Synthetic resin ophthalmic lens having an inorganic coating

• US 5,622,784 A
• Filed: 01/18/1994
• Issued: 04/22/1997
• Est. Priority Date: 01/21/1986
• Status: Expired due to Term

• Current Assignee: Hoya Lens Manufacturing Philippines, Inc. (Hoya Corporation)
• Original Assignee: Seiko Epson Corporation (Seiko Group)
• Inventors: Kubota, Satoshi, Okaue, Etsuo, Mogami, Takao, Nakajima, Mikito
• Primary Examiner(s): Hulina, Amy
• Application Number:
  US08/183,105
• Time in Patent Office: 1,190 Days
• Field of Search: 428/411.1, 428/412, 428/446, 428/447, 428/448, 428/688, 428/429, 106/287.1, 106/287.11, 106/287.12, 106/287.14, 106/287.16, 351/44.62, 351/166, 351/44, 351/62, 427/164
• US Class Current: 428/447
• CPC Class Codes: C03C 17/30 with silicon-containing compounds
• CPC Class Codes: C03C 17/42 at least one coating of an organic material and at least one non-metal coating
• CPC Class Codes: C03C 2217/76 Hydrophobic and oleophobic coatings
• CPC Class Codes: G02B 1/10 Optical coatings produced by application to, or surface treatment of, optical elements G02B1/08 takes precedence
• CPC Class Codes: G02B 1/18 Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films G02B1/16 takes precedence
• CPC Class Codes: G02B 5/3033 in the form of a thin sheet or foil, e.g. Polaroid
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

An inorganic coating film having improved water repellency is provided. The improved surface is provided by treating an inorganic coating film with a material that is reached or adsorbed on the surface of the inorganic coat to increase water repellency. The inorganic coating to be treated may be a silicon dioxide film. The materials used to treat the film include: (1) halogenated silane compounds; (2) silane compounds having a structure including at least one bond selected from Si--H, Si--OH, Si--OR, Si--SH and Si--SR, wherein R is an organic group; (3) silane compounds having a structure including at least one of ##STR1## wherein R1, R2 and R3 are hydrogen or an organic group and (4) reactive organic compounds having a fluorine substituting group, hydrogen fluoride or a metal fluoride.

Claims

1. A method for making a synthetic resin opthalmic lens having an SiO₂ antireflective coating film resistant to spots caused by water, comprising coating a synthetic resin ophthalmic lens substrate with an antireflective coating of SiO₂ and treating the surface of the SiO₂ coating film at a temperature from 10°

to 60°

C. with at least a compound which reacts with or is adsorbed onto the surface of the coating to improve the water repellency of the treated film, the compound selected from the group consisting of;

(1) halogenated silane compounds;

(2) silane compounds having a linkage selected from the group of Si-SH and Si-SR wherein R is an organic group; and

(3) silane compounds having an Si-N linkage in the form of ##STR16## wherein R3 is hydrogen or an organic group; and

(4) organic compounds having fluorine substituting groups selected from

(i) acyl halides represented by the formula;

##STR17## wherein Rf is an organic group partially substituted by fluorine and X is halogen;

(ii) ammonium salt represented by the formula;

space="preserve" listing-type="equation">RfR.sub.3 N.sup.30 Y.sup.-

wherein Rf is an organic group partially substituted by fluorine, R is an alkyl group having 1 to 3 carbon atoms, and Y^- is anion selected from the group consisting of halogen ion, sulfate ion and carboxylic acid ion;

(iii) isocyanate esters represented by Rf--N═

C═

O and thioisocyanate esters represented by Rf--N═

C═

S wherein Rf is an organic group partially substituted by fluorine;

(iv) hydrogen fluoride; and

(v) metal fluorides.

2. The method of claim 1, wherein the surface of the SiO₂ coating film is treated with the compound by dipping the film into a solution containing the compound.

3. The method of claim 1, wherein the surface of the SiO₂ coating film is treated with the compound by spinning.

4. The method of claim 1, wherein the surface of the SiO₂ coating film is treated with the compound by spraying the compound onto the surface of the SiO₂ coating film.

5. The method of claim 1, wherein the surface of the SiO₂ coating film is treated by applying the compound directly onto the surface of the SiO₂ coating film in a gaseous state.

6. The method of claim 1, wherein the SiO₂ coating film is treated in a vacuum.

7. The method of claim 1, wherein the SiO₂ coating film is treated in an inert atmosphere.

8. The method of claim 1, wherein the compound for treating the surface of the SiO₂ coating film is a halogenated silane compound.

9. The method of claim 1, wherein the compound for treating the surface of the SiO₂ coating film is a silane compound having a Si-SH linkage.

10. The method of claim 1, wherein the compound for treating the surface of the SiO₂ coating film is a silane compound having a Si-SR linkage, wherein R is an organic group.

11. The method of claim 1, wherein the compound for treating the surface of the SiO₂ coating film is a silane compound having a Si-N linkage in the form of ##STR18## wherein R3 is a hydrogen or an organic group.

12. The method of claim 1, wherein the compound for treating the surface of the SiO₂ coating film is selected from the group consisting of:

(i) acyl halides represented by the formula;

##STR19## wherein Rf is an organic group partially substituted by fluorine and X is halogen;

(ii) ammonium salt represented by the formula;

space="preserve" listing-type="equation">RfR.sub.3 N.sup.+ Y.sup.-

wherein Rf is an organic group partially substituted by fluorine and R is an alkyl group having 1 to 3 carbon atoms and Y^- is an anion selected from the group consisting of halogen ions, sulfate ions and carboxylic acid ions;

(iii) isocyanate esters represented by Rf--N═

C═

O and thioisocyanate esters represented by Rf--N═

C═

C═

S wherein Rf is an organic group partially substituted by fluorine;

(iv) hydrogen fluoride; and

(v) metal fluorides.

13. The method of claim 1, wherein the compound is selected from the group consisting of ##STR20## wherein A is fluorine atom or hydrogen atom, n is an integer from 1 to 18, a is 1 or 2, b is 0 or 1 and c is an integer from 0 to 2 ##STR21## wherein m is an integer from 0 to 17, d is an integer from 0 to 5 and R'"'"' is alkyl group having 1 to 5 carbon atoms. ##STR22## wherein 1 is an integer from 0 to 5.

14. An improved synthetic resin opthalmic lens having an inorganic coating film disposed thereon resistant to spotting due to water droplets on the surface of the inorganic film, comprising a transparent organic resin opthalmic lens supporting a top layer anti-reflective SiO₂ coating film, the SiO₂ coating film having been treated with a compound which reacts with or is adsorbed to the surface of the film to improve the water repellency properties of the SiO₂ coating film so as to have a contact angle with water between 89°

and 132°

, the compound selected from the group consisting of

(1) halogenated silane compounds;

(2) silane compounds having a structure including at least one bond selected from the group consisting of Si-SH and Si-SR wherein R is an organic group;

(3) silane compounds having the structure ##STR23## wherein R3 is hydrogen or an organic group;

(4) organic compounds having fluorine substituting groups selected from

(i) acyl halides represented by the formula;

##STR24## wherein Rf is an organic group partially substituted by fluorine and X is halogen;

(ii) ammonium salt represented by the formula;

space="preserve" listing-type="equation">RfR.sub.3 N.sup.+ Y.sup.-

wherein Rf is an organic group partially substituted by fluorine, R is an alkyl group having 1 to 3 carbon atoms, and Y^- is an anion selected from the group consisting of halogen ions, sulfate ions and carboxylic acid ions;

(iii) isocyanate esters represented by Rf--N═

C═

O and thiocyanate esters represented by Rf--N═

C═

S, wherein Rf is an organic group partially substituted by fluorine;

(iv) hydrogen fluoride; and

(v) a metal fluorides.

15. The improved synthetic resin opthalmic lens of claim 14, wherein the compound is an organic compound having a metal fluoride substituting group and the metal fluoride is selected from the group consisting of NaF, NaHF₂, CaF₂, AlF₃, ZnF₂ SbF₃, SbF₅, CrF₃, KF, CoF₃, MgF₂, TlF, FeF₂, FeF₃, NiF₂ and BaF₂.

16. The improved synthetic resin ophthalmic lens of claim 14, wherein the inorganic coating film on the resin ophthalmic lens consists essentially of the SiO₂ coating film and the compound which reacts with or is adsorbed to the surface of the film.

17. The improved synthetic resin opthalmic lens of claim 14, wherein the compound is a halogenated silane compound having the formula Si-X wherein X is halogen.

18. The improved synthetic resin opthalmic lens of claim 14, wherein the compound is a silane having an Si-SH linkage.

19. The improved synthetic resin opthalmic lens of claim 14, wherein the compound is a silane having an Si-SR linkage, wherein R is an organic group.

20. The improved synthetic resin opthalmic lens of claim 14, wherein the compound is a silane including the structure ##STR25## wherein R3 is hydrogen or an organic group.

21. The improved synthetic resin opthalmic lens of claim 14, wherein the compound is selected from the group consisting of:

(i) acyl halides represented by the formula;

##STR26## wherein Rf is an organic group partially substituted by fluorine and X is halogen;

(ii) ammonium salts represented by the formula;

space="preserve" listing-type="equation">RfR.sub.3 N.sup.+ Y.sup.-

wherein Rf is an organic group partially substituted by fluorine, R is an alkyl group having 1 to 3 carbon atoms, and Y^- is anion such as halogen ion, sulfate ion and carboxylic acid ion; and

(iii) isocyanate esters represented by Rf--N═

C═

O and thioisocyanate esters represented by Rf--N═

C═

S wherein Rf is an organic group partially substituted by fluorine including compounds wherein Rf are those represented by the formulae (I), (II) and (III) ##STR27## wherein A is a fluorine atom or a hydrogen atom, n is an integer from 1 to 18, a is 1 or 2, b is 0 or 1 and c is an integer from 0 to 2 ##STR28## wherein m is an integer from 0 to 17, d is an integer from 0 to 5 and R'"'"' is alkyl group having 1 to 5 carbon atoms ##STR29## wherein 1 is an integer from 0 to 5.

22. The improved synthetic resin opthalmic lens of claim 14, wherein an SiO₂ layer is disposed on the synthetic resin opthalmic lens substrate, a ZrO₂ layer is disposed on the SiO₂ layer;

a second SiO₂ layer is disposed on the ZrO₂ layer;

a second ZrO₂ layer is disposed on the second SiO₂ layer; and

a third SiO₂ layer is disposed on the second ZrO₂ layer, the third SiO₂ layer being the top layer treated with the silane compound.