FLUORINE-CONTAINING BORIC ACID COMPOSITE PARTICLES

Abstract

The present invention provides fluorine-containing boric acid composite particles comprising a condensate of boric acid and a fluorine-containing alcohol represented by the general formula:

R.sub.F-A-OH [I]

wherein R.sub.F is a perfluoroalkyl group having 6 or less carbon atoms, or a polyfluoroalkyl group, in which some of the fluorine atoms of the perfluoroalkyl group are replaced by a hydrogen atom or atoms, and which contains a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms; and A is an alkylene group having 1 to 6 carbon atoms. The fluorine-containing boric acid composite particles may also be a condensate of boric acid, the said fluorine-containing alcohol, and an alkoxysilane at a molar ratio of 1.0 or less based on the fluorine-containing alcohol. These fluorine-containing boric acid composite particles has excellent adhesion to inorganic substrates, and the like.

Claims

1. Fluorine-containing boric acid composite particles comprising: a condensate of boric acid and a fluorine-containing alcohol represented by the general formula:
R.sub.F-A-OH [I] wherein R.sub.F is a perfluoroalkyl group having 6 or less carbon atoms, or a polyfluoroalkyl group, in which some of the fluorine atoms of the perfluoroalkyl group are replaced by a hydrogen atom or atoms, and which contains a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms; and A is an alkylene group having 1 to 6 carbon atoms, or a condensate of boric acid, the said fluorine-containing alcohol, and an alkoxysilane at a molar ratio of 1.0 or less based on the fluorine-containing alcohol.

2. The fluorine-containing boric acid composite particles according to claim 1, wherein the fluorine-containing alcohol represented by the general formula [I] is a polyfluoroalkyl alcohol represented by the general formula:
C.sub.nF.sub.2n+1(CH.sub.2).sub.jOH [II] wherein n is an integer of 1 to 6, and j is an integer of 1 to 6.

3. The fluorine-containing boric acid composite particles according to claim 1, wherein the fluorine-containing alcohol represented by the general formula [I] is a polyfluoroalkyl alcohol represented by the general formula:
C.sub.n F.sub.2n+1(CH.sub.2CF.sub.2).sub.a(CF.sub.2CF.sub.2).sub.b(CH.sub.2CH.sub.2).sub.cOH [III] wherein n is an integer of 1 to 6, a is an integer of 1 to 4, b is an integer of 0 to 2, and c is an integer of 1 to 3.

4. The fluorine-containing boric acid composite particles according to claim 1, wherein the alkoxysilane is a silane derivative represented by the general formula:
(R.sub.1O).sub.pSi(OR.sub.2).sub.q(R.sub.3).sub.r [IV] wherein R.sub.1 and R.sub.3 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group; R.sub.2 is an alkyl group having 1 to 6 carbon atoms or an aryl group, with the proviso that not all of R.sub.1, R.sub.2, and R.sub.3 are aryl groups; and p+q+r is 4, with the proviso that q is not 0.

5. The fluorine-containing boric acid composite particles according to claim 1, wherein the boric acid is used at a ratio of 0.1 to 50 parts by weight based on 100 parts by weight of fluorine-containing alcohol.

6. Fluorine-containing boric acid composite particles comprising: a condensate of boric acid and a fluorine-containing alcohol represented by the general formula:
R.sub.F-A-OH [Ia] or the general formula:
HO-A-R.sub.F-A-OH [Ib] wherein R.sub.F is a linear or branched perfluoroalkyl group containing a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms, and containing an O, S, or N atom; R.sub.F is a linear or branched perfluoroalkylene group containing a perfluoroalkylene group having 6 or less carbon atoms, and containing an O, S, or N atom; and A is an alkylene group having 1 to 6 carbon atoms, or a condensate of boric acid, the said fluorine-containing alcohol, and an alkoxysilane at a molar ratio of 1.0 or less based on the fluorine-containing alcohol.

7. The fluorine-containing boric acid composite particles according to claim 6, wherein the fluorine-containing alcohol represented by the general formula [Ia] is a hexafluoropropene oxide oligomer alcohol represented by the general formula:
C.sub.mF.sub.2m+1O[CF(CF.sub.3)CF.sub.2O].sub.dCF(CF.sub.3)(CH.sub.2).sub.eOH [IIa] wherein m is an integer of 1 to 3, d is an integer of 0 to 100, and e is an integer of 1 to 3.

8. The fluorine-containing boric acid composite particles according to claim 6, wherein the fluorine-containing alcohol represented by the general formula [Ib] is a perfluoroalkylene ether diol represented by the general formula:
HO(CH.sub.2).sub.fCF(CF.sub.3)[OCF.sub.2CF(CF.sub.3)].sub.gO(CF.sub.2).sub.hO[CF(CF.sub.3)CF.sub.2O].sub.iCF(CF.sub.3)(CH.sub.2)OH wherein f is an integer of 1 to 3, g+i is an integer of 0 to 50, and h is an integer of 1 to 6.

9. The fluorine-containing boric acid composite particles according to claim 6, wherein the alkoxysilane is a silane derivative represented by the general formula:
(R.sub.1O).sub.pSi(OR.sub.2).sub.q(R.sub.3).sub.r [IV] wherein R.sub.1 and R.sub.3 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group; R.sub.2 is an alkyl group having 1 to 6 carbon atoms or an aryl group, with the proviso that not all of R.sub.1, R.sub.2, and R.sub.3 are aryl groups; and p+q+r is 4, with the proviso that q is not 0.

10. The fluorine-containing boric acid composite particles according to claim 6, wherein the boric acid is used at a ratio of 0.1 to 50 parts by weight based on 100 parts by weight of fluorine-containing alcohol.

11. The fluorine-containing boric acid composite particles according to claim 1, which have a particle size of 10 to 600 nm, measured by a dynamic light scattering method.

12. A surface-treating agent comprising the fluorine-containing boric acid composite particles according to claim 11 as an active ingredient.

13. The fluorine-containing boric acid composite particles according to claim 6, which have a particle size of 10 to 600 nm, measured by a dynamic light scattering method.

14. A surface-treating agent comprising the fluorine-containing boric acid composite particles according to claim 13 as an active ingredient.

Description

EXAMPLES

[0051] The following describes the present invention with reference to Examples.

Example 1

[0052] 1,100 mg of CF.sub.3(CF.sub.2).sub.5(CH.sub.2).sub.2OH [FA-6], 200 mg of boric acid, and 2 ml of tetrahydrofuran [THF] were charged in a 30-ml reaction vessel, and the mixture was stirred at room temperature for a day. Then, the solvent was distilled off, thereby obtaining 767 mg (yield: 59%) of the target fluorine-containing boric acid composite particles. With respect to the obtained fluorine-containing boric acid composite particles, the following items were measured.

[0053] Particle size and its variation: Table 1

[0054] The particle size and its variation were measured using a methanol dispersion having a solid matters content of 1 g/L at 25 C. by a dynamic light scattering (DLS) method

[0055] Contact angle of droplets (unit: ): Table 2

[0056] Prepared glass slides were dipped in methanol dispersions (particle concentration: 5 g/L), and then dried under room temperature condition. 4 l of droplets of n-dodecane or water were gently brought into contact with the obtained thin layer surfaces, and the contact angle of the droplets adhering to the thin layer surfaces was measured by the /2 method using a contact angle meter (Drop Master 300, produced by Kyowa Interface Science Co., Ltd.). The contact angle with water was measured with time.

[0057] The contact angles of both n-dodecane and water for the glass substrates in the Examples indicated water-repellency or oil-repellency.

Examples 2 to 9

[0058] In Example 1, the amount of FA-6 and the amount of boric acid were changed in various ways.

Examples 10 to 19

[0059] In Example 1, various fluorine-containing alcohols were used in place of FA-6, and tetraethoxysilane [TEOS; density: 0.94 g/cm.sup.3] was appropriately used. The amount of THF used in Examples 14 to 16 was 4 ml.

OXF3PO: HOCH.sub.2CF(CF.sub.3)OCF.sub.2CF(CF.sub.3)OCF.sub.2CF.sub.2OCF(CF.sub.3)CH.sub.2OH

OXF14PO:

HOCH.sub.2CF(CF.sub.3) [OCF.sub.2CF(CF.sub.3)] .sub.nOCF.sub.2CF.sub.2O [CF(CF.sub.3)CF.sub.2O] .sub.mCF(CF.sub.3)CH.sub.2OH (n+m=12)

DTFAC: C.sub.4F.sub.9(CH.sub.2CF.sub.2)(CF.sub.2CF.sub.2).sub.2(CH.sub.2CH.sub.2)

TABLE-US-00001 TABLE 1 Fluorine-containing Boric alcohol acid TEOS Amount Yield Particle size Example Abbreviation mg mM (mg) ml mM (mg) (%) (nm) 1 FA-6 1100 3.02 200 767 59 130.0 15.0 2 FA-6 1100 3.02 100 900 75 196.0 26.0 3 FA-6 2200 6.04 100 1955 85 145.0 19.0 4 FA-6 1100 3.02 200 0.10 0.45 1129 81 54.7 5.0 5 FA-6 1100 3.02 100 0.10 0.45 1035 80 72.1 17.2 6 FA-6 1100 3.02 50 0.10 0.45 908 73 24.3 2.4 7 FA-6 2200 6.04 400 0.20 0.90 2565 92 578.4 155.1 8 FA-6 2200 6.04 200 0.20 0.90 2381 92 72.1 17.2 9 FA-6 2200 6.04 100 0.20 0.90 2115 85 24.3 2.4 10 OXF3PO 1250 2.23 60 1061 81 313.0 46.0 11 OXF3PO 1250 2.23 30 1152 90 288.0 78.0 12 OXF3PO 5600 10.0 30 0.05 0.23 1011 79 266.0 30.0 13 OXF3PO 1250 2.23 60 0.10 0.45 1166 89 65.7 8.9 14 OXF14PO 1000 0.42 6.5 393 39 128.0 14.0 15 OXF14PO 1000 0.42 13 365 36 262.0 59.0 16 OXF14PO 1000 0.42 26 349 34 15.7 1.0 17 DTFAC 100 0.19 12 108 96 105.0 25.0 18 DTFAC 100 0.19 5.9 103 97 10.8 1.1 19 DTFAC 100 0.19 2.9 99 96 313.0 78.0

TABLE-US-00002 TABLE 2 Water (elapsed time: min.) Example n-dodecane 0 5 10 15 20 25 30 Ex. 1 39 62 59 57 54 55 52 50 Ex. 2 39 46 46 46 46 47 48 48 Ex. 3 31 44 40 35 27 21 14 7 Ex. 4 31 45 41 36 32 27 19 14 Ex. 5 28 54 46 41 35 29 24 16 Ex. 6 31 42 38 34 30 22 20 15 Ex. 7 33 49 46 41 32 28 19 11 Ex. 8 37 53 48 42 38 32 21 23 Ex. 9 45 98 93 88 82 71 63 48 Ex. 10 49 62 56 50 45 36 30 29 Ex. 11 20 67 65 62 60 59 56 56 Ex. 12 47 44 42 41 37 36 33 31 Ex. 13 40 25 21 19 17 16 15 14 Ex. 14 53 53 50 49 47 46 45 42 Ex. 15 53 55 56 53 50 48 47 44 Ex. 16 56 58 49 48 47 44 43 42 Ex. 17 38 77 74 69 63 57 57 60 Ex. 18 49 71 69 66 60 53 47 43 Ex. 19 50 100 93 93 86 80 80 80

Comparative Example 1

[0060] With respect to an uncoated glass substrate, a droplet contact angle was measured in the same manner as in Example 1.

Comparative Example 2

[0061] With respect to a glass substrate coated with boric acid, a droplet contact angle was measured in the same manner as in Example 1.

Comparative Examples 3 to 7

[0062] In the droplet contact angle measurement in Example 1, glass substrates coated with methanol dispersions (5 g/L) of the following samples in place of the fluorine-containing boric acid composite particle methanol dispersion were used. [0063] Comparative Example 3: boric acid/TEOS [0064] Comparative Example 4: FA-6 [0065] Comparative Example 5: FA-6/TEOS

Comparative Example 6: OXF3PO

Comparative Example 7: OXF14PO

[0066] However, in Comparative Example 3, FA-6 was not used in Example 1, and 50 mg (0.81 mmol) of boric acid and 0.10 ml (0.45 mmol) of TEOS were used. The amount of the product was 130 mg, and the yield was 90%. Moreover, in Comparative Example 5, boric acid was not used in Example 1, and 1,100 mg (3.02 mmol) of FA-6 and 0.10 ml (0.45 mmol) of TEOS were used. The amount of the product was 763 mg, and the yield was 68%.

[0067] The result of the foregoing Comparative Examples is shown in the following Table 3.

TABLE-US-00003 TABLE 3 Water (elapsed time: min.) Example n-dodecane 0 5 10 15 20 25 30 Com. Ex. 1 0 50 Com. Ex. 2 22 66 Com. Ex. 3 20 55 Com. Ex. 4 30 43 39 35 31 22 21 16 Com. Ex. 5 11 36 32 28 21 17 13 7 Com. Ex. 6 45 62 60 58 56 55 50 53 Com. Ex. 7 58 63 54 51 49 47 45 42