JP5812367B2 - Fluorine-containing nanosilica composite particles and production method thereof - Google Patents

Description

  The present invention relates to fluorine-containing nanosilica composite particles and a method for producing the same. More specifically, the present invention relates to fluorine-containing nanosilica composite particles using a fluorine-containing alcohol and a method for producing the same.

  Patent Document 1 discloses a liquid, fluorine-containing and single-component composition having a fluorine content of 5 to 75% by mass relative to a solid resin for permanent oil- and water-resistant surface treatment of porous and non-porous substrates. In combination with a suitable stabilizing component and a hydrophilic silane component, a composition having excellent storage stability, hydrophobicity, oleophobicity and dust resistance is described.

However, where not only are the fluorine-containing alcohol is used having a C ₈ or more perfluoroalkyl group is perfluorooctanoic acid and its precursors have reduction from the current environmental sought, mineral and non-mineral In preparing the surface treatment agent for the substrate, a silyl group is introduced into the fluorine compound by using a highly toxic isocyanate compound. Therefore, it is necessary to prepare the production environment for the implementation.

Special table 2011-511113 gazette WO 2007/080949 A1 JP 2008-38015 A U.S. Pat. No. 3,574,770

  An object of the present invention is to provide fluorine-containing nanosilica composite particles using a fluorine-containing alcohol having a unit that does not generate perfluorooctanoic acid or the like even when released into the environment and is easily decomposed into a short-chain compound, and a method for producing the same Is to provide.

According to the invention, the general formula
R _F -A-OH (Ia)
Or general formula
HO-AR _F '-A-OH [Ib]
(Wherein R _F is a linear or branched perfluoroalkyl group having a terminal perfluoroalkyl group having less than 8 carbon atoms and a perfluoroalkylene group having less than 8 carbon atoms, and containing an O, S or N atom. R _F ′ has a perfluoroalkylene group having less than 8 carbon atoms, is a linear or branched perfluoroalkylene group containing O, S or N atoms, and A is an alkylene group) The fluorine-containing nanosilica composite particle which consists of a condensate of the fluorine-containing alcohol and alkoxysilane and nano silica particle which are represented by these is provided.

  Such fluorine-containing nanosilica composite particles are produced by a method in which the fluorine-containing alcohol [Ia] or [Ib] and alkoxysilane are subjected to a condensation reaction in the presence of nanosilica particles using an alkaline or acidic catalyst.

  The fluorine-containing alcohol used in the present invention has a terminal perfluoroalkyl group or a perfluoroalkylene group having a carbon number of less than 8, and has a unit that is easily decomposed into a short-chain fluorine-containing compound having a carbon number of less than 8. Therefore, it does not lead to environmental pollution. Further, the fluorine-containing nanosilica composite particles obtained by coexisting the organonanosilica particles during the condensation reaction between the fluorine-containing alcohol and the alkoxysilane can be stably dispersed in a polar solvent such as water, alcohol, and tetrahydrofuran. It excels in heat resistance at a high temperature such as ° C. Specifically, it decreases the value of increase in composite particle size and weight loss.

The fluorine-containing alcohol [Ia] is a fluorine-containing alcohol in which the R _F group is a perfluoroalkyl group having 3 to 305 carbon atoms, preferably 8 to 35 carbon atoms, and A is an alkylene group having 1 to 3 carbon atoms, preferably 1 carbon atom. Alcohol, for example, the general formula
C _m F _{2m + 1} O (CF (CF ₃ ) CF ₂ O] _d CF (CF ₃ ) (CH ₂ ) _e OH (IIa)
m: 1-3, preferably 3
d: 0 to 100, preferably 1 to 10
e: 1 to 3, preferably 1
The hexafluoropropene oxide oligomer alcohol etc. which are represented by these are used.

Further, as the fluorine-containing alcohol [Ib], a fluorine-containing alcohol in which the R _F ′ group is a perfluoroalkylene group having 5 to 160 carbon atoms and A is an alkylene group having 1 to 3 carbon atoms, preferably 1 carbon, for example, General formula
HO (CH ₂ ) _f CF (CF ₃ ) [OCF ₂ CF (CF ₃ )] _g O (CF ₂ ) _h O [CF (CF ₃ ) CF ₂ O] _i CF (CF ₃ ) (CH ₂ ) _f OH
[IIb]
f: 1-3
g + i: 0-50
h: 1-6
A perfluoroalkylene ether diol represented by the formula:

In the hexafluoropropene oxide oligomer alcohol represented by the general formula [IIa], a compound having m = 1 and e = 1 is described in Patent Document 2 and synthesized through the following steps.
Fluorine-containing ether carboxylic acid alkyl ester represented by the general formula CF ₃ O [CF (CF ₃ ) CF ₂ O] _n CF (CF ₃ ) COOR (R: alkyl group, n: integer of 0 to 12), hydrogen Reduction reaction is performed using a reducing agent such as sodium borohydride.

Furthermore, in the perfluoroalkylene ether diol represented by the general formula [IIb], f = 1 is described in Patent Documents 3 to 4, and synthesized through the following series of steps.
FOCR COF → H ₃ COO CR COOCH ₃ → HOCH ₂ RfCH ₂ OH
Rf: -C (CF ₃ ) [OCF ₂ C (CF ₃ )] _a O (CF ₂ ) _c O [CF (CF ₃ ) CF ₂ O] _b CF (CF ₃ )-

  These fluorine-containing alcohol and alkoxysilane are reacted in the presence of an alkaline or acidic catalyst to form fluorine-containing nanocomposite particles.

The alkoxysilane has the general formula
(R ₁ O) _p Si (OR ₂ ) _q (R ₃ ) _r (III)
R _1, R _3: H, alkyl group or aryl group C ₁ -C ₆
R _2: an alkyl group or an aryl group of C ₁ -C ₆
However, R ₁ , R ₂ and R ₃ are not all aryl groups
p + q + r: 4 where q is not 0, for example, trimethoxysilane, triethoxysilane, trimethoxymethylsilane, triethoxymethylsilane, trimethoxyphenylsilane, triethoxyphenylsilane, tetramethoxysilane Tetraethoxysilane or the like is used.

  The reaction between these components may be an alkaline or acidic catalyst such as aqueous ammonia or an aqueous solution of an alkali metal or alkaline earth metal hydroxide such as sodium hydroxide, potassium hydroxide or calcium hydroxide, or hydrochloric acid or sulfuric acid. In the presence, the reaction is carried out at a temperature of about 0 to 100 ° C., preferably about 10 to 30 ° C., for about 0.5 to 48 hours, preferably about 1 to 10 hours.

  The amount of the fluorinated alcohol in the obtained fluorinated nanocomposite is about 1 to 50 mol%, preferably about 5 to 30 mol%, and the composite particle size is about 30 to 200 nm.

  When such a fluorine-containing nanocomposite is produced, if a condensation reaction is carried out in the presence of organonanosilica particles in the reaction system, the fluorine-containing nanosilica composite as a condensate consisting of three components of fluorine-containing alcohol-alkoxysilane-nanosilica particles Particles can be produced.

  The nanosilica particles have an average particle size (measured by dynamic light scattering method) of 5 to 200 nm, preferably 10 to 100 nm, and a primary particle size of 40 nm or less, preferably 5 to 30 nm, more preferably 10 to A 20 nm organosilica sol is used. Actually, Nissan Chemical Industries product methanol silica sol, Snowtex IPA-ST (isopropyl alcohol dispersion), Snowtex EG-ST (ethylene glycol dispersion), Snowtex MEK-ST (methyl ethyl ketone dispersion), which are commercially available products, Snowtex MIBK-ST (methyl isobutyl ketone dispersion) or the like is used.

  Each of these components is about 1 to 99 parts by weight, preferably about 10 to 50 parts by weight of fluorine-containing alcohol, and about 1 to 99 parts by weight of alkoxysilane, preferably 100 parts by weight of nanosilica particles. About 10 to 50 parts by weight are used. When the proportion of the fluorinated alcohol used is less than this, the water / oil repellency becomes low. On the other hand, when it is used in a proportion larger than this, the dispersibility in the solvent becomes poor. Further, if the proportion of alkoxysilane used is less than this, the dispersibility in the solvent is deteriorated, whereas if it is used in a proportion higher than this, the water / oil repellency is lowered.

  Fluorine-containing nanosilica composite particles, which are reaction products, are considered to have a fluorine-containing alcohol bonded to the hydroxyl group on the surface of the nanosilica particles using a siloxane bond as a spacer. Therefore, the chemical and thermal stability of silica and fluorine Excellent water and oil repellency, antifouling properties, etc. are effectively demonstrated, and the actual glass surface treated with fluorine-containing nanosilica composite particles shows good water and oil repellency, and weight loss at 800 ° C The effect of reducing the amount is seen. In addition, the particle diameter of nanosilica composite particles and the variation thereof are also small. The nanosilica composite particles are formed as a reaction product of fluorine-containing alcohol and alkoxysilane and nanosilica particles, but other components can be mixed as long as the object of the present invention is not impaired.

  Next, the present invention will be described with reference to examples.

Reference example 1
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ OH [FA-4] 0.25 g was added to 30 ml of methanol and dissolved, and silica sol (Nissan Chemicals product methanol silica sol; containing 30 wt% nano silica, average) Particle size 11nm) 1.67g (0.50g as nano silica) and tetraethoxysilane (Tokyo Kasei product; density 0.93g / ml) 0.25ml are added, stirring with a magnetic stirrer, 0.25ml of 25wt% ammonia water is added, The reaction was performed for 5 hours.

  After completion of the reaction, methanol and aqueous ammonia were removed under reduced pressure using an evaporator, and the obtained powder was redispersed in about 20 ml of methanol overnight. The next day, centrifugation was performed using a centrifuge tube, the supernatant was discarded, and fresh methanol was added to perform rinsing. After performing this rinsing operation three times, the mouth of the centrifuge tube was covered with aluminum foil and placed in a 70 ° C. oven overnight. The next day, it was put in a vacuum dryer at 50 ° C. overnight and dried to obtain 0.582 g (yield 71%) of white powder.

  The particle size and variation of the obtained white powder fluorine-containing nanosilica composite were measured by a dynamic light scattering (DLS) measurement method at 25 ° C. for a solid content concentration of 1 g / L methanol dispersion. Further, thermogravimetric analysis (TGA) was performed before and after baking at 800 ° C. At that time, the heating rate was 10 ° C./min. Furthermore, the percentage of the weight reduced by firing relative to the initial weight was also calculated.

Furthermore, the dispersibility of the composite particles dispersed at a solid content concentration of 1% by weight in water [H ₂ O], methanol [MeOH], ethanol [EtOH], 1,2-dichloroethane [DCE] and tetrahydrofuran [THF] was visually observed. And evaluated according to the following evaluation criteria.
○: Dispersed uniformly, transparent dispersion
Δ: Slightly dispersed, dispersion is cloudy
×: Not dispersed but precipitated in the dispersion medium

Reference Examples 2-5
In Reference Example 1, 25 wt% aqueous ammonia was variously changed.

Reference Examples 6-10
In Reference Examples 1 to 5, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ OH [FA-6; C ₂ F ₅ (CF ₂ CF ₂ ) ₂ (CH ₂ CH ₂ ) OH] is the same as the fluorinated alcohol. An amount (0.25 g) was used.

Reference Examples 11-15
In Reference Examples 1 to 5, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ OH [FA-8; C ₂ F ₅ (CF ₂ CF ₂ ) ₃ (CH ₂ CH ₂ ) OH] is the same as the fluorinated alcohol. An amount (0.25 g) was used.

Reference Examples 16-20
In Reference Examples 1 to 5, CF ₃ (CF ₂ ) ₃ CH ₂ (CF ₂ ) ₅ (CH ₂ ) ₂ OH [DTFA; C ₄ F ₉ (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) ₂ (CH ₂ CH ₂ ) OH] was used in the same amount (0.25 g).

Examples 1-5
In Reference Example 2, the same amount (0.25 g) of the following compound was used as the fluorinated alcohol.
Example 1: CF ₃ (CF ₂ ) ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CH ₂ OH [PO-3-OH]
〃 2: CF ₃ (CF ₂ ) ₂ O [CF (CF ₃ ) CF ₂ O] ₄ CF (CF ₃ ) CH ₂ OH [PO-6-OH]
３ 3: HOCH ₂ CF (CF ₃ ) OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ OCF (CF ₃ ) CH ₂ OH [OXF3PO-OH]
〃 4: HOCH ₂ CF (CF ₃ ) [OCF ₂ CF (CF ₃ )] _n OCF ₂
CF ₂ O (CF (CF ₃ ) CF ₂ O) _m CF (CF ₃ ) CH ₂ OH (n + m = 6) (OXF8PO-OH)
５ 5: HOCH ₂ CF (CF ₃ ) [OCF ₂ CF (CF ₃ )] _n OCF ₂
CF ₂ O (CF (CF ₃ ) CF ₂ O) _m CF (CF ₃ ) CH ₂ OH (n + m = 12) (OXF14PO-OH)

The amount of ammonia water, the recovered amount, the yield, and various measurement results in the above Examples and Reference Examples are shown in Table 1 below. The dispersibility evaluation is shown in Table 2.
The yield is calculated as follows, assuming that tetraalkoxysilane undergoes a self-condensation reaction to form a three-dimensional siloxane-bonded Si-O, and that a -O-Si-O- [SiO ₂ ] skeleton is generated. Obtained from the equation. When silica is not used, C = 0 is calculated.
Yield (%) = A / [B + C + (D × E × F / G)] × 100
A: Generated composite weight (g)
B: Fluorine-containing alcohol weight (g)
C: Silica weight (g)
D: Tetraalkoxysilane capacity (ml)
E: Tetraalkoxysilane density (g / ml)
F: SiO ₂ molar weight (g / mol) derived from tetraalkoxysilane
G: Tetraalkoxysilane molar weight (g / mol)

Table 1
Fluorine-containing nanosilica
aq . NH ₃ recovery Yield Composite particle size (nm) Weight reduction
Example (ml) (g) (%) Before firing After firing at 800 ° C (%)
Reference Example 1 0.25 0.582 71 36.8 ± 9.9 39.0 ± 3.1 7
〃 2 0.50 0.559 68 30.1 ± 7.3 39.5 ± 9.9 7
３ 3 1.0 0.352 43 69.1 ± 13.9 45.3 ± 10.9 7
2.0 4 2.0 0.419 51 41.5 ± 10.2 42.6 ± 9.2 7
５ 5 4.0 0.571 70 34.0 ± 7.6 139.8 ± 25.5 7
６ 6 0.25 0.500 61 35.3 ± 8.3 53.3 ± 11.4 8
７ 7 0.50 0.580 71 40.5 ± 11.3 40.5 ± 12.0 6
1.0 8 1.0 0.590 72 40.5 ± 13.0 62.3 ± 18.5 6
2.0 9 2.0 0.488 60 105.3 ± 19.0 97.5 ± 30.2 7
〃 10 4.0 0.426 52 45.4 ± 13.2 60.9 ± 17.1 6
〃 11 0.25 0.521 64 41.7 ± 13.7 81.7 ± 21.6 7
〃 12 0.50 0.481 59 28.2 ± 6.0 32.2 ± 9.8 6
〃 13 1.0 0.475 58 56.6 ± 11.5 53.7 ± 10.2 6
〃 14 2.0 0.516 63 53.6 ± 11.4 55.1 ± 14.5 6
〃 15 4.0 0.565 69 39.7 ± 9.2 35.4 ± 12.8 7
〃 16 0.25 0.580 71 54.5 ± 19.3 71.9 ± 15.3 7
〃 17 0.50 0.604 74 44.3 ± 13.8 46.2 ± 10.4 7
1.0 18 1.0 0.523 64 55.6 ± 12.3 53.1 ± 14.7 8
〃 19 2.0 0.504 62 53.6 ± 10.3 54.0 ± 12.9 6
〃 20 4.0 0.578 71 63.6 ± 14.1 72.0 ± 15.5 6

Example 1 0.5 0.556 68 42.2 ± 4.2 35.2 ± 8.4 5
〃 2 0.5 0.580 71 130.5 ± 27.5 29.8 ± 5.8 7
３ 3 0.5 0.466 57 55.5 ± 7.9 23.7 ± 7.1 5
0.5 4 0.5 0.359 44 96.9 ± 10.9 30.0 ± 6.9 11
５ 5 0.5 0.507 62 90.8 ± 14.9 47.2 ± 9.7 20

Table 2
Example H ₂ O MeOH EtOH DCE THF
Reference Example 1 △ ○ ○ ○ ○
〃 2 ○ ○ ○ ○ ○
〃 3 ○ ○ ○ ○ ○
○ 4 ○ ○ ○ ○ ○
５ 5 ○ ○ ○ ○ ○
○ 6 ○ ○ ○ ○ ○
７ 7 ○ ○ ○ ○ ○
８ 8 △ ○ ○ ○ ○
９ 9 ○ ○ ○ ○ ○
〃 10 ○ ○ ○ ○ ○
〃 11 ○ ○ ○ ○ ○
〃 12 ○ ○ ○ ○ ○
〃 13 ○ ○ ○ ○ ○
〃 14 ○ ○ ○ ○ ○
〃 15 ○ ○ ○ ○ ○
〃 16 ○ ○ ○ ○ ○
〃 17 ○ ○ ○ ○ ○
〃 18 ○ ○ ○ ○ ○
〃 19 ○ ○ ○ ○ ○
〃 20 ○ ○ ○ ○ ○

Example 1 ○ ○ ○ ○ ○
〃 2 ○ ○ ○ ○ ○
〃 3 ○ ○ ○ ○ ○
○ 4 ○ ○ ○ ○ ○
５ 5 ○ ○ ○ ○ ○

Reference Examples 31-33
In Reference Examples 13 to 15, methanol silica sol was not used.

Reference Examples 34-36
In Reference Examples 18 to 20, methanol silica sol was not used.

Reference Examples 37-39
In Example 1, methanol silica sol was not used, and the amount of 25% aqueous ammonia was used with various changes.

Reference Examples 40-42
In Example 2, methanol silica sol was not used, and the amount of 25% ammonia water was variously changed.

Reference Example 43
In Example 3, methanol silica sol was not used, and the amount of 25% aqueous ammonia was changed to 4.0 ml.

Reference Example 44
In Example 4, methanol silica sol was not used, and the amount of 25% aqueous ammonia was changed to 4.0 ml.

Reference Example 45
In Example 5, methanol silica sol was not used, and the amount of 25% aqueous ammonia was changed to 4.0 ml.

The amount of aqueous ammonia, the produced fluorine-containing nanocomposite particles, the recovered amount, the yield, and various measurement results in the above Reference Examples 31 to 45 are shown in Table 3 below. The dispersibility evaluation is shown in Table 4.
Table 3
Fluorine-containing nano
aq . NH ₃ recovery Yield Composite particle size (nm) Weight reduction
Reference example (ml) (g) (%) Before firing After firing at 800 ° C (%)
31 1.0 0.065 20 54.5 ± 12.0 16.6 ± 3.8 18
32 2.0 0.059 19 21.1 ± 6.0 26.4 ± 6.0 17
33 4.0 0.065 20 37.3 ± 8.1 49.6 ± 11.2 17
34 1.0 0.072 23 41.0 ± 8.7 16.3 ± 3.9 17
35 2.0 0.044 14 47.5 ± 10.1 24.4 ± 5.7 20
36 4.0 0.069 22 81.5 ± 14.5 24.2 ± 5.6 25
37 1.0 0.073 23 48.3 ± 4.8 34.2 ± 4.4 16
38 2.0 0.073 23 53.1 ± 5.1 38.0 ± 9.2 12
39 4.0 0.067 21 45.1 ± 6.5 51.1 ± 16.8 12
40 1.0 0.070 22 141.5 ± 31.8 26.6 ± 6.3 16
41 2.0 0.048 15 80.2 ± 31.2 80.5 ± 21.2 13
42 4.0 0.063 20 69.2 ± 10.1 69.4 ± 12.5 12
43 4.0 0.051 16 60.5 ± 12.4 55.1 ± 12.1 12
44 4.0 0.063 20 55.7 ± 8.9 65.4 ± 12.1 13
45 4.0 0.171 54 63.2 ± 6.7 53.5 ± 7.8 −

Table 4
Example H ₂ O MeOH EtOH DCE THF
Reference Example 31 ○ ○ ○ ○ ○
〃 32 ○ ○ ○ ○ ○
〃 33 △ ○ ○ ○ ○
〃 34 ○ ○ ○ ○ ○
〃 35 ○ ○ ○ ○ ○
〃 36 ○ ○ ○ ○ ○
〃 37 ○ ○ ○ ○ ○
〃 38 ○ ○ ○ ○ ○
〃 39 ○ ○ ○ ○ ○
〃 40 ○ ○ ○ ○ ○
〃 41 △ ○ ○ ○ ○
〃 42 ○ ○ ○ ○ ○
〃 43 ○ ○ ○ ○ ○
〃 44 △ ○ ○ ○ ○
〃 45 ○ ○ ○ ○ ○

Reference Examples 51-70, Examples 6-10
Methanol dispersion of the fluorinated nanosilica composite particles before firing (Reference Examples 51 to 70) and the fluorinated nanocomposite particles before firing (Examples 6 to 10) obtained in Reference Examples 1 to 20 and Examples 1 to 5 The liquid (particle concentration 5g / L) is dipped into a glass preparation, dried at room temperature, and a 4μl droplet is gently brought into contact with n-dodecane or water on the surface of the resulting thin layer at room temperature. The contact angle (unit: °) of the obtained droplet was measured by a contact angle meter (DropMaster 300, manufactured by Kyowa Interface Chemical) by the θ / 2 method. The water was measured over time. The results obtained are shown in Table 5 below.
Table 5
Water (Elapsed time: minutes)
Example composite dodecane 0 5 10 15 20 25 30
Reference Example 51 Reference Example 1 35 21 10 0 0 0 0 0
〃 52 〃 2 7 22 17 15 13 11 10 7
〃 53 〃 3 4 7 0 0 0 0 0 0
〃 54 ４ 4 0 7 0 0 0 0 0 0
〃 55 ５ 5 0 0 0 0 0 0 0 0
〃 56 〃 6 49 28 0 0 0 0 0 0
〃 57 〃 7 46 48 27 26 24 20 20 17
〃 58 〃 8 16 19 19 16 14 13 10 8
〃 59 〃 9 14 11 0 0 0 0 0 0
〃 60 〃 10 19 16 7 0 0 0 0 0
〃 61 〃 11 114 37 34 33 31 30 30 28
〃 62 〃 12 108 61 58 52 49 46 45 41
〃 63 〃 13 123 59 17 0 0 0 0 0
〃 64 〃 14 125 23 13 10 8 0 0 0
〃 65 〃 15 127 91 18 4 0 0 0 0
〃 66 〃 16 82 30 21 20 14 9 0 −
〃 67 〃 17 71 64 61 58 56 55 52 52
〃 68 〃 18 55 79 77 75 68 61 58 52
〃 69 〃 19 80 95 75 63 57 50 47 42
〃 70 〃 20 47 113 82 72 64 57 53 49

Example 6 Example 1 72 23 0 0 0 0 0 0
７ 7 〃 2 62 0 0 0 0 0 0 0
８ 8 〃 3 49 18 0 0 0 0 0 0
〃 9 ４ 4 51 24 11 0 0 0 0 0
〃 10 ５ 5 66 17 0 0 0 0 0 0

Reference Examples 81-95
For the fluorine-containing nanosilica composite particles before firing obtained in Reference Examples 31 to 45, the contact angle (unit: °) of the droplets adhering to n-dodecane or water was measured in the same manner as Reference Examples 51 to 70. . The results obtained are shown in Table 6 below.
Table 6
Water (Elapsed time: minutes)
Example composite dodecane 0 5 10 15 20 25 30
Reference Example 81 Reference Example 31 50 52 48 45 38 34 29 25
〃 82 〃 32 45 62 54 47 44 37 33 25
〃 83 〃 33 43 35 29 26 22 18 14 9
〃 84 〃 34 98 81 69 61 57 53 50 44
〃 85 〃 35 73 86 69 51 45 36 28 22
〃 86 〃 36 43 61 51 48 44 36 29 24
〃 87 〃 37 42 27 17 17 17 15 15 14
〃 88 〃 38 51 30 25 23 23 22 20 19
〃 89 〃 39 34 23 0 0 0 0 0 0
〃 90 〃 40 59 43 18 15 13 13 12 11
〃 91 〃 41 64 51 37 35 35 34 31 31
〃 92 〃 42 61 34 28 27 24 24 23 23
〃 93 〃 43 54 33 12 11 10 10 9 8
〃 94 〃 44 63 90 42 40 40 38 37 37
〃 95 〃 45 64 91 47 45 44 42 42 42

Claims (4)

General formula
R _F -A-OH (Ia)
Or general formula
HO-AR _F '-A-OH [Ib]
(Wherein R _F is a linear or branched perfluoroalkyl group having a terminal perfluoroalkyl group having less than 8 carbon atoms and a perfluoroalkylene group having less than 8 carbon atoms, and containing an O, S or N atom. R _F ′ has a perfluoroalkylene group having less than 8 carbon atoms, is a linear or branched perfluoroalkylene group containing O, S or N atoms, and A is an alkylene group) The fluorine-containing nanosilica composite particle which consists of a condensate of the fluorine-containing alcohol and alkoxysilane and nanosilica particle which are represented by these. As the fluorine-containing alcohol represented by the general formula [Ia], the general formula
C _m F _{2m + 1} O (CF (CF ₃ ) CF ₂ O] _d CF (CF ₃ ) (CH ₂ ) _e OH (IIa)
2. The fluorine-containing nanosilica composite particle according to claim 1, wherein a hexafluoropropene oxide oligomer alcohol represented by (wherein m is 1 to 3, d is 0 to 100, and e is an integer of 1 to 3) is used. . As the fluorine-containing alcohol represented by the general formula [Ib], the general formula
HO (CH ₂ ) _f CF (CF ₃ ) [OCF ₂ CF (CF ₃ )] _g O (CF ₂ ) _h O [CF (CF ₃ ) CF ₂ O] _i CF (CF ₃ ) (CH ₂ ) _f OH
[IIb]
The fluorine-containing fluorine-containing composition according to claim 1, wherein a perfluoroalkylene ether diol represented by the formula (wherein f is 1 to 3, g + i is 0 to 50, and h is an integer of 1 to 6) is used. Nanosilica composite particles.   The fluorine-containing alcohol [Ia], [Ib], [IIa] or [IIb] according to claim 1, 2 or 3 is subjected to a condensation reaction using an alkaline or acidic catalyst in the presence of nanosilica particles. A process for producing fluorine-containing nanosilica composite particles characterized by the above.