FR2630443A1 - NOVEL FLUORINATED SILANES, PROCESSES FOR PREPARING SAME, WATER-REPELLENT AND WATER-REPELLENT AGENT CONTAINING THEM, AND VARIOUS MATERIALS TREATED OR CONTAINING AN INGREDIENT TREATED WITH THEM - Google Patents

Abstract

The invention relates to N-alkyl-N- [3- (substituted silyl) propyl] -perfluoroalkylsulfonamides of the formula: Cn F2n & I1 A1 SO2 NR ** 1CH2 CH2 CH2 SiR ** 23-m Am in which R ** 1 is a C1 -C5 alkyl group, R ** 2 is a C1 -C5 alkyl group, A is chlorine, bromine or a C1 -C5 alkoxy group, n is an integer from 4 to 12 and m is an integer of 1 to 3. These compounds provide good water and oil repellency characteristics and serve as surface property improvers for treating various materials such as mineral fillers for resin compositions, powders and fibers minerals, metals, paper, glass, building materials and pigments for paints. Field of application: surface treatment agents.

Description

The present invention relates to a class of

  new N-alkyl-N- [3- (substituted silyl) propyl] -perfluo-

  ralkylsulfonamides, processes for their preparation and their uses. The compounds of the present invention can be used as surface modifiers

for various materials.

  Silanes comprising one or more perfluoroalkyl groups are known and their use as agents

  mold release is currently being considered.

  Recently, there has been a desire to improve the hydrophobicity, oleophobicity and nonadhesiveness of resins as well as mineral materials. Conventional silanes are not satisfactory with regard to hydrophobicity, oleophobia and non-adhesiveness when used as agents

  improvement of surface properties.

  Silanes having one or more perfluoroalkyl groups have good characteristics

  hydrophobia and oleophobia but are still unsatisfactory

  doing with regard to adhesion to materials

  of substrates and thermal and chemical stability. Some-

  some of them have the disadvantage that the starting materials used for their preparation decompose during the hydrosilylation reaction of their synthesis,

  which results in a low product yield.

  The Applicant has carried out an in-depth study in order to overcome the abovementioned drawbacks and has discovered that certain silanes, the molecule of which comprises a perfluoralkyl group and a sulfonamide group, obviate the abovementioned drawbacks and meet the aim of the present invention. The present invention provides a class of

  new N-alkyl-N- [3- (substituted silyl) propyl] -perfluo-

  ralkylsulfonamides represented by the formula:

C F SO NR1 CHCH CHSR2A)

  Cn 2n + 1S 2 C22CH2SiR 3-mAm () in which R is a C1C5 alkyl group, R is a C1-C5 alkyl group, A is chlorine or bromine or a C1-C5 alkoxy group, n is a whole number of

  4 to 12, and m is an integer from 1 to 3.

  i Preferably, R is a C1-C1-alkyl group, R2 is a C1-C3 alkyl group, A is methoxy or ethoxy or chlorine, n is 6 to 10, and

m is 3.

  More preferably, R is the n-propyl group, R is the methyl or ethyl group, A is the

  methoxy or ethoxy group, n is 8, and m is 3.

  The present invention also provides

  processes for preparing N-alkyl-N- [3- (substituted silyl) -

  propyl] -perfluoralkylsulfonamides referred to above.

  The compounds of the present invention can be prepared by a process consisting in reacting an N-allyl-N-alkyl-perfluoralkylsulfonamide represented by the formula: CnF2n lSO2NR CH2CH = CH (II) n 2n-I-2 2 H (l in which R1 and n are as defined above,

  with a halogeno-, alkoxy- or alkoxyhalosilane represented

  sensed by the formula: HSiR2 A (III) 3-mm in which R2, A and m are as defined above, in the presence of an addition reaction catalyst, and to further react the addition product resulting with

  a C1-C5 alcohol when A is chlorine or bromine.

  The compounds of formula (II) can be pre-

  prepared by reacting a perfluoralkylsul fluoride

  fonyl prepared by electrolytic fluorination with an N-alkylallylamine, or by reacting a perfluoralkylsulfonyl fluoride with a Nalkylamine to form

  an N-alkylperfluoralkylsulfonamide, then by reacting

  gir the latter with an allyl halide in the presence

of an alkaline base.

  These compounds are produced by New Akita Chemical.Co., Ltd. (Shin-Akita Kasei Kabushiki Kaisha) and N-n-propyl-N-perfluoroctylallylsulfonamide

  is marketed by this company.

  The compounds of general formula (III) are also commercially available, for example

  with Tokyo Kasei Kabushiki Kaisha.

  In the process described above, the cataly-

  preferred addition reaction sors are chloro-

  platinum, azobisisobutyronitrile, benzoyl peroxide and an octacarbonyl complex of cobalt, platinum

or rhodium.

  In the process described above, the reaction of the adduct, where A is chlorine or bromine, with a C1-C5 alcohol can preferably be carried out, by blowing dry air into the reaction mixture, or under reduced pressure. The vacuum must be sufficient to remove the hydrogen halide formed, but not excessive to avoid causing loss of the alcohol used. The reaction of the adduct, where A is chlorine or bromine, with said alcohol can also be carried out, preferably, in the presence of a base

such as an organic amine.

  The compounds of the present invention o A is a C1-C5 alkoxy group can also be prepared by reacting the adduct of the compound of formula (II) and of the compound of formula (III)

  with a corresponding metal alcoholate.

  The compounds of the present invention where A is a C1-C5 alkoxy group can also be prepared by reacting the adduct of the compound of formula (II) and the compound of formula (III) with a

  orthoformic acid ester of the corresponding alcohol.

  The compounds of the present invention represent

  ted by formula (I) o A is a C1-C5 alkoxy group can be prepared by a process consisting in reacting a compound represented by the formula: CnF2n + lSO2Y (IV) in which Y is fluorine, chlorine or bromine and n is as defined above, with an aminosilane represented by the formula: 1.2A NR CH2CH2CH2SiR 3-mAm (V)

R1 2

  in which RI, R2 A and m are as defined pre-

  cedent. In the compounds of the present invention represented by formula (I), the alkyl group R1 can

  be straight or branched chain.

  A compound represented by formula (III) is used in an amount of 1 or more molar equivalents, preferably 1.3 to 1.5 moles, per mole of the compound of formula (II). The reaction of a compound of formula (II) and a compound of formula (III) is carried out at a temperature of 30 to 150 C, preferably 40 to 80 C,

under agitation.

  The amount of catalyst to be used is generally from 1 x 10- 5 to 1 x 10 2%, preferably

4 4

  1 x 104 to 5 x 10 4%, by weight relative to the quan-

tity of the compound of formula (II).

  The reaction of a compound of formula (I) o A is chlorine or bromine with a C1-C5 alcohol can be easily carried out by blowing an anhydrous inert gas into the reaction mixture at a temperature of 5 to 40 C, preferably from 10 to 20 C, or by shaking

  the reaction mixture under reduced pressure.

  The gas must be inert with respect to the compound of formula (I) o A is chlorine or bromine and C1-C5 alcohol; in particular, N2, He, Ar, etc.,

dried are preferred.

  The blowing of the anhydrous inert gas is carried out to remove the released HC1 or HBr, and evacuation has the same effect. If the pressure is

  excessively reduced, vapor loss occurs

the alcohol used.

  When the compounds of the present invention represented by formula (I), where A is a C1-C5 alkoxy group, are prepared by the reaction of a perfluoralkylsulfonyl chloride (compound of formula (IV)) and an aminosilane (composed of formula (V)), it

  it is preferable that the first is used in a quan-

  tity greater than the molar equivalent, preferably from 1.05 to 1.2 molar equivalent, of the amount of the second. The reaction of the compound of formula (IV) and of the compound of formula (V) is preferably carried out in the presence of an organic base such as pyridine, triethylamine, etc., in order to remove the hydrogen halide formed Although it is not necessary to use a solvent, an inert solvent can be used in the reaction without any particular limitation. Particular examples of such solvents are ethers such as tetrahydrofuran, isopropyl ether, etc. Although the reaction temperature differs depending on the nature of the solvent used, it is generally between room temperature and 100 C, preferably between 20 and 50 C. The sulfonamide fragment of the compounds of the present invention increases the yield of the reaction. hydrosilylation of their synthesis and achieves a better orientation of the perfluoralkyl group than carboxylic acid or carboxylic amide fragments in their use as modifiers of properties of

  surface, thereby improving hydrophobicity, oleopho-

  bie and the non-stickiness of the substrate.

  In addition, the alkyl group linked to the atom

  nitrogen promotes miscibility with organic solvents.

  The compounds of the present invention are useful as modifiers of surface properties

  water and oil repellents, and for other uses.

  The present invention also relates to powder fillers or short fiber fillers to the surface of which one of the silanes is bonded or adhered.

described above.

  The present invention also relates to fluorinated resin compositions containing a filler

  mineral treated with one of the silanes described above.

  The present invention also relates to hydrophobic and oleophobic paper and glass, treated

  with the silanes described above or containing them.

  The present invention also relates to building materials resistant to the action of atmospheric agents, the surface of which has been treated.

with the silanes described above.

  The present invention also relates to hydrophobic, oleophobic and unsoudable electrically conductive metallic materials, the surface of which has been treated.

  by one of the silanes described above.

  The present invention also relates to mineral pigments and mineral fillers, which have been treated with the silanes described above and which. offer good dispersibility in organic solvents and give less viscous coating products (paints). The hydrophobicity, oleophobicity and nonadhesiveness of the silanes of the present invention are manifested by their perfluoralkyl group, and their halo or

  alkoxy react with water to be converted to grou-

  pes hydroxysilyles which combine with the hydroxyl groups existing on the surface of mineral matter by condensation with dehydration, hydrogen bonding, etc. When a compound of the present invention is applied to or incorporated into the surface of a material, it is normally used as a solution in an organic solvent. The method of application or mixing is not particularly limited. Preferably, the compound is dissolved in an anhydrous chlorinated solvent, a fluorinated solvent, acetone, tetrahydrofuran, hexane, an alcohol, etc. , or a mixture thereof, or a solvent to which is added a small amount of an aqueous solution of an amine or an acid, and the solution is applied to the surface of an object by a known method such than spraying, soaking, etc. The present invention will now be illustrated

by examples.

Example 1

  108.1 g (0.200 mole) are placed in a 500 ml flask with three tubes fitted with a magnetic stirrer, a thermometer and a reflux condenser.

  of N-n-propyl-N-perfluoroctylsulfonamide ("EF-111" commercially

  marketed by New Akita Chemical Co.), 15.4 g (0.233 mole) 85% potassium hydroxide and 200 ml acetone, and 30.71 g (0.254 mole) bromide is added dropwise allyl to this mixture in a period of

  minutes at room temperature. After having-

  followed further by stirring for 4 hours, the reaction mixture is filtered, the filtrate is concentrated by distillation to reduce its volume to 100 ml and it is poured

  in a 5% aqueous solution of ammonium chloride.

  The organic phase is collected, the distillation of which

  under vacuum gives N-n-propyl-N-allyl-perfluoroctylsul-

fonamide.

  Then, in a balloon with three tubes of

  ml equipped with a magnetic stirrer, a thermometer

  tre and a reflux condenser, 96.9 g are placed

  (0.167 mole) of N-n-propyl-N-allyl-perfluoroctylsulfo-

  namide above and 5 mg of a 0.1M isbpropanolic solution of chloroplatinic acid hexahydrate (9.67 x 10 3 mmol), and 25.3 ml (0.250 mol) of trichlorosilane are added dropwise over one period 30 min. Stirring is further continued for 2 hours after the addition of the trichlorosilane is completed, then the reaction mixture is distilled under vacuum to obtain

  , 3 g (0.1539 mole) of N-n-propyl-N- [3- (trichlorosilyl) -

  propyl] -perfluoroctylsulfonamide. Yield: 92.3%; Eb. 153 C / 26.7 Pa. The compound is identified as: c CH b a

CH2CH2CH3

2 f e3 d C8F17SO2N-CH2CH2CH2SiC13

  by NMR analysis, SM analysis and spectrophotometric analysis

IR stick.

  The conditions and results of the analyzes are as follows: 1 H NMR analysis:

  Solvent: Freon-113 (1,1,2-trichloro-1,2,2-

  trifluoroethane), Internal standard: benzene 61.30 (t, 3H, H-a); 1.6-2.5 (m, 6H, H-b, d, e);

3.5-4.0 (m, 4H, H-c, f).

  Analysis SM: Ionization voltage: 70 eV m / e, the relative intensity and the fragment are as follows, in this order: 554, 60.5%, M - CH2CH2SiCl3; 133, 15.0%, SiCl3; 69,

%, CF3.

  IR spectrophotometry: Sample: solvent-free -1

3350, 2950, 1390, 1260-1130 (cml.

Example 2

  48.1 g (0.0671) are placed in a 300 ml balloon with four tubes fitted with a mechanical stirrer, a separator, a thermometer and a reflux condenser to which a suction pump is connected. mole)

  N-n-propyl-N- [3- (trichlorosilyl) propyl] -perfluoroctyl-

  sulfonamide and 50 ml of methanol are added dropwise over 2 hours at a temperature

  from 15 to 20 C under reduced pressure. Then by distil-

  lation under vacuum, 40.1 g (0.057 mole) of

  N-n-propyl-N- [3- (trimethoxysilyl) propyl] -perfluoroctyl-

  sulfonamide. Yield: 85.0%; Eb. 134 C / 33.3 Pa (0.25 mm Hg). The compound is identified as: CH2cCH2bCH3 C8F17SO2N-CH2C2CH2Si (OCH3) 3

  by NMR analysis, SM analysis and spectrophotometric analysis

IR stick.

  The conditions and results of the analyzes are as follows: NMR analysis of H: Solvent: Freon-113; Internal standard: benzene, 9 (t, 2H, H-e); 1.25 (t, 3H, H-a); 1.6-2.5 (m, 6H, H-b, e, f); 3.5-4.0 (min, 4H,

H-c, g); 3.8 (s, 9H, H-d).

  Analysis SM: Ionization voltage: 70 eV m / e, the relative intensity and the fragment are as follows, in this order: 672, 22.6%, M + - OCH3; 554.1.8%, M - CH2CH2Si (OCH3) 3;

121, 100%, Si (OCH3) 3; 69, 23%, CF3.

  IR spectrophotometry: Sample: solvent-free

  3350, 2950, 1390, 1260-1130, 1090 (cm 1).

Example 3

  In a 300 ml flask with four tubes fitted with a magnetic stirrer, a thermometer, a reflux condenser to which a separator is connected, and a nitrogen inlet tube, place 50.2 g (0.070 mole)

  N-n-propyl-N- [3- (trichlorosilyl) propyl] -perfluoroctyl-

  sulfonamide and 50 ml of methanol are added dropwise at a temperature of 10 to 15 C over a period of 5 hours while vigorously blowing in nitrogen

  gas in the bottom of the balloon. After completing the addi-

  methanol, the reaction mixture is further stirred

  for 5 hours. Then, by removing excess metha-

  nol by vacuum distillation, 38.2 g are obtained

  (0.054 mole) of N-n-propyl-N- [3-trimethoxysilyl) propyl] -

  perfluoroctylsulfonamide. Yield: 77%.

Example 4

  In a 500 ml flask with three tubes fitted with a mechanical stirrer, a thermometer, a reflux condenser and a stopcock bulb,

  place 143.3 g (0.20 mole) of N-n-propyl-N- [3- (trichlo-

  rosilyl) propyl] -perfluoroctylsulfonamide sprayed and 121.2 g (1.2 mole) of triethylamine and 96 g (3.0 mole) of methanol are added dropwise over 2 hours at a temperature of 15 to 20 C while stirring and cooling the flask with ice water. After the addition of methanol, the salt produced is filtered off and obtained by distillation.

  in vacuum 130.9 g (0.186 mole) of N-n-propyl-N-

  [3- (trimethoxysilyl) propyl] -perfluoroctylsulfonamide.

  Yield: 92.0%; Eb. 134 C / 33.3 Pa (0.25 mm Hg).

Example 5

  71.7 g are placed in a 300 ml flask with three tubes fitted with a mechanical stirrer, a reflux condenser and a stopcock bulb.

  (0.10 mole) of N-n-propyl-N- [3- (trichlorosilyl) -propyl] -

  perfluoroctylsulfonamide and 75 g of a 28% methanolic CH3ONa solution are added dropwise to a

  temperature from 15 to 20 Cen a period of 2 hours.

  After the addition of the methylate, the salt produced is separated by filtration and by distillation under

  empty, 65.4 g (0.093 mole) of N-n-propyl-N- are obtained

  [3-trimethoxysilyl) propyl] -perfluoroctylsulfonamide.

Yield: 93.0%.

Example 6

  In a 300 ml flask with four tubes fitted with a mechanical stirrer and a refrigerant

  reflux, 83.6 g (0.10 mole) of N-ethyl-N- are placed

  [3- (tribromosilyl) propyl] -perfluoroctylsulfonamide and 133.2 g (0.9 mole) of ethyl orthoformate. To this mixture, 3.0 g of aluminum chloride is added as catalyst and the mixture is left to react at 80 ° C. for

12 hours.

  After completion of the reaction, 55.6 g (0.076 mol) of N-ethyl-N- [3- (triethoxysilyl) propyl] perfluoroctylsulfonamide are obtained by vacuum distillation.

  Yield: 76.1%; Eb. 146 C / 24.0 Pa (0.18 mm Hg).

Example 7

  53.1 g (0.10 mole) of Nn-propyl-perfluoroheptylsulfonamide, which has been treated, is placed in a 100 ml flask with three tubes fitted with a magnetic stirrer, a thermometer and a reflux condenser. supplied by New Akita Chemical Co., and 10 mg (1.9 x 10 mole) of chloroplatinic acid, and 14.9 g (0.11 mole) of trichlorosilane are added dropwise through a stopper funnel in a 1 hour period at 60 C. After

  still stirred for 1 hour, the excess tri-

  chlorosilane by distillation to obtain 61.3 g

  N-n-propyl-N- [E3- (trichlorosilyl) propyl] -perfluoroheptyl-

  sulfonamide. Yield: 92%. We confirm that the product was: c b a f2 e2 d3

ccH2cbH2caH3-

  CH tf e d C7H15SO 2NC H2C H2C H2SiC13 i

  by H NMR analysis, SM analysis and spectrophoto analysis-

IR metric.

  The conditions and results of the analyzes are as follows: 1 H NMR analysis: Solvent: Freon-113; Internal standard: benzene 6 1.25 (t, 3H, H-a); 1.62.5 (m, 6H, H-b, d, e);

  3.5-4.0 (m, 4H, H-c, g); 6 (s, 9H, H-d).

  Analysis SM: Ionization voltage: 70 eV m / e, the relative intensity and the fragment are as follows, in this order: 504, 68.1%, M ++ CHC2il SC3 M CH2CH2SiCl3; 133, 21.1%, SiCl3; 69, 100%, CF3. IR spectrophotometry: Sample: solvent-free

3350, 2950, '1390, 1260-1130 (cm 1-

3350, 2950, 1390, 1260-1130 (cm-1).

Example 8

  In a 500 ml flask with three tubes fitted with a magnetic stirrer, a thermometer and a reflux condenser, 133.3 g (0.20 mole) of Nn-prolyl-N- [3- trichlorosilyl) propyl] -perfluoroheptylsulfonamide, having been supplied by New Akita Chemical Co., and 200 ml of methanol are added dropwise through a dropping funnel over a period of 5 hours at

   C under a reduced pressure of 9.33 kPa. After the addi-

  tion of methanol, obtained by vacuum distillation

  , 8 g of N-n-propyl-N- [3- (trimethoxysilyl) propyl] -

  perfluoroheptylsulfonamide. Yield: 81%. It is confirmed that the product is: c cH2CHC H3

2 2 3

C7H15SO2NC CH2C H2 Si (OCHd 3) 3

  by H NMR analysis, SM analysis and spectropho-

IR tometer.

  The conditions and results of the analyzes are as follows: NMR analysis of H: Solvent: Freon-113; Internal standard: benzene 6 0.9 (t, 2H, H-e); 1.25 (t, 3H, H-c); 1.6-2.5 (m, 6H, H-b, f); 3.5-4.0 (m, 4H, H-c,

g); 3.8 (s, 9H, H-d).

  Analysis SM: Ionization voltage: 70 eV m / e, the relative intensity and the fragment are as follows, in this order: 622, 24.5%, M + - dOCHd; 504, 3.4%, M + - + CH2CH2Si (OCH3) 3;

  121, 100%, Si (OCH3) 3; 69, 100%, CF3.

  IR spectrophotometry: Sample: solvent-free

  3350, 2950, 1390, 1260-1130, 1090 (cm 1-

  3350, 2950, 1390, 1260-1130, 1090 (cm-1).

Example 9

  73.4 g (0.20 mole) of N-ethyl-N-allyl-perfluorobutylsulfonamide are placed in a 300 ml flask with three tubes fitted with a magnetic stirrer, a thermometer and a reflux condenser. and 5 ml

  0.1M isopropanolic solution of chloroplatinic acid

  (9.67 x 10- 3 mmol), and 27.6 g (0.24 mol) of methyldichlorosilane at 60 ° C. are added dropwise over a period of 1 hour. After having completed the addition, the stirring is still continued for 1 hour at the same

  temperature. N-ethyl-N- is distilled off

  allyl-perfluorobutylsulfonamide and methyldichlorosi-

  unreacted lane to obtain 73.1 g

  N-ethyl-N- [3- (dichloromethylsilyl) propyl] -perfluoro-

  butylsulfonamide. Yield: 76%. We confirm that the product is:

CH2CH3

C4P9SO2N-C92CH2CH2Si (CH3) C12

  by 1H NMR analysis, SM analysis and spectropho-

IR tometer.

  The conditions and results of the analyzes are as follows: 1 H NMR analysis: Solvent: Freon-113; Internal standard: benzene 6 0.10 (s, 3H); 1.30 (t, 3H); 1.65-2.5 (m, 4H);

3.5-4.0 (m, 4H).

  SM analysis: Ionization voltage: 70 eV m / e and the relative intensity are as follows,

  in this order: 339.56.2%, 113.24.6%; 69, 100%.

  IR spectrophotometry: Sample: without solvent 3350 295, 139, 120-113 (cm1

3350, 2950, 1390, 1260-1130 (cm-).

Example 10

  In a 300 ml three-tube flask equipped with a magnetic stirrer, a thermometer and a reflux condenser, 48.2 g (0.10 mole) of N-ethyl-N- [3- (dichloromethylsilyl) propyl] -perfluorobutylsulfonamide, 40.4 g (0.40 mole) of triethylamine and ml of isopropyl ether, and 30 ml of ethanol are added dropwise over a period of 2 hours while cooling the flask with ice water. Then stirring is continued for 1 hour at the same temperature. The salt produced is filtered off and the excess ethanol, isopropyl ether and triethylamine are distilled off, thereby obtaining 38.6 g

  of N-ethyl-N- [3- (diethoxymethylsilyl) propyl] l-perfluoro-

  butylsulfonamide. Yield: 77%. We confirm that the product is:

CH2CH3

C4F9SO2N-CH2CH2CH2Si (CH3) (0C2H5) 2

  by H NMR analysis, SM analysis and spectropho-

IR tometer.

  Conditions and results. analyzes are as follows: NMR analysis of H: Solvent: Freon-113; Internal standard: benzene 6 0.10 (s, 3H); 1.31 (t, 3H); 1.42 (t, 6H);

1.6-2.5 (m, 4H); 3.5-4.1 (m, 8H).

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

370.58.9%; 131, 100%; 69.84.1%.

  IR spectrophotometry: Sample: solvent-free

  3350, 2950, 1390, 1260-1130, 1090 (cm 1).

Example 11

  In a 200 ml three-tube flask equipped with a magnetic stirrer, a thermometer and a reflux condenser, 18.9 g (0.20 mole) of N-ethyl-N- [3- (monoethoxydimethylsilyl) -propyl] amine,

  , 8 g (0.20 mole) of pyridine and 100 ml of iso- ether

  propyl, and 30.2 g (0.10 mole) of perfluorobutylsulfonyl fluoride are added dropwise through a stopper over a period of 1 hour at 20 C. The reaction mixture is stirred for 1 hour at this temperature , then stirred it again for 2 hours at 40 C. Then, the salt produced is filtered off, the excess pyridine and the isopropyl ether are distilled off and

  18.4 g of N-ethyl-N- [3- (monoethoxydimethyl-

  silyl) propyl] -perfluorobutylsulfonamide. Yield: 39%.

We confirm that the product is:

CH2CH3

* C4H9SO2NCH2CH2CH2Si (OCH3) (CH3) 2

  by H NMR analysis, SM analysis and spectropho-

IR tometer.

  The conditions and results of the analyzes are as follows: 1 H NMR analysis: Solvent: Freon-113; Internal standard: benzene 6 0.1 (s, 6H); 0.9 (t, 2H); 1.3 (dt, 3H);

  1.6-2.5 (m, 2H); 3.5-4.1 (m, 4H); 3.8 (s, 3H).

  SM analysis: Ionization voltage: 70 eV m / e and the relative intensity are as follows,

  in this order: 426, 12.3%; 103.62.2%; 69, 100%.

IR spectrophotometry.

Sample: solvent-free

  3350, 2950, 1390, 1260-1130, 1090 (cm 1).

Example 12

  In a 50 ml flask with three tubes fitted with a magnetic stirrer, a thermometer and a reflux condenser, 20.4 g (30 mmol) -of Nn-propyl-N-allyl-perfluorodecylsulfonamide are placed, supplied by New Akita Chemical Co., and 5 mg (1.0 x 10-6 mole) of chloroplatinic acid, and

  drop by drop 4.5 g (33 mmol) of trichlorosi-

  lane with a stopcock bulb over a period of 20 min at 80 C. Then the reaction system is stirred for 1 hour at the same temperature. By distilling off the excess trichlorosilane, 22.8 g of

  N-n-propyl-N- [3- (trichlorosilyl) propyl] -perfluorodecyl-

  sulfonamide. Yield: 93%. We confirm that the product is:

CH CH 2CH3

C10H21SO2NCH2CH2CH2SiCl3

  by 1H NMR analysis, SM analysis and spectropho-

IR tometer.

  The conditions and results of the analyzes are as follows: 1 H NMR analysis: Solvent: Freon-113; Internal standard: benzene 6 1.31 (t, 3H); 1r7-2.6 (m, 6H); 3.6-4.1

(m, 4H).

  Analysis SM: Ionization voltage: 70 eV m / e and the relative intensity are as follows, in this order: 654, 72.3%; 133, 24.6%; 69, 100%

IR spectrophotometry: -

Sample: solvent-free

3350, 2950, 1390, 1260-1130 (cm 1).

Example 13

  In a 100 ml flask with three tubes fitted with a magnetic stirrer, a thermometer and a reflux condenser, 16.3 g (20 mmol) of Nn-propyl-N- [3- (trichlorosilyl) are placed ) propyl] -perfluorodecylsulfonamide, and 20 ml of methanol are added dropwise under reduced pressure of 8.00 kPa over a period of 1 hour at 40 C. By removing excess

  methanol by distillation, 12.1 g of N-n-propyl are obtained

  N- [3- (trimethoxysilyl) propyl] -perfluorodecylsulfonamide.

  Yield: 75%. It is confirmed that the compound is:

CH2CH2CH3

C10E21SO2NCH2CH2CH2Si (OCH3) 3

  by iH NMR analysis, SM analysis and spectropho-

IR tometer.

  The conditions and results of the analyzes are as follows: NMR analysis of H: Solvent: Freon-113; Internal standard: benzene 6 0.9 (t, 2H); 1.24 (t, 3H); 1.63-2.52 (m, 6H);

3.4-3.9 (m, 4H); 3.8 (s, 9H).

  Analysis SM: Ionization voltage: 70 eV m / e and the relative intensity are as follows, in this order: 772, 29.4%; 654, 5.6%; 121, 100%;

69.89.1%.

  IR spectrophotometry: Sample: solvent-free

  3350, 2950, 1390, 1260-1130, 1090 (cm 1). The fluorinated silanes of the present invention

  have excellent hydrophobicity and oleophobia.

Example 14

  A plate of

  ordinary glass measuring 24 mm x 75 mm in a solution

  tion consisting of 1.0 g of C8F17SO2N (C3H7) CH2CH2CH2Si (OCH3) 3100 g of ethanol and 0.5 g of a 10% aqueous solution of HCl. The glass plate is dried at room temperature and the angle of connection of the plate is measured. It is 110 for water and 75 for oil

paraffin.

  Comparative Example 1 The procedure of Example 14 is repeated, except that 1.0 g of CH3Si (OCH3) 3 is used in place of said fluorinated silane. The connection angle is 35

  for water and 37 for paraffin oil.

Comparative Example 2 -

  We use the procedure of Example 13,

  except that 1.0 g of NH2CH2CH2NHCH2CH2CH2CH2- is used

  Si (OCH3) 3 in place of said fluorinated silane. The connection angle is 27 for water and 34 for oil

paraffin.

Example 15

  An ordinary glass plate measuring 25 mm x 75 mm is immersed for 1 min in a solution

  consisting of 1.0 g of N-ethyl-N- [3- (triethoxysilyl) -

  propyl] -perfluorohexylsulfonamide, 200 ml of ethanol and 0.5 g of 10% hydrochloric acid, and dried with

ambient temperature.

  The connection angle of the glass plate thus treated is 110 for water and 76 for

paraffin oil.

  Comparative Example 3 The procedure of Example 15 is repeated using 1.0 g of trimethoxymethylsilane in place of said fluorinated silane. The connection angle is 35

  for water and 370 for paraffin oil.

  Comparative Example 4 The procedure of Example 5 is repeated, using 1.0 g of perfluoroheptylcarbonate

  3-trimethoxysilylpropyl in place of said fluorinated silane.

  The connecting eagle is 81 for water and 49

for paraffin oil.

Example 16

  3 g of N-n-propyl-N- [3- (trimethoxy-

  silyl) propyl] -perfluorobutylsulfonamide with 100 g of an epoxy resin type paint base (melamine curable epoxy resin, supplied by Tokyo Paint Kabushiki Kaisha) and the mixture is applied to a steel test panel of 50 mm x 100 mm x 1 mm (sold by Nippon Test Panel Kabushiki Kaisha) in a thickness of 0-, 1 mm and -cooked at 120 C for 20 min. We measure

  the angles of connection of the surface as an

  dices of hydrophobia and oleophobia. The connection angle

  This is 112 for water and 85 for paraffin oil. Comparative Example 5 The epoxy resin used in Example 16 is applied to a steel test panel of mm x 100 mm x 1 mm (sold by Nippon Test Panel

  Kabushiki Kaisha) in a thickness of 0.1 mm, without addi-

  tion of the fluorinated silane, and it is cooked at 120 ° C. for

  min. The test for determining the hydro-

  phobia and oleophobia in the same way as in example 16. The connection angle is 33 for

  water and 12 for paraffin oil.

  Comparative Example 6 The procedure of Example 16 is repeated.

  using 3 g of 2-trifluoromethyl-1-trimethoxysilyl-

  ethane. The connection angle is 45 for water and

of 23 for paraffin oil.

  When mineral fillers such as

  fiberglass, glass beads, alumina, -the gra-

  phite, carbon fiber, molybdenum disulfide and metallic powders such as bronze powder, lead powder, etc., are treated with a fluorinated silane of the present invention, they can be easily mixed with resins fluorinated materials such as polytetrafluoroethylene, polychlorotrifluoroethylene, poly (vinylidene fluoride), poly (fluoride

  vinyl), a hexafluorethylene-hexafluoropro- copolymer

  pene, a tetrafluoroethylene-ethylene copolymer, a tetrafluoroethylene-perfluoro copolymer (alkyl ether

  and vinyl), a chlorotrifluoroethylene copolymer-

  ethylene, etc., with good affinity, and the composition

  The resulting resin has excellent resistance

  compression strength and excellent abrasion resistance. Usually 0.1 to 20% by weight is used

  fluorinated silane relative to the weight of the fillers.

Example 17

  50 g of glass fiber (about 3 dm in diameter and about 50 gm in length) are immersed in 500 ml of an ethanolic solution of 2.5 g of C8F17SO2N (C3H7) CH2CH2CH2Si (OCH3) 3 containing 1% by weight d '' a 10% aqueous solution of HCl, and the mixture is stirred vigorously using

  an electric shaker for 10 min at room temperature

  ambient ture. The glass fiber thus processed is mixed

  silane with polytetrafluorethy powder

  lene (Teflon) in a weight ratio of 50:50 and the mixture is packed under a pressure of 39 MPa to

  make a piece 172 mm in diameter and 10 mm thick

  sister. The part is baked at 3700C for one hour and a part of fiber-reinforced Teflon resin is obtained.

of glass.

  The compressive strength (compression speed: 3 mm / min), the friction properties and the abrasion properties are measured. The compressive strength was measured at a compression rate of 3 mm / min and the friction and abrasion properties were measured using a Suzuki abrasion tester. The results are exposed on the

  Table 1, as well as the results of the comparative example

next tif.

  Comparative Example 7 The procedure of Example 17 is repeated using the same glass fiber which has not been treated with said fluorinated silane, and a piece of Teflon resin reinforced with glass fiber is thus obtained on which the tests are carried out. The results are

set out in Table 1.

Table 1 Example

Example

  Example 17 Comparative 7 Compressive strength Load required for 1% of 9.61 8.24 deformation (MPa) Load required for 25% of 33.93 29.91 deformation (MPa) Coefficient of friction * static 0.07 0, 07 dynamic 0.24 0.24

  Abrasion coefficient * (kg / cm2) 1.1 x 10 5 1.1 x 105-

  * Test conditions: Counterpart: SUS27 stainless steel piece, 256 mm x 20 mm x 15 mm Load: 392 kPa (4 kg / cm2) Speed: 60 m / min Duration: 16 hours after 30 min of preliminary execution

Example 18

  50 g of graphite are placed in a 1 liter flask with three tubes fitted with a thermometer, an agitator and a reflux condenser.

  powder and 100 ml of a solution are added dropwise

  tion at 10% by weight of the same fluorinated silane as that used in Example 17 in a period of 1 hour with stirring. Then the mixture is heated to 100 ° C. to remove the solvent. We mix the graphite powder

  thus obtained with the same Teflon resin and made

  kills the same tests. The results are exposed on the

table 2.

  Comparative Example 8 The procedure and the tests of Example 17 are repeated using non graphite powder.

  processed. The results are set out in Table 2.

Table 2

  Example Example 18 Comparative 8 Compressive strength Load required for 1% of 8.34 7.45 deformation (MPa) Load required for 25% of 38.34 34.81 deformation (MPa) Coefficient of friction * static 0.05 0 , 06 dynamic 0.23 0.23 Abrasion coefficient * (kg / cm2) 6.7 x 10- 5 6.7 x 10-5 When mineral fillers such as silicon oxide, oxide of tin, titanium oxide, aluminum oxide, silicon nitride, graphite, zinc oxide, iron oxides, mica, fiberglass, carbon fiber, asbestos , etc., are treated with a fluorinated silane of the present invention, these fillers have excellent hydrophobicity properties,

  oleophobia and non-stickiness.

  Usually 0.1 to 20% by weight is used

  fluorinated silane relative to the weight of the filler.

Example 19

  50 g of silica powder (approximately 1 gm in diameter) are mixed with 500 ml of ethanolic solutions containing respectively 0.1, 1, 5 and 10% by weight of C8F17SO2N (C3H7) CH2CH2CH2Si (OCH3) 3 relative to the weight of the load and 1% by weight of a

  10% aqueous HCl solution, and stirred vigorously

  mix the mixture with an electric shaker

  for 10 min at room temperature.

  The mixture is heated to 100 ° C. to remove the solvent by evaporation and thus silica powders treated with fluorinated silane are obtained. Almost all of the added fluorinated silane adheres to the

silica powder.

  The IR absorption spectra of the silica powders thus treated are noted by proceeding by the powder reflection method and it is noted that there is an absorption due to the bond 2850-2950 cm 1, an absorption due to the sulfonamide bond at 1390 cm

  and an absorption due to the C-F bond at 1100-1300 cm1.

  In other words, it has been shown that fluorinated silane is

  present on the surface of silica powders.

  The hydrophobicity of the silica powders thus treated is measured; The powders are respectively mixed with 500 ml and shaken vigorously using an electric shaker for 15 minutes at temperature.

  ambient. Hydrophobicity is assessed based on an observation

tion with the naked eye.

  Comparative Example 9 The procedure of Example 19 is repeated, using CH -CH -CH2 OCH2CH2CH2Si (OCH3)

2 2 2 2 2 2 33

  \ 2 / o0 The results are summarized in Table 3, next to

those of Example 19.

Table 3

  Example 19 Comparative Example 9 Content of content of fluorinated silane silane (% by weight) Hydrophobicity (% by weight) Hydrophobicity

0.1 0 1 X

1 0

0 10 X

o

  X: The silica powder disperses completely in water.

  O: The silica powder partially disperses in water and floats

partly on the surface of the water.

  1: The silica powder floats completely on the surface of the water.

Example 20

  In a 1 liter flask with three tubes

  equipped with a thermometer, an agitator and a refrigerator

  At reflux, 50 g of alumina powder (about 1 gm in diameter) are placed and 50 ml of solutions (5, 10, 20 and 25% by weight) of the same silane are added dropwise, respectively. fluorinated in a 1 hour period with stirring. Each mixture is then heated to 100 ° C. to remove the solvent. Alumina powders are thus obtained treated with the same fluorinated silane. It is confirmed that the fluorinated silane adheres to the surface of the alumina powder according to the IR absorption spectra recorded by the reflection method on

  powders, in the same way as in Example 19.

  Comparative Example 10 The procedure and the tests of Example 19 are repeated, using as silane: CF3CH2CH2CH2Si (OCH3) 3 The results are shown in Table 4, next to

those of Example 19.

Table 4

  Example 19 Comparative Example 10 Content of content of fluorinated silane silane (% by weight) Hydrophobicity (% by weight) Hydrophobicity

O 5 X

0 20 O

  The symbols have the same meanings as in Table 3.

Example 21

  50 g of silica powder (approximately gm in diameter) are mixed with 500 ml of ethanolic solutions containing respectively 0.1, 1, 5 and 10% by weight of C8F17SO2N (C3H7) CH2CH2CH2Si (OCH3) C relative to the weight of the load and 1% by weight of a

  10% aqueous HCl solution, and stirred vigorously

  Mix the mixture using an electric shaker

  for 20 min at room temperature.

  The mixture is heated to 100 ° C. to remove

  ethanol by evaporation and we thus obtain

  dres of silica treated with said fluorinated silane. The IR absorption spectra of the silica powders thus treated are noted by proceeding by the reflection method on powders and it is noted that there is an absorption due to the CH bond at 2850-2950 cm 1, an absorption due to the SO2N bond at 1390 cm 1 and an absorption due

2 1

  at the C-F link at 1100-1300 cm. In other words, it is confirmed that the fluorinated silane is present on the surface

silica powders.

  The silica powders thus treated are respectively mixed with an epoxy resin type paint base (melamine hardenable epoxy resin supplied by Tokyo Paint Kabushiki Kaisha) in an amount of 50% by weight of the paint base resin, and applying the mixture to the surface of steel test panels to a thickness of 100 µm. The coated test panels are baked at 140 ° C for 20 min and subjected to a water resistance test. In this test, the panels are heated in an autoclave containing water at a pressure of 0.5 MPa for 2 hours. Next, the water content of the coating is measured. The results are

set out in Table 5.

  Comparative Example 10 The procedure of Example 21 is repeated using: CH3Si (OCH3) 3

  The results are. set out in Table 5.

Table 5

  Example 21 Comparative Example 10 Content of fluorinated silane content Silane content Water content (% by weight) (% by weight)

0.1 <0.3% 1> 3%

1 <0.2%

<0.2% 10> 2%

<0.2%

  Example 22 In a 1 liter flask with three tubes

  - equipped with a thermometer, an agitator and a refrigerator

  rant at reflux, 50 g of alumina powder (about 10 Nm in diameter) are placed and 50 ml of solutions (5, 10, 20 and 25% by weight) of the same fluorinated silane are added dropwise used in Example 21 over a period of 1 hour with stirring. The mixture is then heated to 100 ° C. to remove the solvent. As regards the silica powders thus treated, the presence of the fluorinated silane is confirmed on their surface according to the IR absorption spectra recorded by the reflection method on powders, in the same manner as in Example 21 In addition, the same water resistance test is carried out as in Example 21. The results are shown in Table 6. Comparative Example 11 The procedure and the tests of Example 22 are repeated using CH3Si (OCH3) 3, which was used as silane in Comparative Example 10. The results are shown in Table 6 in comparison

of those of Example 22.

Table 6

  Example 22 Comparative Example 11 Content of fluorinated silane content Silane content Water content (% by weight) (% by weight)

<0.2% 5> 2%

<0.2%

<0.2% 20> 2%

25 *

  * Poor dispersion. No coating product is formed.

Example 23

  The procedure of Example 22 is repeated using alumina powder (approximately 5 gm of

  diameter. The results are shown in Table 7.

  Comparative Example 12 The procedure of Example 23 is repeated, using as silane: NH2 (CH2) 3Si (OCH3) 3

  The results are set out in Table 7 in comparison

sound of those in Example 23.

Table 7

  Example 23 Comparative Example 12 Content in fluorinated silane content Silane content Water content (% by weight) (% by weight)

0.1 <0.2% 1> 1%

1 <0.1%

<0.1% 10> 1%

<0.1%

Example 24

  The procedure of Example 22 is repeated using 50 g of alumina powder (size not

  greater than 5 Dm in diameter). The results are expo-

listed in table 8.

  Comparative Example 13 The procedure of Example 22 is repeated using as silane: NH2 (CH2) 3Si (OCH3) 3

  The results are set out in Table 8 in comparison

its from those in Example 24.

Table 8

  Example 24 Comparative Example 13 Content of Fluorinated Silane Content Content of Silane Content (% by Weight) of Water (% by Weight) of Water

5 <0.2% 5> 1%

<0.1%

<0.1% 10> 1%

*

  * Poor dispersion. A coating composition is not formed.

Example 25

  50 g of fiberglass (about 3 hm in diameter and about 50 gm in average length) are mixed with

  500 ml of acetononi solutions containing various quan-

  tities of 8 17SO2N (C2H5) CH2CH2CH2Si (OCH3) 3 and containing 1% by weight of an aqueous solution of HCl

  at 10% and the mixture is stirred for 20 min at room temperature.

  ambient rature. The concentrations of fluorinated silane in

  these solutions are 0.1, 1, 5 and 10% by weight relative to

  weight of fiberglass. After 30 min, the acetone is removed by heating to 100 ° C. and the IR spectra of the glass fibers thus treated are raised by the diffusion-reflection method. Absorption is observed at 2950 cm1 (C-H), 1390 cm1 (SO2N) and 1100-1300 cm1 (C-F) and it is thus confirmed that the fluorinated silane is present on the surface of the

  fiberglass. The glass fiber thus processed is mixed

  tee with a base of acrylic resin type paint (self-hardening acrylic resin base of paint, supplied by Tokyo Paint Kabushiki Kaisha) in an amount of 50% by weight, and the mixture is poured into a 10 cm x 10 mold cm x 10 cm and bake at 150 C for min. The piece of acrylic resin thus obtained is subjected to a water resistance test with water vapor at 0.5 MPa for 2 hours, proceeding in the same manner as in Example 21. The content

  in water and the results are shown in Table 9.

  Comparative Example 14 The procedure of Example 25 is repeated using CH3Si (OCH3) 3 as silane. The results

are shown in Table 9.

Table 9

  Example 25 Comparative Example 14 Content of Fluorinated Silane Content Content of Silane Content of Water (% by Weight) in Water (% by Weight)

0.1 <0.8% 1> 5%

1 <0.5%

<0.5% 10> 3%

<0.5%

  When metallic materials such as copper, aluminum, iron, lead, zinc, tin, titanium, cobalt, nickel, chromium, etc .; alloys such as stainless steels, Hastelloy, Inconel, Stellite, etc-; magnetic alloys such as an Sm-Co alloy, an Nd-Fe-B alloy, etc., are treated with a fluorinated silane of the present invention,

  they have excellent hydropho-

* bie and oleophobia. The metallic materials can be in the form of a sheet, sphere, ribbon, etc. Likewise, when organic resins such as phenolic resin, furan resin, xyleneformaldehyde resin, ketone-formaldehyde resin, urea resin, melamine resin, aniline resin, epoxy resin, poly resin (acetate

  vinyl), polyacrylic resin, poly-

  methacrylic, poly (vinyl chloride) resin,

  poly resin (vinylidene chloride), a polyacry-

  lonitrile, poly (vinyl ether) resin, resin

  polycarbonate, polyamide resin, polyurea resin-

  thanne, etc., including almost all the hydrocarbon resins, are treated with a fluorinated silane of

  the present invention, these resins are provided with excel-

  slow hydrophobicity and oleophobicity characteristics.

  The resins can be in sheet, film, fiber or any other form. The adhesion and the effect of the compounds of the present invention are not influenced

  by the shape of the substrate materials.

  Likewise, when paper is treated with a fluorinated silane of the present invention, this paper has excellent hydrophobicity and oleophobicity characteristics. The subject paper includes machine made paper, handmade paper, cardboard, corrugated cardboard, etc. The fluorinated silanes of the present invention

  can be applied to glass to give it excel-

  slow hydrophobicity and oleophobicity characteristics.

  The fluorinated silanes of the present invention can be added to the liquid papermaking pulp when their incorporation into the paper is desired. The fluorinated silanes of the present invention can be applied to the surface of various materials by mixing with a coating composition based on

resin.

Example 26

  A 0.5% acetone solution of C8F17SO2N (C4H9) CH2CH2CH2Si (OC2H5) 3 containing 0.5% by weight of an aqueous acid solution is applied to an aluminum plate of mm x 50 mm x 1 mm.

10% acetic.

  The angles of connection of this plate for water and paraffin oil are measured in order to evaluate its hydrophobicity and its oleophobia. The results are

set out in Table 10.

  Comparative Example 15 The same aluminum plate as that used in Example 26 is coated with a base of paint of the acrylic resin type (a self-hardening acrylic resin, supplied by Tokyo Paint Kabushiki Kaisha) in one weight.

coating of 3% by weight.

  The hydrophobicity and oleophobicity of this aluminum plate are measured and the results are shown in Table 10 with the results of Example 26.

Table 10

  Connection Angle (o) Paraffin Water Oil Example 26 143 112 Comparative Example 15 96 0 28

Example 27

  A 5% acetone solution of C8F17SO2N (C3H7) CH2CH2CH2Si (OCH3) 3 is applied to a 100 mm × 50 mm × 1 mm copper plate.

  containing 1% by weight of an aqueous 10% HCl solution.

  The plate is dried at 80 ° C. for 1 hour. We

  examines the copper plate coated by spectrophotome-

  sorts IR and we observe the absorption due to the C-F bond at 1100-1300 cm 1. In other words, the adhesion of the

fluorinated silane is confirmed.

  The plate is immersed in an aqueous solution

  5% common salt and we measure the weight loss.

  Comparative Example 16 The same copper plate is used as that used in Example 27, not having been treated with fluorinated silane, by proceeding in the same way; The results of Example 27 and the Comparative Example

16 are shown in Table 11.

Table 11

  Number of days Example 27 Comparative example 16 i 0% 5%

2 1% 8%

3 3% 12%

5% 18%

8% 24%

Example 28

  A 5% by weight ethanolic solution of C8F17SO2N (C2H5) CH2CH2CH2Si (OC2H5) 3 is applied to a 100 mm × 50 mm × 1 mm steel plate.

  containing 0.5% by weight of an aqueous solution of n-propy-

10% laminate.

  We leave the plate outside and we

  observe the formation of spots on this surface.

  Comparative Example 17 The procedure of Example 28 is repeated.

  using an untreated steel plate. The results

  States are shown in Table 12.

Table 12

  Number of days Example 27 Comparative example 17

1 O O

O A

30 O X

O X

A X

  O: Clear (no stains) A: Stains in some places X: Completely stained

Example 29

  5 g of C8F17SO2N (CH3) CH2CH2CH2Si (OCH3) 3 are added to 100 g of a paint base of the epoxy resin type (melamine curable epoxy resin, supplied by Tokyo Paint Kabushiki Kaisha). The paint is applied to a 100 mm x 50 mm x 1 mm test panel (sold by Nippon Test Panel Kabushiki Kaisha) in a thickness of 0.1 mm and the panel is baked at 120 C for 20 min. We measure the connection angles for water and

  oil to assess hydrophobicity and oleophobia.

  Comparative Example 18 A test panel is prepared and tested in the same manner as in Example 29 using the epoxy resin type paint base used in Example 29 not containing fluorinated silane . The

  results are shown in Table 13.

Table 13

  Connection Angle (o) Paraffin Water Oil Example 29 106 78 Comparative Example 18 720 18 Example 30 We apply to a 100mmx50mmxlmm test panel (sold by Nippon Test Panel Kabushiki Kaisha) the epoxy resin type paint base used to Example 29 in a thickness of 0.1 mm and the panel is subjected to a pre-baking at 80 C for 30 min. This panel is immersed for 10 seconds in a 10% by weight solution in Freon-113 of C8F17SO2N (C3H7) C H2CH2CH2Si (OCH3) 3 and it is cooked at 120 C for 20 min. The panel thus treated is examined by IR spectrophotometry and

  observe the absorption due to the C-F bond at 1100-1300 cm1.

  We also examine hydrophobia and oleopho-

of this panel.

  Comparative Example 19 The procedure of Example 30 is repeated using a fluorinated surfactant, C8 F 7SO3Na. We assess 817 3

  hydrophobia and oleophobia in the same way.

  Table 14 Connection Angle (0) Paraffin Water Oil Example 30 110 82 Comparative Example 19 74 20

Example 31

  We apply to a 100mmx50mmxlmm test panel (supplied by Nippon Test Panel Kabushiki Kaisha) a base of

  acrylic resin type paint, (acrylic resin self-

  curable sold by Tokyo Paint Kabushiki Kaisha) in a thickness of 0.1 mm and the panel is baked at 170 C for 20 min. This panel is immersed for 30 seconds in an acetone solution at 10% by weight of C8F17SO2N (C2Hs) CH2CH2CH2Si (OCH3) 3 and it is dried at room temperature. We examine the panel thus treated by IR spectrophotometry and we

  observes an absorption due to the C-F bond at 1100-1300 cm1.

  The adhesion of the fluorinated silane is confirmed.

  Comparative Example 20 The procedure of Example 31 is repeated using a fluorinated surfactant, C7F15CO2K, in place of said fluorinated silane. We do not characterize

  C-F bond by IR spectrophotometry.

  We assess hydrophobicity in the same way and

  oleophobia. The results are shown in the table. 15.

Table 15

  Connection Angle (0) Paraffin Water Oil

Example 31 105 800.

Comparative Example 20 72 28

Example 32

  We immerse commercially available A4 size letter paper (marketed by Kokuyo

  Kabushiki Kaisha) for 5 min in an acetone solution

  3% by weight of C8F17S02N (C3F7) CH2CH2CH2Si (OCH3) 3

  and dries it at room temperature for 2 hours.

  This gives paper impregnated with said fluorinated silane. The paper is examined by IR spectrophotometry and the absorption due to the C-F bond is observed at 1100-1300 cm.1 The adhesion of the fluorinated silane is confirmed. We pour water and paraffin oil

  on this paper and we observe and evaluate the absorption.

  Comparative Example 21 The procedure of Example 32 is repeated with the same paper, but not treated. The results of Example 32 and Comparative Example 21 are exposed

on table 16.

Table 16

  Absorption time Oil of paraffin Water Example 32 42 s 1 min 12 s Comparative Example 21 less is less than 5 s

Example 33

  2% of C8F17SO2N (C2H5) CH2CH2CH2Si (OCH2CH5) 3 is added to a paste suspension.

  relative to the weight of pulp, and paper is made.

  In IR spectrophotometry, we observe

  absorption due to the C-F bond at 1100-1300 cm-1.

  The hydrophobia and oleophobia of the

same as in Example 32.

  Comparative Example 22 The procedure of Example 33 is repeated, but without using the fluorinated silane. The results of Example 33 and Comparative Example 22 are exposed

on table 17.

  Table 17 Absorption time Paraffin Water Oil Example 33 1 min 7 s 1 min 59 s. 15 Comparative Example 22 less than 1 s less than 5 s

Example 34

  Commercial corrugated cardboard (sold by Kashiwaya Shiki Kogyo Kabushiki Kaisha) is immersed for 3 min in a benzene solution of C8Ft7SO2N (C3H7) CH2CH2CH2Si (OCH3) 3

  and it is dried at 50 ° C. for 1 hour.

  This cardboard is examined by IR spectrophotometry and an absorption due to the C-F bond is observed at 1100-1300 cm 1. Thus, the presence of the fluorinated silane is confirmed. We assess hydrophobicity in the same way and

the oleophobia of cardboard.

  Comparative Example 22 The procedure of Example 34 is repeated using C8F17SO2N (C2H5) CH2CH2PO (ONa) 2

  in place of said fluorinated silane. The results of the Ex-

  ple 34 and Comparative Example 23 are exposed on the

table 18.

Table 18

  Absorption time Oil of paraffin Water Example 34 1 min 16 s 1 min 39 s Comparative Example 23 47 s 1 min 3 s When colored ceramic materials such as

  only tiles, earthenware and porcelain

  wool, etc., are treated with a fluorinated silane of the

  present invention, they are provided with an excellent soli-

  color and better resistance to chemical agents. The leaching of pigments or pigment elements (eg cadmium, lead, etc.) is

  effectively prevented. In the case of tiles, the development

  the development of moss and mold on the surface is prevented.

Example 35

  Colored tiles are prepared by coating commercially available non-colored semiporcelain tiles with a paste prepared by mixing parts by weight of cadmium pigment, 95 parts by weight of lead-free boric acid glaze melting at

  low temperature (SK01Oa), 0.2 parts by weight of methyl-

  cellulose and 60 parts by weight of water and by grinding the mixture in a ball mill for 30 min, and by baking

  at 1000 C the tiles coated after drying.

  The colored tiles thus obtained are coated

  with N-n-propyl-N- [3- (trimethoxysilyl) propyl] -

  perfluorosulfonamide diluted in ethanol to the concentra-

  tion indicated in Table 19 and dried. Soak each of the treated tiles in 300 ml

  4% acetic acid solution for 24 hours.

  Next, the quantity of cadmium extracted by leaching is measured using an atomic absorption spectrometer. In addition, the tiles and the tiles are dried.

  examines as to the deposit of alkaline substance upon

  face (efflorescence). The results are summarized on the

table 19.

Example 36

  Colored tiles are prepared by coating commercially available non-colored semiporcelain tiles with a paste prepared by mixing 0.68 part by weight of ferric oxide, 0.32 part by

  weight of cobalt oxide, 100 parts by weight of gla-

  lead-free glass melting at low temperature (SK010a), 0.2 parts by weight of methylcellulose and 60 parts by weight of water and by grinding the mixture in a ball mill for 30 min, and baking the tiles at 1050 C

coated after drying.

  The colored tiles thus obtained are coated

  with N-n-propyl-N- [3- (trichlorosilyl) propyl -

  perfluoroctylsulfonamide diluted in ethanol at the concentration indicated in table 19 and they are dried. Each of the tiles thus treated is soaked in 300 ml of a 4% acetic acid solution for 24 hours. Next, the amount of lead extracted by leaching is measured using an atomic absorption spectrometer. In addition, the tiles are dried and examined for the deposition of alkaline material upon

  area. The results are shown in Table 19.

Example 37

  Colored tiles are prepared by coating commercially available non-colored semiporcelain tiles with a paste prepared by mixing 2 parts by weight of manganese oxide, 98 parts by

  weight of lead-free glaze melting at medium temperature

  ture (SK4), 0.2 parts by weight of methylcellulose and parts by weight of water and by grinding the mixture in a ball mill for 30 min, and baking at 1200 C

  coated tiles - after drying.

  The colored tiles thus obtained are coated

  with N-n-propyl-N- [3- (trichlorosilyl) propyl] -

  perfluoroctylsulfonamide diluted in ethanol at a concentration of 5%. We dip the tiles thus treated

  tees to their middle and let them sit to observe

  to the growth of mosses and molds. After 3 months, there is no development of foam

and mold.

  Comparative Example 24 Colored tiles prepared as in Example 35, without surface treatment, are immersed in a 4% acetic acid solution for 24 hours and

  lextrac atomic absorption spectrometry measurement

  tion of cadmium by leaching. We also look at the

deposition of alkaline substance.

  Comparative Example 25 Colored tiles prepared as in Example 36 were examined to determine the extraction of lead by leaching and the deposition of alkaline substance in the same manner as in Comparative Example 24. The

  results are shown in Table 19.

Table 19

  Substance deposition Alkaline leaching (visual Concentration (millionths)) Sampling Example till (%) Cd Pb 1 1.0 0.05 - None

2 5.0 0.00 - "

35 3 10.0 0.00 - "

  Compa- - 15 - Observation 24 24 i 1.0 - 0.08 None

36 2 5.0 - 0.00 "

36 3 10.0 - 0.00

Compa- - - 58.6 Statement 25

Example 38

  Colored tiles are prepared by coating commercially available non-colored semiporcelain tiles with a paste prepared by mixing 2 parts by weight of manganese oxide, 92 parts by

  weight of lead-free glaze melting at medium temperature

  ture (SK4), 0.2 parts by weight of methylcellulose and parts by weight of water and by grinding the mixture in a ball mill for 30 min, and baking at 1200 C

  coated tiles after drying.

  The colored tiles thus obtained are coated

  with N-n-propyl-N- [3- (trichlorosilyl) propyl] -

  perfluoroctylsulfonamide diluted in ethanol at a concentration of 5%. We immerse the tiles in water

  thus treated to their middle and left to rest

  serve to observe the growth of mosses and molds.

  After 3 months, no development of

mosses and molds.

  Comparative Example 26 We examine the colored tiles prepared for

  Example 37, without surface treatment, to determine

  the growth of mosses and molds in the same way as in Example 37. Mosses develop

in 1 month.

  When mineral building materials

  such as masonry joint materials,

  ALC (light air entrained concrete), plates

  slate, calcium silicate plates, materials

  rials of shaped cement, hardened cement mortar,

  concrete, etc., are treated with a fluorinated silane of the pre-

  invention, they have better characteristics

  hydrophobia, oleophobia, stain resistance, resistance to atmospheric agents, good adhesion of coating products, etc., and they are also endowed with resistance to frost, to the growth of

  mosses and molds, etc. These building materials

  tion can be coated with certain other coating products before being treated with a fluorinated silane

of the present invention.

  For the treatment of these materials with a fluorinated silane of the present invention, the silane is usually diluted with a suitable organic solvent

  in a concentration of 0.001 to 20% by weight, preferably

between 0.1 and 10% by weight.

Example 39

  We prepare a plaster for masonry joints -

  by mixing 100 parts by weight of Portland cement, 300 parts by weight of sand, 0.2 parts by

  weight of methylcellulose and 60 parts by weight of water.

  This coating is applied to a concrete block of cm x 30 cm x 5 cm in a thickness of 5 mm using a trowel. Once the coating spread on the block has hardened in humid air for 2 weeks, a 5% ethanolic solution of C8F17SO2N (CH3) CH2CH2CH2Si (OCH3) 3 is applied to the coating and dried. This test block is immersed in water for 5 cm from the base and left to stand in a room at 35 ° C. and 95% RH for 3 months. Onne

  no development of mosses and molds.

  Comparative Example 27 On the surface of the test block prepared in Example 39, an ethanolic solution containing 5% of CH3Si (OCH3) 3 is applied and the block is tested in the same manner as in

  Example 39. Mold develops in 3 months.

Example 40

  An emulsion paint is prepared by mixing

  giant 40 parts by weight of a coating product to

  acrylic emulsion base ("EC720"), sold 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 parts by weight of methylcellulose. This paint is applied to the surface of a slate plate of 150 x 50 x 3 mm. Once the paint has dried, a 0.1% ethanolic solution of C8 17SO2N (C2H5) CH2CH2CH2Si (OCH3) 3 is applied once to the painted surface of the slate sheet. of this test plate and the plate is subjected to an outdoor exposure test for 1 year. At the end

  1 year, we see that the paint covering the

  face is not blistered, scaly, or stained.

  Comparative Example 28 On the painted surface of a test slate plate prepared as in Example 40, an ethanolic solution of CH3CONHC3H6Si (OCH 3) 3 is applied and dried.

  The plate is subjected to the external exposure test.

  laugh for 1 year in the same way as in Example 40.

  Although there is no blistering or flaking,

  the surface is remarkably stained.

  Comparative Example 29 On the painted surface of a test slate plate prepared as in Example 40, an ethanolic solution containing 5% of the known silane is applied and dried: C8F17COO- (CH2) 3Si (OCH3) 3

  The plate is subjected to the external exposure test.

  laugh for 1 year in the same way as in Example 40.

  Although there is no blistering or flaking,

  the surface is slightly stained.

Example 41

  A silica paint is prepared by mixing 20 parts by weight of a colloidal silica ("Snow Tex", sold by Nissan Kagaku Kabushiki Kaisha), 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. We apply this

  silica paint on the surface of a back plate

  150 mm x 50 mm x 3 mm doise. When the paint has dried, a 5% ethanolic solution of C8F17SO2N (C3H7) CH2CH2CH2Si (OCH3) 3 is applied to the painted surface of the slate plate at once. test and we dive the lower half

  of the plate in water. After 3 months, it does not appear

  there is no blistering or chipping and there are almost no spots near the level line

some water.

  Comparative Example 30 On the surface of a slate plate coated with the silica paint prepared in Example 41, an ethanolic solution of CH C CCOC H Si (OCH cH2 icl 3 6si 3 3 O On) is applied and dried. immerse the bottom half of the slate plate in water and after 3 months the paint layer has peeled off near the water level line.

Example 42

  A block of ALC measuring mm x 40 mm x 40 mm is soaked in a 10% ethanolic solution of C8F17SO2N (CH3) CH2CH2CH2Si (OC2H5) 3 to impregnate it, and it is dried. The whole test block is immersed in water and subjected to a cyclic freeze-thaw test comprising cooling to -20 ° C. for 2 hours and holding at 30 ° C. for 2 hours. Two cycles are performed per day. After 50 cycles, there is no cracking or

break.

  Comparative Example 31 Soak a block of ALC identical to

  that used in Example 42 in an ethanol solution

  only at 10% of C8F17CH2CH2CH2Si (OCH3) 3 to impregnate it, and it is dried and subjected to the same test as in Example 42. Although there does not appear any cracking or breakage after 20 freeze-thaw cycles, cracking appears after

  40 cycles and the block breaks after 50 cycles.

  Comparative Example 32 Soak a block of ALC identical to

  that used in Example 42 in an ethanol solution

  that with 10% of C3H7Si (OCH3) 3 to impregnate it, and it is dried and subjected to the same test as in Example 42. Fragments detach from the block after 20 cycles of freeze and thaw and the block stands

* breaks after 30 cycles.

Example 43

  On the surface of a 300 mm x 300 mm x 5 mm slate plate, a 10% ethanolic solution of C8F17SO2N (C3H7) CH2CH2CH2SiC13 is applied at once and dried. The permeability of this plate is determined. 'slate according to the test method of standard' JIS A-6910. Even after 24 hours, there is no water absorption. Comparative Example 33 A slate plate identical to that used in the example is subjected to the same test as in Example 43.

  43, but without having treated it with fluorinated silane.

  After 1 hour, more than 30 ml of water has been absorbed.

Example 44

  A cement block is made by mixing parts by weight of Portland cement, 200 parts by

  weight of sand and 40 parts by weight of water and molding.

  -The block is allowed to harden for 1 day at room temperature. On the block surface, apply and dry a 5% ethanolic solution of C8F17SO2N (CH3) CH2CH2CH2Si (OCH3) 3 Protect the side and rear surfaces of the block and let it rest at 5 C and 95% humidity. There is no deposit of alkaline substance, even at

after 1 month.

  Comparative Example 34 A block of cement made as in Example 44 is subjected to the same test, but without having been treated with fluorinated silane. After 1 week, it appears

  a deposit of alkaline substance on the surface.

  When metals such as copper, which is the type of electrically conductive materials, gold, silver, iron, aluminum and various kinds of alloys, are treated with a fluorinated silane of the present invention, these metals refuse molten solder and solder paste and they lose their weldability. That is, the treated surface becomes unsoudable. The weldability can be easily recovered by removing the layer of fluorinated silane, for example by scraping, and thus the treated metal sheet can be used for the

manufacture of integrated circuits.

Example 45

  A 0.5% ethanolic solution of C8F17SO2N (C3H7) CH2CH2CH2Si (OCH3) 3 containing 0.3% by weight of a 10% sulfuric acid solution is applied to a copper plate of mm x 50 mm x 1 mm %. On the surface of this treated copper plate, a drop of molten tin-lead solder is poured. After cooling, the solder drop does not adhere to the copper plate and is easily removed when it is lightly touched. When inorganic pigments treated with a fluorinated silane of the present invention are incorporated into coating compositions, the pigments are

  well dispersed and coating compositions are obtained

  very stable. The mineral pigments treated with a

  fluorinated silane of the present invention provide qualities

  superior whiteness in the case of a white pigment, of coloring power and of covering power. The treatment of mineral pigments with a fluorinated silane of the present invention has been explained in what

precedes.

Example 46

  While stirring 100 parts by weight of pigmentary titanium oxide at high speed in a mixer

  Henschel, a solution is added dropwise to the pigment.

  0.1 part by weight of C8F17SO2N (C3H7) CH2CH2CH2Si (OCH3) 3 in 10 parts by weight of acetone. After the addition of the solution has been completed, the mixture is kept at 150 ° C. to remove the solvent. We spray the

2630443-

  pigment by means of a fluid jet mill and a titanium oxide pigment treated with the fluorinated silane of the present invention is thus obtained. This titanium oxide pigment is mixed with the materials listed below (Formula 1) and a white paint is obtained. Formula 1 Ingredient parts by weight Titanium oxide pigment treated 30 "Lumiflon LF-200C" (a solution of fluorinated resin, supplied by Asahi Glass Co., solids content: 60%) 142.9 Xylene 35.7 Methyl isobutyl ketone 107 , 1 Isocyanate (hardener) 13.3 This coating composition is applied in a thickness of 0.0254 mm on paper for tests of hiding power. The paper thus coated is used as a test piece and the values L, a and b of its white part are measured. The whiteness is calculated as being equal to 100 - - (100-L) 2 + a2 + b2. The gloss is measured at 60 of the white part using a gloss meter and the covering power (reflectivity of the black part) / reflectivity of the white part) is determined, at

  by means of a reflectometer. In addition, a paint is prepared

  black ture of the same formula as above but in

  which is used 1.5 parts by weight of car black

  bone in place of 30 parts by weight of titanium white.

  30 parts by weight of the black paint are mixed with 100 parts by weight of the white paint described above, and the coloring power of the white paint is determined. The results are exposed on the

table 20.

  Comparative Example 35 A white paint of Formula 1 is prepared, in which untreated titanium oxide is used, and its whiteness, its gloss at, its covering power and its coloring power are determined by the same procedure. as in Example 46. The results are shown in Table 20.

Example 47

  In a solution of 10 parts by weight of C8F17SO2N (CH3) CH2CH2CH2Si (OCH3) 3

  in 300 parts by weight of ethanol, 100 parts are dispersed

  parts by weight of titanium oxide by proceeding in the same manner as in Example 46, and one thus obtains titanium oxide having been treated with said fluorinated silane. A white paint is prepared according to the formula and the procedure described in Example 46.

  - carry out the same test as in Example 46 on test specimens -

  coated with this white paint. The results

are shown in Table 20.

  Comparative Example 36 A white paint is prepared in the same manner as in Example 47, except that the non-fluorinated silane: CH3CONH (CH2) 3Si (OCH3) 3 is used as surface treatment agent. The same test is carried out as in Example 46 on test pieces coated with this white paint. The results are exposed on

table 20.

Example 48

  30 parts by weight of titanium oxide are dispersed in 114.2 parts by weight of toluene, 6 parts by weight of C8F17SO2N (CH3) CH2CH2CH2Si (OC2H5) 3 are added to the dispersion and the mixture is stirred for 60 min. . Then, 171.5 parts by weight of a fluorinated resin solution ("Lumiflon LF-100", a resin solution, are added.

  fluoride sold by Asahi Glass Co., solids content: -

  %) and stir the mixture for 60 min, and add 5.2 parts by weight of melamine and stir the mixture

  for 15 min, thus obtaining a white paint.

  A test tube is prepared by applying this paint in a thickness of 70 g / m2 on a polished steel sheet and baking the coated sheet at 200 C for 5 min. We measure the whiteness, the gloss at 60, the covering power and the coloring power. The results are

set out in Table 20.

  Example of Reference 100 parts by weight of powdered calcium carbonate are dispersed in a solution of 5 parts by weight of C7F15Co2 (CH2) 3Si (OCH3) 3 in 300 parts by weight of ethanol, and the dispersion is stirred for 60 mins. By filtration and drying, calcium carbonate powder treated with said fluorinated silane is obtained. We prepare a white paint by mixing this calcium carbonate powder with

  the materials listed below (Formula 2).

  Formula 2 Ingredient Parts by weight Calcium carbonate powder 25 treated Titanium oxide 5 "Lumiflon LF-100" (a fluorinated resin solution, 171.2 sold by Asahi Glass Co., solids content: 50%) Toluene 114, 2 Melamine (hardener) 5.2 This white paint is applied to the surface of a paper for tests of hiding power and the paper is baked at 130 C for 40 min. The whiteness, the gloss at 60, the covering power and the coloring power of this paint are measured in the same way as in Example 46

Table 20

  Power Power Example Whiteness Brightness to 60 covering dye *

46 88 78 92 125

47 87 77 91 125

48 88 80 - 118

51 85 75 90 -

  Comparative 35 84 74 82 100 comparative 36 85 75 85 107

39 84 72 85 -

  * The numbers represent the values obtained assuming that the coloring power corresponding to the untreated pigment

is equal to 100.

Example 49

  Red iron oxide is treated with C8F17SO2N (CH3) CH2CH2CH2Si (OCH3) 3 in the same manner as in Example 48 and mixed with the materials listed below

  (Formula 3) to prepare a painting.

  Formula 3 Ingredient Parts by weight Pigment treated 2 Calcium carbonate 10 Toluene 50 "Lumiflon LF-100" 40 (a solution of fluorinated resin, supplied by Asahi Glass Co., solids content: 50%) Isocyanate (hardener) 3.7 We apply the paint in a thickness of

  g / m2 on a 50 mm x 150 mm slate plate.

  The test tube thus prepared is examined using a colorimeter to measure the values L, a and b. The LE color difference is calculated between the case where titanium oxide is added and the case where it is not added, according to the formula LE-V (LL) 2 + (La) 2 + (Ab) 2 On prepare a paint in the same way as above, except that untreated red iron oxide is used. We measure the color difference LE 'on

  a test tube prepared in the same manner as above.

  The LE / LE 'ratio is given in Table 21 as an index of the coloring power of the treated pigment. In general, the coloring power is all the more

  low that this ratio is smaller and less than 1.

  The LE / LE 'ratio of this pigment is 0.85, as indicated

as shown in table 21.

Example 50

  A paint is prepared in the same manner as in the Reference example, except that black iron oxide treated with 10% 8 17SO2N (C3H7) CH2CH2CH2Si (OCH3) 3 is used and it is put the test in the same way. The report

LE / LE 'is 0.95.

  Comparative Example 37 A paint is prepared in the same manner as in the Reference Example, except that red iron oxide treated with 0.1% C3H7Si (OCH3) 3 is used and it is put the test in the same way. The report

AE / LE 'is 0.98.

  Comparative Example 38 A paint is prepared in the same manner as in the Reference Example, except that black iron oxide treated with 10% CH3CONH (CH2) 3Si (OCH3) 3 is used and it is tests in the same way. The AE / 4E 'ratio is 0.95.

  The results of Example 49 to Example Compa-

  rat 38 are summarized in Table 21.

Table 21

  Example Pigment 'Fluorinated silane Quantity E / AIE' 49 Red iron oxide C8F! 7SO2N (CH3) (CH2) 3- 0.1 0.85 Si (OCH3) 3 50. Black iron oxide C8F17SO2N (C3H7) (CH2) 3 10.0 0.75 Comparative Example Si (OCH3) 3 37 Red iron oxide C3H7Si (OCH3) 3. 0.1 0.95 38 Black iron oxide CH3CONH (CH2) 3Si (OCH3) 3 10.0 0.95

Example 51

  An ultrafine silica powder ("Aerosil n 200", sold by Nippon Aerosil Kabushiki Kaisha), which is an additive for paints with a thickening effect, is treated with 3.0% by weight of the fluorinated silane used in Example 47, c '' ie: C8F17SO2N (CH3) CH2CH2CH2Si (OCH3) 3 and a paint is prepared using the materials

  listed below (Formula 4>.

  Formula 4 Ingredient Parts by weight Ultrafine silica powder treated 2 Pigmentary titanium oxide 10 "Lumiflon LF-300" 30 (a solution of fluorinated resin with low viscosity, sold by Asahi Glass Co.) Toluene 60 Isocyanate (hardener) 2,8 The same test is carried out with this paint as that used in Example 46. The results are

set out in Table 20.

  Comparative Example 39 A paint was prepared in the same manner as in Example 51, except that untreated ultrafine silica powder was used, and the paint was tested in the same manner. The paint of Example 51 is superior to that of this comparative example, by 2.3% in whiteness, by 3.6% in gloss at 60

and 8.4% in covering power.

  Centrifuge these paints and leave them

  stand to examine the sedimentation property.

  Paint prepared using ultrafine silica powder treated with fluorinated silane does not sediment when centrifuged at 1000 rpm for 30 min. Paint prepared using silica powder

  untreated ultrafine settles under the same conditions

  tions. It is established that the ultrafine silica powder treated with the fluorinated silane of the present invention is superior in its thickening property to the

  untreated ultrafine silica powder.

  When added to wax, the fluorinated silanes of the present invention improve its hydrophobicity, oleophobicity, stain resistance and resistance to organic solvents. For this purpose, the silanes are added to the wax in an amount of 0.1

  at 20% by weight, preferably 1 to 5% by weight, relative to

  weight of wax. Usually the compounds are

  mixed with wax in the melt state. However

  they can be mixed with the wax in the state of

  solution in an appropriate solvent.

Example 52 -

  3.5 g of C8F17SO2N (C3H7) CH2CH2CH2Si (OCH3) 3 are mixed with a melt of 100 g of a commercially available wax ("Hoechst Waw S", sold by Nippon Hoechst Kabushiki Kaisha) and applied The mixture

  on the surface of a 5 mm thick glass slide.

  The connection angles for water and paraffin oil are measured. They are 123 and 82 respectively. Those of pure wax are 91 and 280 respectively. Comparative Example 40 The procedure of Example 52 is repeated using a commercially available fluorosurfactant ("EFTOP-201", sold by New Akita Chemical,

  Co.) in place of said fluorinated silane. The connection angles

  of the wax thus modified are 101 for water

  and 45 for paraffin oil. -

Claims (29)

  1. N-alkyl-N- [3- (substituted silyl) propyl] -   perfluoralkylsulfonamides represented by the formula: 1-. 2 C F SO NC HC IR A   n 2n + lSO2NR CH2CH2CH2SR 3-mAm i in which R is an alkyl group having 1 to carbon atoms, R is an alkyl group having 1 to 5 carbon atoms, A is chosen from chlorine, bromine and alkoxy groups having 1 to 5 carbon atoms, n is an integer from 4 to 12 and m is a whole number from 1 to 3.   2. Compounds according to claim 1, character-   risés in that A is the methoxy or ethoxy group or chlorine.   3. Compounds according to claim 1, character-   laughed in that n is an integer from 6 to 10.   4. Compounds according to claim 3, character- laughed at in that n is 8.   5. Compounds according to claim 1, character-   laughed at in that R is a propyl group.   6. Compounds according to claim 1, character-   rised in that R2 is methyl or ethyl.   7. Compounds according to claim 1, character- laughed at that m is 3.   8. Compound according to claim 1, character-   laughed at in that it is N-n-propyl-N- [3- (trichloro-   - silyl) propyl] -perfluoroctylsulfonamide.   9. Compound according to claim 1, character-   laughed at in that it is N-n-propyl-N- [3- (trimethoxy-   silyl) propyl] -perfluoroctylsulfonamide.   10. Process for preparing an N-alkyl-N- [3- (substituted silyl) -propyl] perfluoralkylsulfonamide represented by the formula: CnF2n + lSO2NR CH2CH2CH2SiR23 mAm (I in which R1 is an alkyl group having 1 to carbon atoms, R2 is an alkyl group having 1 to 5 carbon atoms, A is selected from chlorine, bromine and alkoxy groups having 1 to 5 carbon atoms, n is an integer from 4 to 12 and m is an integer from 1 to 3, characterized in that it consists in reacting a compound represented by the formula: CnF2n + lSO2NR CH2CH = CH (II) in which R1 and n are as defined above, with a compound represented by the formula: 3-SRmAm - (III) in which R2, A and m are as defined above,   in the presence of an addition reaction catalyst.   11. The method of claim 10, character-   rised in that the addition reaction catalyst is   a compound chosen from chloroplatinic acid, azo-   bisisobutyronitrile, benzoyl peroxide and a   octacarbonyl complex of cobalt, platinum or rhodium.   12. Method according to claim 10, character-   in that, when A is chlorine or bromine, the adduct is caused to react additionally   with an alcohol having 1 to 5 carbon atoms.   13. The method of claim 12, character-   laughed in that the reaction of the adduct and the alcohol is carried out by blowing dry air into the reaction mixture.   14. The method of claim 12, character-   laughed in that the reaction of the adduct and   alcohol is conducted under reduced pressure.   15. The method of claim 10, character-   risé in that, when A is chlorine or bromine, the adduct is caused to react additionally with an alcoholate of an alcohol having 1 to 5 carbon atoms.   16. The method of claim 10, character-   risé in that, when A is chlorine or bromine, the adduct is caused to react additionally with an orthoformic acid ester of a counting alcohol 1 to 5 carbon atoms.   17. Process for preparing an N-alkyl-N- [3-   (substituted silyl) propyl] -perfluoralkylsulfonamide represented by the formula: - CF S iR A CnF2n + lSO2NR CH2CH2CH2SiR 3mAm (I) i in which R is an alkyl group having 1 carbon atoms, R2 is an alkyl group having 1 atoms of carbon, A is an alkoxyl group having 1 to 5 carbon atoms, A is an alkoxy group having i to 5 carbon atoms, n is an integer from 4 to 12 and m is an integer from 1 to 3, characterized in what it consists in reacting a compound represented by the formula: C20 n 2n + 1SO2Y (IV) in which Y is fluorine, chlorine or bromine, with a compound represented by the formula: NR1CH2CH2CH2SiR 3-mAm (V )   in which R, R, m and A are as defined above above.   18. The method of claim 17, character-   laughed at in that the reaction is conducted in the presence of a organic base.   19. The method of claim 18, character-   laughed at in that the organic base used is pyridine or triethylamine.   20. The method of claim 17, character-   risé in that the compound of formula (IV) is used in an amount of more than 1 molar equivalent relative   the amount of the compound of formula (V).   21. The method of claim 17, character-   risé in that the compound of formula (IV) is used in an amount of 1.05 to 1.2 molar equivalent relative to the amount of the compound of formula (V). 22. Water and oil repellent agent for mineral materials, characterized in that it comprises a compound   according to any one of claims 1 to 9.   23. Composition of fluorinated resin, characterized in that it contains a mineral filler treated with 0.1 to 10% by weight of a compound according to any one of claims 1 to 9.   24. Powder or mineral fiber, characterized in that its surface is treated with 0.1 to 20% by weight   of a compound according to any one of claims 1 to 9.   25. Metallic material, characterized in that   its surface is treated with a compound according to one conch of claims 1 to 9.   26. Paper-based material, characterized in that its surface is treated with a compound according to one   any of claims 1 to 9.   27. Glass material, characterized in that its   surface is treated with a compound according to any one as in claims 1 to 9.   28. Mineral building material, characteristic   laughed at in that it is treated with a compound according to one   any of claims 1 to 9.   29. Coating composition, characterized in that it contains a pigment treated with 0.1 to 20% by   weight of a compound according to any one of the claims 1 to 9.