 were repeated using untreated steel plated. The results are shown in Table 12.

2.4 Table 12

No. of days 1 10 30 60 100 O:-Clean (no stain) &: Stains in several places x: Stained overall Example 280 0

0 0 A.

Comp. Ex. 17 0 AL X X X Example 29

FiVe (5) grams of C. F, - SOR N (CH3) CH2 M. CH2 Si (OCR, was added to 100g of an epoxy resin paint base (melamine-hardenable epoxy resin supplied by Tokyo Paint Kabushiki Kaisha). The paint was applied to a 100-..n.x5OrL7ixinm test panel (marketed by Nipponn Test Panel Kabushiki Kaisha) to a thickness of O.lmm and the panel was baked at 120QC for 20min. Contact angles for water and oil were measured for evaluation of water- and oil-repellency. - Comparative Example 18 Using the epoxy resin paint base used in Example 29 containing no fluorine-containing siiane compound, a test panel was prepared and tested in the same manner as in Example 29. The results are shown in Table 13.

Table 13

Contact Angle (c) Water Liquid paraffin 1060 78 72' 180 Example 29 Comp. Ex. 18 Example 30 The epoxy resin paint base used in Example 29 was applied to a 10Ommx5Ommxlmm test panel (marketed by Nipponn Test Panel Kabushiki 27 -5 Kaisha) to a thickness of 0.1m and the panel was pre-baked at 80,c for 30min.

This panel was immersed in a 10% by weight Flon113 solution of % FL 7 SO, N (C3 H-,) CH2 CHz CH2 S i (OCH,) 3 for 10sec and baked at 120C for 20min. The thus treated panel was che cked by IR spectrophotometry and there was observed absorption of the C-F bond at 1100-1300cm-1. Water- and oil-repellency df this panel was checked in the same manner. Comparative Example 19 The procedures of Example 30 was repeated using a fluorinecontaining surfactant CaFl 7 S%Na. tlater- and oil-repellency were evaluated in the same manner.

I Lable 14 Contact Angle (0) ,.Iater Liquid paraffin Example. 1100 8210 Com-p. Ex. 19 74 20 Example -31, An acryl resin paint base (self-curing ac-yl resin markLeted by E rL L Tokyo Paint Kabushiki Kaisha) was applied to a 10Oninx,.0,-lxlr.7i test panel (supplied by Nippon Test Panel Kabushiki Kaisha) to a thickness of O.lmm and the panel was baked at 1701C. for 20min.

This panel was immersed in a 10% by weight acetone solution of C, F, -, S02 N (C, Hs) CH;, CH, CH, Si (OCR3) 3 for 30sec and dried at room temperature. The thus treated panel was checked by IR spectrophotometry and there was observed an absorption of the G-F bond at 1100-1300cm-1. Adhesion of the fluorine containing silane compound was confirmed.

Comparative Example 20 The procedures of Example 31 was repeated using a fluorine containing surfactant CF,.COK instead of said-fluorine-containing silane compound. No C-F bond Was recognized by IR spectrophotometry.

Water- and oil-repellency were evaluated in the same manner.

The results are shown in Table 15.

2r Table 15

Contact Angle () Water Liquid paraffin Example 31 1050 800 Comp. Ex. 20 7T 28 Example 32

Commercially available A4-size letter paper (marketed by Kokuyo Kabushiki Kaisha) was immersed in a 3% by weight acetone solution of % F, 7 SO. N (C,, F,) CHz CH2 CH2 Si (OC1%) 3 for 5min and dried at ro.om temperature for 2 hours. Thus paper impregnated with said fluorinecontaining silane compound was obtained. The paper was checked by IR spectrophotometry and there was observed absorption of the C-F bond at 1100-1300cm-1. Adhesion -aining silane compound was confirmed.

of the fluorine-con-L Water and liquid paraf-tin were dropped on this paper and the absorption was observed and evaluated. Comparative Example 21 The procedures of Example 32 was repeated with respect to the same but untreated paper. The results of Example 32 and Comparative Example 21 are shown in Table 16.

1 Table 16

Absorption time Example 32 Comp. Ex. 21 Water Liquid paraffin 42sec lmin 12sec within 1sec within 5sec Example 33

On the basis of the weight of pulp, 2% of C. F,, SO, N (Ca %) CH. CH,1 CH, Si (OCRt M) 3 was added to a pulp slurry and paper was made.

In IR spectrophotometry, absorption of the C-F bond was observed at 11001300cm-1.

In the same manner as in Example 32, water- and oil-repellency were evaluated.

2.4 Comparative Example 22 The procedures of Example 33 was repeated without using the fluorine- containing silane compound. The results of Example 33 and Comparative Example 22 were shown in Table 17.

Table 17

Absorption time Water Liquid paraffin Example 33 lmin 7sec lmin 59sec Comp. Ex. 22 less than 1sec within 5sec Example 34

Comnercially available corrugated cardboard (marketed by Kashiwaya Shiki Kogyo Kabushiki Kaisha) was imnersed in a 5% by weight benzene solution of G. F,, S02 N (C., H,) CH, CH, CH, Si (OCH, for 3min and dried at 50t, for 1 hour.

Said cardboard was checked by IR spectrophotometry and absorption due to the CF bond was observed at 1100-1300cm-l. That is, presence of the fluorine-containing compound was confirmed.

Water- and oil- repellency of the cardboard was evaluated in the same manner. Comparative Example 23 The procedures of Example 34 was repeated using CA FI 7 SO, N (C2 H5) CH, CH, PO (ONa),, instead of said fluorinecontaining silane compound. The results of Example 34 and Comparative Example 23 are shown in Table 18.

Table 18

Absorption time Water Liquid paraffin Example 34 lmin 16sec 1min 39sec 35Comp. Ex. 23 47sec 1min 3sec When colored ceramic materials such as tiles, pottery and porcelain wares, etc. are treated with the fluorine-containing silane compound of the present Invention, they are provided with excellent color-fastness and increased chemical resistance. Leaching of pigments or pigment-elements (cadmium, lead, etc. for instance) is well prevented. In the case of tiles, growth of molds and mosses on the surface-is prevented.

Example 35

Colored tiles were prepared by coating commercially available colorless semi-porcelain tiles with a paste made by mixing 5 parts by weight of cadmium pigment, 95 parts by weight of non-lead boric acid low temperature glaze (SK010a), 0.2 part by weight of methyl cellulose and 60 parts by weight water and ball-milling the mixture for 30min and firing the coated tiles at 1000'C after drying.

The thus prepared colored tiles were coated with N-n-pr3pyl-N<3 1. L (trimethoxy)silylpropyl]-per-LLluorooctylsulfonamide diluted with et 4 thanol to the concentration indicated in Table 19 and drLed. Each of the thus treated tiles was soaked in 300ml of a 4% acetic acid solution for 24 hours. Thereafter, the amount of cadmium leached out was measured by atomic absorption spectrometer. Also the tiles were dried and checked for deposition of alkali on the surface (efflorescence). The results are summarized in Table 19.

Examples 36

Colored tiles were prepared by coating commercially available colorless semi-porcelain tiles with a paste made by mizing 0.68 par-.

by-weight of ferric oxide, 0.32 part by weight of cobalt oxide, 100 parts by weight of non-lead low temperature glaze (SK010a), 0.2 part by weight of methyl cellulose and 60part by weight of water and ball milling the mixture for 30min and firing the coated tiles at 1050C _after drying.

The thus prepared colored tiles were coated with N-n-propyl-N-[3 (trichloro)si-lylpropyl]-perfluorooctylsulfonamide diluted with ethanol to the concentration indicated in Table 19 and dried. Each of the thus treated tiles was soaked in 300ml of a 4% acetic acid solution for 24 hours. Thereafter, the amount of lead leached out was measured by an atomic absorption spectrometer. Also the tiles were dried and checked for deposition of alkali on the surface. The results are shown in Table 19.

Example 37

Colored tiles were prepared by coating commercially available 7 1 colorless semi-porcelain tiles with a paste made by mixing 2 parts by weight of manganese oxide, 98 parts by weight of non-lead medium temperature glaze (SK4), 0.2 part by weight of methyl cellulose and parts by weight of water and ball-milling the mixture for 30min and firing the coated tiles at 12001C after drying.

The thus Prepared colored tiles were coated with N-n-propyl-N13(trichloro)silylpropyll-perfluorooctylsulfonamide diluted with ethanol to 5% in concentration. The thus treated tiles were immersed in water to the middle thereof and allowed to stdnd for observing growth of molds and mosses. After 3 months, growth of molds and mosses was not observed. Comparative Example 24 The colored tiles prepared in Example 354 Were immersed in a 4% - surface treatment and acetic acid solution for 24 hours without leaching of cadmIum was measured by atomic absorption spectrometry. I-ali was checked.

Also deposition of a1r. Comparative Example 25 The colored tiles prepared in Example 36 were checked for leaching of lead and deposition of alkali in the same manner as in Comparative Example 24. The results are shown in Table 19.

Table 19

Leaching(ppm) Deposition of Alkali 25 (Visual Observation) Ex. Sample Conc.% Cd Pb Ex. - 35 1 1.0 0.05 - None 2 5.0 0.00 - 3 10.0 0.00 Comp.Ex.24 - 15 - Recognized Ex. 36 1 1.0 - 0.08 None 36 2 5.0 - 0.00 36 3 10.0 - 0.00 Comp.Ex.25 - - 58.6 Recognized Example 38

Colored tiles were prepared by coating commercially available " pqrts by colorless semi-porcelain tiles with a paste made by mixing I 31 weight of manganese oxide, 92 parts by weight of non-lead medium temperature glaze (SK4), 0.2 part by weight of methyl cellulose and 60 parts by weight of water and ball-milling the mixture for 30min and firing the coated tiles at 12001C after drying.

The thus prepared colored-tiles were coated with N-n-propyl-N[3(trichloro)silylpropyl]-perfluorooctylsulfonamide diluted with ethanol to 5% in concentration. The thus treated tiles were immersed in water to the middle thereof and allowed to stand for observing growth of nolds and mosses. After 3 months, growth of molds and mosses was not observed. Comparative Example 26 The colored tiles prepared in Example 27 were checked for growth of mold and mosses Without treating surface treatment in the same manner in as in Example 37. Mosses gret-v within 1 month.

is lvv'hen inorganic cons truction materials such as masonary joint.

materials, (air-entrai-ned light concrete) plates, slate boards, calcium silicate boards, shaped cement materials, cured cement mortar, concrete, etc. are treated w_Lth the I'luorine-containing silane compound of the present invention, they are provided with improved water-repellency, oil-repellencY, stain resistance, weathering resistance, good adhesion of coating materials, etc. and further provided with resistances to freezing, growth of molds and mosses, etc. These construction materials can be coated with some other coating material before treated with the fluorine-containing silane compound of the present invention.

When these materials are treated with the fluorine-containing silane compound of the present invention, the compound is usually diluted with a suitable organic solvent in a concentra tion of 0.00120%, preferably-0.110% by weight.

Example 39

A masonary joint material was prepared by mixing 100 parts by weight of portland cement, 300 part by weight of sand, 0.2 part by weight of methyl cellulose and 60 parts y weight of water. This - material was applied to a 30cmx3Ocmx5cm concrete block to the thickness of 5mm by a trowel. After the material spread on the block was cured in moist air for 2 weeks, a 5% ethanol solution of Ce F, -, S02 N (CH,,) CH2CH2CH,, Si (OCH.3),, was applied on the material and dried. This test block was immersed 1 3 3 inwater to Scm from the base and allowed to stand in a room of 35T, and 95%RH for 3 months. No growth of molds and mosses was observed. Comparative Example 27 On the surface of the test block prepared in Example 39, 5% ethanol solution of CH3 Si (OCIL)a was applied and the block was tested in the same manner as in Example 39. Molds grew in 3 months. Example 40 An emulsion paint was prepared by mixing 40 parts by weight of an acrylic emulsion coating material ("EC720" marketed by Dai-,Nippon Ink Kogyo Kabushiki Kaisha), 25 parts by weight of titanium oxide, 0.2 parts by weight of sodium oleate and 0.3 part by weight of methyl cellulose. This paint was applied on the surface of a 1'00x50x3mm slate board. After the paint was dried, a 0.1010 ethanol solution of C a AFF1 -, S 0 2 X ( 'C26 Hr,) CH, CH2 CHz Si (OC1113) 3 was applied on the painted surface of the slate board once.

The edges and back s'Lde of this test plate were protected and the plate was subjected to an outdoor exposure test for 1 year.

After 1 year, blistering, peeling-off and stain of the paint on the surface were not observed. Comparative Example 28 On the painted surface of the test sLate plate prepared in Example 40, a 5% ethanol solution of CH3CONHG3 FIG Si (OCH3) 3 was applied and dried. The plate was subjected to the outdoor exposure test for 1 year in the same manner as in Example 40. Although blistering and peeling-off did not occur, the surface was remarkably stained.

-Comparative Example 29 On the painted surface of the test slate plate prepared in Example 40, a 5% ethanol solution of known Cs F17 COO- (CH2) 3 Si (OCH3) 3 was applied and dried. The plate was subjected to the outdoor exposure test for 1 year in the same manner as in Example 40. Although blistering and peeling-off did not occur, the surface was slightly stained. Example 41 3 4 A silica paint was prepared by mixing 20 parts by weight of a colloidal silica ("Snow Tex" marketed by Nissan Kagaku Kabushiki Kaisha), 10 parts by weight of titanium oxide, 20 parts by weight of calcium carbonate, 0.2 part by-weight of sodium oleate, 0.4 part by weight of methyl cellulose and 50 parts by weight of water. This silica paint was applied on the surface of a 150mmX50mmx3mm slate board. After the paint was dried, a 5% ethanol solution of Ca FL 7SOit N (C3H7) CH2 C% CHt Si (OCHa),3 was applied on the painted surface of the slate board once.

The edges and back side of this test plate were protected and the lower half of the plate was immersed in water. After 3 months, blistering and peeling-off did not occur and almost no stain was observed at the water level line.

Comparative Example 30 On the surface of the slate board coated with the SIlica paint prepared in Example 41, a 5% ethanol solution of CHL CH2 =C"j-C-O-C_, IL Si (OCHa)3 0 was applied and dried. The lower half of the slate board was immersed in water. After 3 months, the paint layer peeled off in the vicinity of the water level line.

*Example 42

A 150mmx40mmx40n.m ALC block was soaked in a 10% ethanol solution of C8 F1 7 S02 N (CH3) CH2CH, CH2 Si (OC, H,).3 for impregnation and dried. The test block was wholy immersed in water and subjected to a cycle test of freezing and thawing comprising chilling to -20'C for 2 hours and keeping at 30'C for 2 hours. Two cycles were conducted per day. After 50 cycles, cracking and breaking did not occur.

Comparative Example 31 The same ALC-block used in Example 42 was soaked in a 10% ethanol solution of Cg F, 7 CHR C;Hz CH2 Si (OCIL) 3 for impregnation and dried and subjected to the same test as in Example 42. Although no cracking and breaking occurred after 20 cycles of freezing and thawing, cracking occurred at 40 cycles and if the block broke at 50 cycles. Comparative Example 32 -10 The same ALC block used in Example 42 was soaked in a 10% ethanol solution of C3H7si(ocH3) a for impregnation and dried and subjected to the same test as in Example 42. The block chipped after 20 cycles of freezing and thawing and broke after 30 cycles. Example 43 On the surface of a 300=300=5mm slate board, a 10% ethanol.solution of Ca F, -, SO. N (C3 H-,) CH2 CH2CH2 SiC13 4 were applLed once and dried. '.,Jater permeamiability of this slate board was tested in accordance with the method of JISA6910. Even after 2-41 hours, no absorption of water was recognized. Comparative Example 3233 The same slate board as used in Example 43 was subjected to the - being treated with the fluorine-containing test of Example 43 without silane compound. After 1 hour, water in excess of 30ml was absorbed.

Example 44

A cement block was made by mixing 100 parts by weight of portland cement, 200 parts by weight of sand and 40 parts by weight of water and mouldirig. The block was cured for 1 day at room temperature. A 5% ethanol solution of Ce F1 7 SO. N (CH) CH CH,. CH. Si (OCH,) 3 was applied on the surface of the block and dried. The side and back surfaces were protected and the block was allowed to stand under the conditions of 51C and 95% humidity. No deposition of alkali occurred even after 1 month.

Comparative Example 34 The cement block made in Example 44 was subjected to the same test without being treated with the fluorine-containing silane compound. After 1 week, deposition of alkali on the surface occurred.

When the surface of metals such as copper, a typical electroconductive material, gold, silver, iron, aluminum and various kinds of alloys is treated with the fluorine-containing silane compound of the present invention, it repels molten solder and soldering paste and loses solderability. That is, the treated 24 surface becomes unsolderable. Solderability can be easily regained by removing, by scraping for instance, the fluorine-containing silane compound layer and thus the treated metal sheet will be used for manufacturing integrated circuits.

Example 45

A'0.5% ethanol solution of Ca F, 7 S02N(C3 H7) CH2 CH2 CH2 Si (OCH3) 3 containing 0.3% by weight of a 10% sulfuric acid solution was applied to a 10060ximm copper plate. On the surface of this treated copper plate, -molten tin -lead solder was dropped. After cooled, the solder drop did not adhere to the copper plate and readily removed when lightly touched upon.

-s treated with the fluorine-containing When inorganic pigment silane compound of the present invention are incorporated in coating compositions, the pigments are well d4Lspersed and stable coating compositions are obtained. Tnorganic pigments treated with the L. LI %.I fluorine-containing silane compound of the present invention are superior in whiteness in the case of white pigment, tinting strength and 11., Liding power. Treatment of inorganJc pigments with the fluorinecontaining silane compound of this invention has been explained in the above. Example 46 While 1CO parts by weight of titanium oxide pigment was being agitated at high speed by a Henschel. mixer, a solution of 0.1 part by weight.of C. F,, SOP, N(C3 R,) CH2 CH2 CHz Si (OCH3).3 in 10 parts by weight of acetone was added to the pigment dropwise. _After the addition thereof was finished, the mixture was kept at 1501C for removing the solvent. The pigment was repulverized by a fluid jet mill and thus a titanium oxide pigment treated with the fluorinecontaining silane compound of the present invention was obtained. This titanium oxide pigment was mixed with the materials listed below (Formula 1) and a white paint was obtained.

1 77 Formula 1 Ingredient Treated titanium oxide pigment "Lumiflon LF-20OC" (a fluorine resin solution supplied by Asahi Glass Co., solid content 60%) lylene Methylisobutylketone Isocyanate (hardener) parts by weight 30 142.9 35.7 107.1 13.3 This coating composition was applied on hiding power testing paper to a thickness of 0.00254cm (10mil). The thus coated paper used as a test specimen and the L, a, b values of the white part thereof were measured. The whiteness was calculated as 100 - 1- 2+e +Y -e part was measured by q 10_0-L)-. Then gloss at 600 of the whit a gloss meter, and the hiding ratio ((reflectiVity of black part)/ -1) was determinded by a reflec-11-oneter.

(reflectivity of whJj.Ue part, %11 Furi.her, a black paint of the same formula as above in which 1.5 parts by weight of carbon black was used instead of 30 parts by weight of titanium white was prepared. Thirty (30) parts by weight of the black paint was mixed with 100 par-Us by weight of the above described white paint and the tinting strength of the white paint was checked. The results are shown in Table 20.

Comparative Example 35 A white paint of Formula 1, in which untreated titanium oxide was used, was prepared and its whiteness, 600 gloss, hiding power, tinting strength were checked in the same manner as in Example 46. The results are shown in Table 20. Example 47 In a solution of 10 parts by weight of C. F,, SO,, N (CH3) CHI, CHI, CH. Si (OCH3)., - in 300 parts by weight of ethanol, 100 parts by weight-of titanium oxide was dispersed in the same manner as in Example 46 and thus titanium oxide which was treated with said fluorine-containing silane. compound was obtained. A white paint was prepared in accordance with the formula and procedures as descibed in Example 46. The same test as in Example 46 were carried out with respect to specimens coated with this white paint. The results are shown in Table 20.

29 Comparative Example 36 A white paint was prepared in the same manner as in Example 47 except that non-fluorine containing CH3 CONII (CH2) 3 Si (OCH3)3 was used as a surface treatment agent. The same test as in Example 46 were carried out with respect to specimens coated with this -white paint. The results are indicated in Table 20. Example 48 Thirty (30) parts by weight of titanium oxide was dispersed it f toluene and 6 -parts by weight of 10, 114.2 parts by weight of.

G. F17S02N(CH3) CR, CH2 CR, Si (OC, Hs)3 was added to the dispersion and the mixture was mixed and stirred for 60min. After 171.5 parts by weight of a fluorine resin solution ("Lumiflon LF-100% a fluorine resin solution marketed by Asahi Glass Co., solid content 50%) was added and the mixture was stirred for 60min, 5.2 parts by weight of melamine was added and the mixture was stirred for 1.5Min and thus a white paint was obtained. A test specimen was prepared by applying this paint on a polished steel sheet to the thickness of 70g/m' and baking the coated sheet at 200T for 5min. The whiteness, 60 gloss, hiding power and tinting strength were measured. The results are shown in Table 20.

Reference Example One hundred (100) parts by weight of calcium carbonate powder was dispersed in a solution of 5 parts by weight of C, F, s GO, (CH2) 3 Si (OCH3) 3 in 300 parts by weight of ethanol and the dispersion was stirred for 60min. Calcium carbonate powder treated with said fluorine containing silane compound was obtained by filtration and drying. A white paint was'prepared by mixing this calcium carbonate powder with the materials listed below (Formula 2).

- 38 1 31 Formula 2 Ingredient Treated calcium carbonate powder Titanium oxide "Lumiflon LF-100" (a fluorine resin solution marketed by Asahi Glass Co., solid content 50%) Toluene Melamine (hardener) parts by weight 5 171.2 114.2 5.2 This white paint was applied on the surface of hiding power test paper and the paper was baked at 130t for 40min. Whiteness, 600 gloss, hiding power and tinting strength of this paint were measured in the same manner as in Example 46.

Table 20

Example Ex.

46 47 48 51 Comp. Ex. 35 36 39 Whiteness 60 gloss Hiding powder Tinting strength 88 87 88 85 84 8ES 84 78 77 75 74 75 72 92 91 82 8'15 85 125 118 107 Numbers represent values when it is assumed that the tinting strength with respect to untreated pigment is 100.

Examples 49 30 Red iron oxide was treated with Ct F17SQ, N (M) C1 CH, CH, Si (OM) 1 in the same manner as in Example 48 and mixed with the materials listed below (Formula 3) to prepare a paint.

Formula 3 Ingredient Treated pigment Carcium carbonate Toluene "Lumiflon LF-10V (a fluorine resin solution supplied by Asahi Glass Co., solid content 50%) Isocyanate (hardener) parts by weight 2 10 50 3.7 The paint-was applied on a 50mmx150mm slate board to a thickness-of 150g/m2. The thus prepared test specinen was tested by a colorimeter to measure L, a and b values. The color difference AE between the case when titanium oxide was added and the case when it was not added was calculated as AE.= (AL)2+(Aa)2+(Lb) 2.

A paint was prepared in the same manner as above except that untreated red iron oxide was used. The color difference AE' was measured with respect to a specimen which was prepared in the same manner as above. The value AE/AE' was indicated in Table 21 as an index of tinting strength of treated pigment. Generally, when this value is smaller than 1 and that it is more smaller, the tinting strength is smaller. The AE/AE' value of this-pigment was 0.85 as shown in Table 21.

Example 00

A paint was prepared in the same manner as in Reference Example except that black iron oxide treated with 10% of C. F17SOP. N (Q3H7) CH CH, CH, Si (OCI-I),, was used and tested in the same manner. The AE/AP value was 0.95.

Comparative Example 37 A paint was prepared in the same manner as in Reference Example except that red iron oxide treated with 0.1% of C3 H7 Si (OM) 3 was.used and tested in the same manner. The AE/AP valuevas 0.98.

Comparative Example 38 A paint was prepared in the same manner as in Reference Example except that black iron oxide treated with 10% of C14 CONH (CH.) 3Si (OCH),, was used and tested in the same manner. The AE/AP value was 0.95.

f 1 is 4-1 The results of Example 49 through Comparative Example 38 are summarized in Table 21.

Table 21

Ex. Pigment F-containing silane Amount. &E/,&E' 49 Red iron-oxide C. F, 7 SQ, N (CH3) (CH2) 3 Si (OCH3) 3 0.1 0.85 Black iron oxide C. F, -, SQ, N (C, H.I) (CH)., Si (OCIlz,), 10.0 0. 75 10. Comp. LL - - -37 Red iron^oxide C3 H7 Si (OCII3) 3 38 Black iron oxide CH,, CON71 (CH.,)., Si (OCH,3) -, Example 51

0.1 0.95 10.0 0.95 A super-fine silica powder ("Aeros--Ll -"r200" marketed by Nippon Aerosil Kabushiki Kaisha), which is a paint additive having thickening effect, was treated with 3.0% by weight of the fluorinecontaining silane compound used in Example 47, that is, C. F! 7 SO, N (CH3) M CH2 CH, Si (OCH3) z and a paint was prepared using the materials listed below (Formula 4).

Formula 4 Ingredient parts by weight Treated super fine silica powder 2 10 titanium oxide pigment "Lur,Liflon LF-3OW' (a low viscosity fluorine resin solution marketed by Asahi Glass Go.) 30 Toluene 60 Isocyanate (hardener) 2.8 With respect to this paint, the same test as employed in Example 46 was carried out. The results are indicated in Table 20.

Comparative Example 39 35- A paint was prepared in the same manner as in Example 51 except that untreated super-fine silica powder was used and the paint was tested in the same manner. The paint of Example 51 was superior to that of this comparative example by 2.3% in whiteness, by 3.6% in 6W 4-L gloss and by 8.4% in hiding'power.

These paints were centrifuged and allowed to stand for checking the settling property. The paint prepared using the super-fine silica powder treated with the fluorine-containing silane compound did not settle when it was centrifuged at 10OOrpm for 30min. The paints-prepared using the untreated super-fine silica powder was settled under the same condition. It was proved that the super-fine silica powder treated with the fluorinecontaining silane compound of the present invention was superior in thickening property to that -prepared with the untreated super-fine silica powder.

The fluorine-containing silane compounds of the present - invention improve water- and oil-repellency, staining resistance, resistance to organic solvents of wax when they are added therero. For this purpose, the compounds are added to wax in an amount of 0.1 is to 2011YG by weight of wax, preferably 1 to 5% by weigh-t. Usually the compounds are admixed with wax in the form of a melt. However, it can be admixed with wax in the form of a solution in a suitable solvent. Example 52 3.5g of C. F, -, SO,. N (C.3 H7) CH, CH2CH2Si (OCH)., was admixed with melt of 100g of a cormercially available wax ("Hoechst 1.,vax S" marketed by Nippon Hoechst Kabushiki Kaisha) and the mixture was applied on the surface of a 5mm thick slide glass. The contact angles for water and liquid paraffin were measured. They were respectively 123 and 82.. Those of the neat wax were 91 and 280 respectively.

_Comparative Example 40 The procedures of Example 52-were repeated with respect to a commercially available fluorine containing surfactant ("MOP-201 marketed by New Akita Chemical Co.) instead of said fluorine containing silane cQmpound and the contact angles of the thus modified wax were lOr for water and 45" for liquid paraffin.

1 i fl e 4.3

Claims

What we claim is:

1. An N-alkyl-N-[3-(substituted-silyl)propyl]-perfluoroalkylsulfonamide represented by the formula C, F2, 1 SO,% NRI CHz CHa CRI SiR2,3 -, A. wherein R' is an alkyl group having 1-5 carbon atoms, R2 is an alkyl group having 1-5 carbon atoms, A is a group selected from chlorine, bromine and an alkoxy group having 1-5 carbon atoms, n is an integer of 4- 12 andis an integer of 1-3.

2. The compound recited in Claim 1, wherein A is methoxy, ethoxy or 10 chlorine.

3. The compound recited in Claim 1, wherein n is an integer of 6-10.

4. The compound recited in Claim 3, wherein n is 8.

5. The compound recited in Claim 1, wherein R' is propyll.

6. The compound recited in Claim 1, wherein R2 is methyl or ethyl.

7. The compound recited in Claim 1, wherein m is 3.

und recited in Claim 1, which is N-n-propyl-N-[3-(tri-

8. The compou chlorosilyl)propyl]-perfluorooctylsulfonamide.

9. The compound recited in Claim 1, which is N-n-propyl-N-[3(trimethoxysilyl)propyl]-per.loluorooctylsulfonamide.

10. A process for preparing NalkyL-N-[3-(substituted-silyl)propyl]perfluoroalkylsulfonamide represented by the formula C, F2 n. IS02NRICHzW,CH2 SiR2 3 -, A, (I) wherein R, is an alkyl group having 1-15) carbon atoms, R' is an alkyl group having 1-5 carbon atoms, A is a group selected from chlorine, bromine and an alkoxy group having 1-5 carbon atoms, n is an integer 1VI.

of 4-12 and z is an integer of 1-3, comprising reacting a compound represented by the formula Q F2,. 1 S02 NRI CH2 CH =CHa (I1) wherein R, and n are as defined above, with a compound represented by the formula RSiR2 A. (III) wherein R, A and m are as defined above, in the presence of an addition catalyst.

11. The process recited in Claim 10, wherein the addition catalyst is a compound selected from chloroplatinic acid, azo- bis isobutyronitrile, benzoyl peroxide, an octacarbonyl complex of cobalt, platinum or rhodium.

12. The process recited in Claim 10, wherein, when A is chlorne or it v bromine, the addition product is further reacted with an alcohol having 15 carbon atoms.

13. The process recited in Claim 12, wherein the reaction of the addition product and the alcohol is conducted by blowing dry air into the reaction mixture.

14. The process recited in Claim 12, wherein the reaction of the addition product and the alcohol is conducted under a reduced pressure.

15. The process recited in Claim 10, wherein, when A is chlorine or bromine, the addition product is further reacted with an alkoxide of an alcohol having 1-5 carbon atoms.

16. The process recited in Claim 10, t-. lherein, when A is chlorine or bromine, the addition product is further reacted with orthoformic acid ester of an alcohol having 1-5 carbon atoms.

-ituted-s-lyl)-propyl]-

17. A process for preparing N-alkyl-N-[3-(subst perliluoroalkylsulfonan,ide represented by the formula C, F2,., 1 SO,.XRI CH2 CH2 CH2 SiR2 3 -, A, (I) wherein R- is an alkyl group having 1-5 carbon atoms, R2 is an alkyl group having 1-5 carbon atoms, A is an alkoxy group having 1-5 carbon - v' atoms, n is an integer of 4-122 and 4 is an integer of comprising reacting a compound represented by the formula Q F2 ELt 1 S02 Y wherein Y is fluorine, chlorine or bromine, with a compound represented by the formula NRI. CH CH, CHa SiR2 3 A.

(IV) (V) wherein R, R2, m and A are as defined above.

+ion is

18. The process as recited in Claim 17, wherein the reac. conducted in the presence of an organic base.

19. The process recited in Claim 17, wherein pyridine or triethylamine is used as an organic amine.

20. The process recited in Claim 17, wherein the compound of formula (IV) is used in an amount of more than 1 mole equivalent to the amount of the compound of formula (V).

21. The process recited in Claim 17. wherein the compoufld of formula (M is used in an amount of 1.05 to 1.2 mole equivalent to the amount of the compound of formula (V).

22. A water- and oil-repellent for inorganic materials comprising a compound recited in any of Claims 1-9.

4 i It.<

23. A fluorine resin composition containing inorganic filler treated with 0.1-10% by weight of a compound recited in any of Claims 1 is -ftc-'Lt"i Ik

24. An inorganic powder of fiber be the surface of which 0.1-20% by weight of a compound recited in any of Claims 1-9.

25. A metallic material the surface of which is treated with a compound recited in any of Claims 1-9.

26. A paper material the surface of which is treated with a compound recited in any of Claims 1-9.

27. A glass material the surface of which is treated with a compound recited in any of Claims 1-9.

28. An inorganic construction material which is treated with a compound recited in any of Clainis 1-9.

29. A coating composition which contains pigment treated with 0.1 20% by weight of a compound recited in Claims 1-9.

Published 1989 at Tj3e patent office, State House. 6671 High HoIbOrn, LordonWGlR4TP. Further copies mkvl>e obtained from The Patent Office. Beaes Branch. St UW7 CraY, Orpington, Rent BR5 3RD. Printed by Multiplex techniques ltd, St Mary Cray, Kent, Con. 1/87 Bales Dranu",.. -.y -- -.