Hybrid sol for the production of abrasion-resistant SiO2 antireflection coatings

• US 7,241,505 B2
• Filed: 09/19/2002
• Issued: 07/10/2007
• Est. Priority Date: 09/21/2001
• Status: Expired due to Fees

• Current Assignee: Merck Patentgesellschaft
• Original Assignee: Merck Patent GmbH (Merck & Co., Inc.)
• Inventors: Gombert, Andreas, Kursawe, Monika, Hofmann, Thomas, Glaubitt, Walther
• Primary Examiner(s): PENG, KUO LIANG
• Application Number:
  US10/490,310
• Publication Number:
  US 20040248995A1
• Time in Patent Office: 1,755 Days
• Field of Search: 428/429, 528/39, 528/12
• US Class Current: 428/429
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01B 33/145 Preparation of hydroorganosols, organosols or dispersions in an organic medium
• CPC Class Codes: C03C 17/001 General methods for coating; Devices therefor
• CPC Class Codes: C03C 17/007 containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
• CPC Class Codes: C03C 17/25 by deposition from the liquid phase
• CPC Class Codes: C03C 2217/213 SiO2
• CPC Class Codes: C03C 2217/425 consisting of a porous layer
• CPC Class Codes: C03C 2218/113 by sol-gel processes
• CPC Class Codes: C08L 2666/54 Inorganic substances
• CPC Class Codes: C09D 183/02 Polysilicates
• CPC Class Codes: Y10T 428/31612 As silicone, silane or siloxane

Abstract

Hybrid sol comprising [SiO_x(OH)_y]_n particles, where 0<y<4 and 0<x<2, which consist of a mixture of a first fraction of particles having a particle size of 4–15 nm and a second fraction of particles having a mean particle size of 15–60 nm, water and a solvent; obtainable by hydrolytic polycondensation of tetraalkoxysilanes in an aqueous, solvent-containing medium with addition of a monodisperse silicon oxide hydroxide sol having a mean particle size of 15–60 nm and a maximum standard deviation of 20%, and the preparation and use thereof.

Claims

1. Hybrid sol comprising:

[SiO_x(OH)_y]_n particles, where 0<

y<

4 and 0<

x<

2, which consist of a mixture of a first fraction of particles having a particle size of 4–

15 nm and a second fraction of particles having a mean particle size of 20–

60 nm where the weight ratio between the first fraction and the second fraction is from 10;

1 to 2;

1,

water and

a solvent,

wherein the sol is obtained by a process comprising;

hydrolytic polycondensation of tetraalkoxysilanes in an aqueous, solvent-containing medium by addition of the tetraalkoxysilanes to the aqueous, solvent-containing medium, resulting in a hydrolysis mixture comprising silicon oxide hydroxide particles having a particle size of 4–

15 nm,

followed by addition to the hydrolysis mixture of a monodisperse silicon oxide hydroxide sol essentially in the form of discrete particles having a mean particle size of 20–

60 nm and a maximum standard deviation of 20%, said addition being at least 5 minutes after addition of the tetraalkoxysilanes to the aqueous, solvent-containing medium.

2. Hybrid sol according to claim 1, where the hydrolytic polycondensation is carried out in the presence of a basic catalyst.

3. Hybrid sol according to claim 1, further comprising a stabiliser which is added subsequent to the addition of the monodisperse silicon hydroxide sol.

4. Hybrid sol according to claim 3, where the stabiliser is a glycol ether or an ether of another alcohol or a mixture of these ethers.

5. Hybrid sol according to claim 1, where the monodisperse silicon oxide hydroxide sol is obtained by a process comprising:

addition of a tetraalkoxysilane to an aqueous-alcoholic ammoniacal hydrolysis mixture, with formation of primary silicon oxide hydroxide particles, and continuous addition of further tetraalkoxysilane to this mixture in such a way that essentially no further particles are formed.

6. Hybrid sol according to claim 5, where the process for obtaining the monodisperse silicon oxide hydroxide sol is conducted at a temperature of 35–

80°

C.

7. Hybrid sol according to claim 5, where alcohol and ammonia are removed from the monodisperse silicon oxide hydroxide sol before it is added to the hydrolysis mixture to form the hybrid sol.

8. Hybrid sol according to claim 1, where the concentration of the total amount of [SiO_x(OH)_y]_n particles in the hybrid sol is 0.3–

4% by weight.

9. Hybrid sol according to claim 1, where the solvent is methanol, ethanol, i-propanol or n-propanol.

10. Hybrid sol according to claim 1, comprising 0.3–

4% by weight of [SiO_x(OH)_y]_n particles, 2–

80% by weight of water and 2–

97% by weight of solvent.

11. Hybrid sol according to claim 3, comprising 1–

2% by weight of [SiO_x(OH)_y]_n particles, 10–

35% by weight of water, 15–

30% by weight of solvent and 40–

70% by weight of stabiliser.

12. Glass having a porous antireflection layer of silicon dioxide having a refractive index of from 1.20 to 1.40, deposited from a hybrid sol according to claim 1.

13. Hybrid sol according to claim 1, wherein the sol has a random distribution of the second fraction of particles in the first fraction of particles.

14. Hybrid sol according to claim 1, wherein the solvent is acetone, methyl isobutyl ketone, diethyl ether, dibutyl ether, tetrahydrofuran, ethyl acetate, dimethylformamide, triethylamine, ethanol, methanol, i-propanol, n-propanol or mixtures thereof.

15. Process for the preparation of a hybrid sol comprising:

[SiO_x(OH)_y]_n particles, where 0<

y<

4 and 0<

x<

2, which consist of a mixture of a first fraction of particles having a particle size of 4–

15 nm and a second fraction of particles having a mean particle size of 20–

60 nm,

water and

a solvent,

which process comprises;

hydrolytic polycondensation of a tetraalkoxysilane in an aqueous, solvent-containing medium by addition of the tetraalkoxysilanes to the aqueous, solvent-containing medium, resulting in a hydrolysis mixture comprising silicon oxide hydroxide particles having a particle size of 4–

15 nm, followed by addition of a monodisperse silicon oxide hydroxide sol having a mean particle size of 20–

60 nm and a maximum standard deviation of 20% to the hydrolysis mixture at a time at least 5 minutes after addition of the tetraalkoxysilane to the aqueous, solvent-containing medium.

16. Process according to claim 15, where the hydrolytic polycondensation is carried out at a temperature of from 5 to 90°

C.

17. Process according to claim 15, where the hybrid sol is mixed vigorously for a period of from 1 minute to 48 hours at temperatures of from 10 to 40°

C. after addition of the monodisperse silicon oxide hydroxide sol.

18. Process according to claim 15, where the hydrolysis mixture comprising silicon oxide hydroxide particles having a particle size of 4–

15 nm is prepared with addition of a basic catalyst and has a pH of ≧

7.

19. Process according to claim 15, where a stabiliser is added to the hybrid sol subsequent to the addition of the monodisperse silicon hydroxide sol.

20. Process according to claim 19, where the stabiliser is a glycol ether or an ether of another alcohol or a mixture of these ethers.

21. Process according to claim 15, where the addition of the monodisperse silicon oxide hydroxide sol to the hydrolysis mixture is carried out at a time from at least 5 minutes to at most 48 hours after addition of the tetraalkoxysilane to the aqueous, solvent-containing medium.

22. Process according to claim 21, where the addition is carried out after from 20 to 180 minutes.