# US 5,708,064 A · High refractive index photochromic ophthalmic article

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- Number: US 5,708,064 A
- Document ID: US5708064A
- Status: Granted
- Kind: A
- Application number: 08/322,834
- Filed: 1994-10-13
- Granted: 1998-01-13
- Earliest claimed: 1993-10-15
- Assignees: PPG Industries, Inc.
- Inventors: Charles R. Coleman; Robert D. Herold; Christopher D. Selvig
- Web page: https://patentgrep.com/patent/US5708064A

## CPC

- G02B 1/041: {Lenses}
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS

## Abstract

Organic ophthalmic articles are photochromic and have high indices of refraction.

## Claims

### Claim 1

In a photochromic organic ophthalmic article comprising in combination:
(a) a thermoset organic polymeric matrix having a front surface and a rear surface; and
(b) photochromic compound;
the improvement wherein:
(c) said matrix comprises polymer formed by polymerizing polymerizable composition comprising:
(1) high refractive index imparting monomer selected from the group consisting of bisphenol A bis((meth)acrylate), ethoxylated bisphenol A bis((meth)acrylate) containing from greater than 0 to 10 ethyleneoxy groups, phenoxyethyl (meth)acrylate, thiodiphenol bis((meth)acrylate), styrene, .alpha.-methylstyrene, divinylbenzene, diisopropenylbenzene, diallyl phthalate which constitutes from 0 to 40 percent by weight of the total monomer of said composition, bisphenol A bis(allyl carbonate), and a mixture of at least two or more thereof, wherein said diallyl phthalate is diallyl o-phthalate, diallyl m-phthalate, diallyl p-phthalate, or a mixture of two or more thereof, and
(2) aromatic ring-containing inert plasticizer selected from the group consisting of poly(ethylene glycol) dibenzoate, poly(propylene glycol) dibenzoate, 1,3-bis(phenylthio)propane, and a mixture of at least two thereof; and
(d) said article has a refractive index at 20.degree. C. and a wavelength of 589.3 nanometers of at least 1.53.

### Claim 2

In a photochromic organic ophthalmic article comprising in combination:
(a) a thermoset organic polymeric matrix having a front surface and a rear surface; and
(b) photochromic compound;
the improvement wherein:
(c) said matrix comprises polymer formed by polymerizing polymerizable composition comprising:
(1) high refractive index imparting monomer selected from the group consisting of bisphenol A bis((meth)acrylate), ethoxylated bisphenol A bis((meth)acrylate) containing from greater than 0 to 10 ethyleneoxy groups, phenoxyethyl (meth)acrylate, thiodiphenol bis((meth)acrylate), styrene, .alpha.-methylstyrene, divinylbenzene, diisopropenylbenzene, diallyl phthalate which constitutes from 0 to 40 percent by weight of the total monomer of said composition, bisphenol A bis(allyl carbonate), and a mixture of at least two or more thereof, wherein said diallyl phthalate is diallyl o-phthalate, diallyl m-phthalate, diallyl p-phthalate, or a mixture of two or more thereof,
(2) aromatic ring-containing inert plasticizer, and
(3) flexible monomer selected from the group consisting of (meth)acrylate of monoalkyl ether of poly(alkylene glycol), monoaryl ether of poly(alkylene glycol) mono((meth)acrylate), and a mixture thereof; and
(d) said article has a refractive index at 20.degree. C. and a wavelength of 589.3 nanometers of at least 1.53.

### Claim 3

In a photochromic organic ophthalmic article comprising in combination:
(a) a thermoset organic polymeric matrix having a front surface and a rear surface; and
(b) photochromic compound;
the improvement wherein:
(c) said matrix comprises polymer formed by polymerizing polymerizable composition comprising:
(1) high refractive index imparting monomer selected from the group consisting of bisphenol A bis((meth)acrylate), ethoxylated bisphenol A bis((meth)acrylate) containing from greater than 0 to 10 ethyleneoxy groups, phenoxyethyl (meth)acrylate, thiodiphenol bis((meth)acrylate), styrene, .alpha.-methylstyrene, divinylbenzene, diisopropenylbenzene, diallyl phthalate which constitutes from 0 to 40 percent by weight of the total monomer of said composition, bisphenol A bis(allyl carbonate), and a mixture of at least two or more thereof, wherein said diallyl phthalate is diallyl o-phthalate, diallyl m-phthalate, diallyl p-phthalate, or a mixture of two or more thereof,
(2) aromatic ring-containing inert plasticizer, and
(3) flexible monomer which comprises poly((meth)acrylate) of alkoxylated polyol containing at least 9 alkoxy groups; and
(d) said article has a refractive index at 20.degree. C. and a wavelength of 589.3 nanometers of at least 1.53.

### Claim 4

In a photochromic organic ophthalmic article comprising in combination:
(a) a thermoset organic polymeric matrix having a front surface and a rear surface; and
(b) photochromic compound imbibed into at least one of said surfaces;
the improvement wherein:
(c) said matrix comprises polymer formed by polymerizing polymerizable composition comprising aromatic ring-containing inert plasticizer;
(d) said aromatic ring-containing inert plasticizer has a refractive index at 20.degree. C. and a wavelength of 589.3 nm of at least 1.48 and is selected from the group consisting of poly(ethylene glycol)dibenzoate, poly(propylene glycol) dibenzoate, 1,3-bis(phenylthio)propane, and a mixture of at least two thereof; and
(e) said article has a refractive index at 20.degree. C. and a wavelength of 589.3 nanometers of at least 1.53.

### Claim 5

In a photochromic organic ophthalmic article comprising in combination:
(a) a thermoset organic polymeric matrix having a front surface and a rear surface; and
(b) photochromic compound imbibed into at least one of said surfaces;
the improvement wherein:
(c) said matrix comprises polymer formed by polymerizing polymerizable composition comprising:
(1) aromatic ring-containing inert plasticizer, and
(2) flexible monomer selected from the group consisting of (meth)acrylate of monoalkyl ether of poly(alkylene glycol), monoaryl ether of poly(alkylene glycol) mono(meth)acrylate), and a mixture thereof; and
(d) said article has a refractive index at 20.degree. C. and a wavelength of 589.3 nanometers of at least 1.53.

### Claim 6

In a photochromic organic ophthalmic article comprising in combination:
(a) a thermoset organic polymeric matrix having a front surface and a rear surface; and
(b) photochromic compound imbibed into at least one of said surfaces;
the improvement wherein:
(c) said matrix comprises polymer formed by polymerizing polymerizable composition comprising:
(1) aromatic ring-containing inert plasticizer, and
(2) flexible monomer which comprises poly((meth)acrylate) of alkoxylated polyol containing at least 9 alkoxy groups; and
(d) said article has a refractive index at 20.degree. C. and a wavelength of 589.3 nanometers of at least 1.53.

### Claim 7

In a photochromic organic ophthalmic article comprising in combination:
(a) a thermoset organic polymeric matrix having a front surface and a rear surface; and
(b) photochromic compound
the improvement wherein:
(c) said matrix comprises polymer formed by polymerizing polymerizable composition comprising:
(1) high refractive index imparting monomer selected from the group consisting of bisphenol A bis((meth)acrylate), ethoxylated bisphenol A bis((meth)acrylate) containing from greater than 0 to 10 ethyleneoxy groups, phenoxyethyl (meth)acrylate, thiodiphenol bis((meth)acrylate), styrene, .alpha.-methylstyrene, divinylbenzene, diisopropenylbenzene, diallyl phthalate which constitutes from 0 to 40 percent by weight of the total monomer of said composition, bisphenol A bis(allyl carbonate), and a mixture of at least two or more thereof, wherein said diallyl phthalate is diallyl o-phthalate, diallyl m-phthalate, diallyl p-phthalate, or a mixture of two or more thereof, and
(2) flexible monomer selected from the group consisting of (meth)acrylate of monoalkyl ether of poly(alkylene glycol), monoaryl ether of poly(alkylene glycol) mono((meth)acrylate), and a mixture thereof; and
(d) said article has a refractive index at 20.degree. C. and a wavelength of 589.3 nanometers of at least 1.53.

### Claim 8

In a photochromic organic ophthalmic article comprising in combination:
(a) a thermoset organic polymeric matrix having a front surface and a rear surface; and
(b) photochromic compound
the improvement wherein:
(c) said matrix comprises polymer formed by polymerizing polymerizable composition comprising:
(1) high refractive index imparting monomer selected from the group consisting of bisphenol A bis((meth)acrylate), ethoxylated bisphenol A bis((meth)acrylate) containing from greater than 0 to 10 ethyleneoxy groups, phenoxyethyl (meth)acrylate, thiodiphenol bis((meth)acrylate), styrene, .alpha.-methylstyrene, divinylbenzene, diisopropenylbenzene, diallyl phthalate which constitutes from 0 to 40 percent by weight of the total monomer of said composition, bisphenol A bis(allyl carbonate), and a mixture of at least two or more thereof, wherein said diallyl phthalate is diallyl o-phthalate, diallyl m-phthalate, diallyl p-phthalate, or a mixture of two or more thereof, and
(2) flexible monomer comprising poly((meth)acrylate) of alkoxylated polyol containing at least 9 alkoxy groups; and
(d) said article has a refractive index at 20.degree. C. and a wavelength of 589.3 nanometers of at least 1.53.

### Claim 9

In a photochromic organic ophthalmic lens or lens blank comprising in combination:
(a) a thermoset organic polymeric matrix having a front surface and a rear surface; and
(b) photochromic compound
the improvement wherein:
(c) said matrix comprises polymer formed by polymerizing polymerizable composition comprising:
(1) high refractive index imparting monomer selected from the group consisting of bisphenol A bis(methacrylate), ethoxylated bisphenol A bis(methacrylate) containing from greater than 0 to 10 ethyleneoxy groups, phenoxyethyl methacrylate, thiodiphenol bis(methacrylate), .alpha.-methylstyrene, diisopropenylbenzene, diallyl phthalate which constitutes from 0 to 40 percent by weight of the total monomer of said composition, bisphenol A bis(allyl carbonate), and a mixture of at least two thereof, wherein said diallyl phthalate is diallyl o-phthalate, diallyl m-phthalate, diallyl p-phthalate, or a mixture of two or more thereof, and
(2) flexible monomer selected from the group consisting of (meth)acrylate of monoalkyl ether of poly(alkylene glycol), monoaryl ether of poly(alkylene glycol) mono((meth)acrylate), poly((meth)acrylate) of alkoxylated polyol containing at least 9 alkoxy groups, and a mixture of at least two thereof;
(d) said photochromic compound is selected from the group consisting of
1,3-dihydro-3,3-dimethyl-5-methoxy-1-propyl-spiro›2H-indol-2,3'-›3H!pyrido{ 3,2-f}(1,4)benzoxazine!;
1. 3-dihydro-3,3,4,5-tetramethyl-1-propyl-spiro›2H-indole-2,3'-›3H!pyrido{3 ,2-f}(1,4)benzoxazine!;
1,3-dihydro-3,3,5,6-tetramethyl-1-propyl-spiro›2H-indole-2,3'-›3H!pyrido{3, 2-f}(1,4)benzoxazine!;
3-(2,4-dimethoxy)phenyl-3-(4-methoxy)phenyl-3H-naphtho›2,1-b!pyran;
1,3,3,4,5-pentamethyl-9'-methoxycarbonyl-8'-acetoxy-spiro›indoline-2-3'-›3H !naphth›2,1,b!›1,4!oxazine!;
1,3,3,5,6-pentamethyl-9'-methoxycarbonyl-8'-acetoxy-spiro›indoline-2,3'-›3H !naphth›2,1,b!›1,4!oxazine!;
3(2-fluorophenyl)-3(4-methoxyphenyl)-8-methoxy-3H-naphtho›2,1-b!pyran;
3(2-fluorophenyl)-3(4-methoxyphenyl)-8-methoxy-9-carbomethoxy-3H-naphtho›2, 1-b!pyran; and
a mixture of at least two thereof;
(e) said lens or lens blank is characterized by an absolute value of optical correction of at least 2 diopters;
(f) said lens or lens blank has a refractive index at 20.degree. C. and a wavelength of 589.3 nanometers of at least 1.53;
(g) said lens or lens blank has a heat distortion temperature of at least 35.degree. C.; and
(h) said lens or lens blank has a bleach transmission of at least 40 percent.

### Claim 10

In a photochromic organic ophthalmic article comprising in combination:
(a) a thermoset organic polymeric matrix having a front surface and a rear surface; and
(b) photochromic compound
the improvement wherein:
(c) said matrix comprises polymer formed by polymerizing polymerizable composition comprising:
(1) high refractive index imparting monomer selected from the group consisting of bisphenol A bis((meth)acrylate), ethoxylated bisphenol A bis((meth)acrylate) containing from greater than 0 to 10 ethyleneoxy groups, phenoxyethyl (meth)acrylate, thiodiphenol bis((meth)acrylate), styrene, .alpha.-methylstyrene, divinylbenzene, diisopropenylbenzene, diallyl phthalate which constitutes from 0 to 40 percent by weight of the total monomer of said composition, bisphenol A bis(allyl carbonate), and a mixture of at least two or more thereof, wherein said diallyl phthalate is diallyl o-phthalate, diallyl m-phthalate, diallyl p-phthalate, or a mixture of two or more thereof,
(2) flexible monomer, and
(3) aromatic-ring containing inert plasticizer which has a refractive index at 20.degree. C. and a wavelength of 589.3 nm of at least 1.48 and which is selected from the group consisting of poly(ethylene glycol) dibenzoate, poly(propylene glycol) dibenzoate, 1,3-bis(phenylthio)propane, and a mixture of at least two thereof; and
(d) said article has a refractive index at 20.degree. C. and a wavelength of 589.3 nanometers of at least 1.53.

### Claim 11

In a photochromic organic ophthalmic article comprising in combination:
(a) a thermoset organic polymeric matrix having a front surface and a rear surface; and
(b) photochromic compound imbibed into at least one of said surfaces;
the improvement wherein:
(c) said matrix comprises polymer formed by polymerizing polymerizable composition comprising flexible monomer selected from the group consisting of (meth)acrylate of monoalkyl ether of poly(alkylene glycol), monoaryl ether of poly(alkylene glycol) mono((meth)acrylate), and a mixture thereof; and
(d) said article has a refractive index at 20.degree. C. and a wavelength of 589.3 nanometers of at least 1.53.

### Claim 12

In a photochromic organic ophthalmic article comprising in combination:
(a) a thermoset organic polymeric matrix having a front surface and a rear surface; and
(b) photochromic compound imbibed into at least one of said surfaces;
the improvement wherein
(c) said matrix comprises polymer formed by polymerizing polymerizable composition comprising flexible monomer which comprises poly((meth)acrylate) of alkoxylated polyol containing at least 9 alkoxy groups; and
(d) said article has a refractive index at 20.degree. C. and a wavelength of 589.3 nanometers of at least 1.53.

### Claim 13

In a photochromic organic ophthalmic lens or lens blank comprising in combination:
(a) a thermoset organic polymeric matrix having a front surface and a rear surface; and
(b) photochromic compound imbibed into at least one of said surfaces;
the improvement wherein:
(c) said matrix comprises polymer formed by polymerizing polymerizable composition comprising:
(1) high refractive index imparting monomer selected from the group consisting of bisphenol A bis(methacrylate), ethoxylated bisphenol A bis(methacrylate) containing from greater than 0 to 10 ethyleneoxy groups, phenoxyethyl methacrylate, thiodiphenol bis(methacrylate), .alpha.-methylstyrene, diisopropenylbenzene, diallyl phthalate, bisphenol A bis(allyl carbonate), and a mixture of at least two thereof, and
(2) flexible monomer selected from the group consisting of (meth)acrylate of monoalkyl ether of poly(alkylene glycol), monoaryl ether of poly(alkylene glycol) mono((meth)acrylate), poly((meth)acrylate) of alkoxylated polyol containing at least 9 alkoxy groups, and a mixture thereof;
(d) said photochromic compound is selected from the group consisting of
1,3-dihydro-3,3-dimethyl-5-methoxy-1-propyl-spiro›2H-indol-2,3'-›3H!pyrido{ 3,2-f}(1,4)benzoxazine!;
1. 3-dihydro-3,3,4,5-tetramethyl-1-propyl-spiro›2H-indole-2,3'-›3H!pyrido{3 ,2-f}(1,4)benzoxazine!;
1,3-dihydro-3,3,5,6-tetramethyl-1-propyl-spiro›2H-indole-2,3'-›3H!pyrido{3, 2-f}(1,4)benzoxazine!;
3-(2,4-dimethoxy)phenyl-3-(4-methoxy)phenyl-3H-naphtho›2,1-b!pyran;
1,3,3,4,5-pentamethyl-9'-methoxycarbonyl-8'-acetoxy-spiro›indoline-2-3'-›3H !naphth›2,1,b!›1,4!oxazine!;
1,3,3,5,6-pentamethyl-9'-methoxycarbonyl-8'-acetoxy-spiro›indoline-2,3'-›3H !naphth›2,1,b!›1,4!oxazine!;
3(2-fluorophenyl)-3(4-methoxyphenyl)-8-methoxy-3H-naphtho›2,1-b!pyran;
3(2-fluorophenyl)-3(4-methoxyphenyl)-8-methoxy-9-carbomethoxy-3H-naphtho›2, 1-b!pyran; and
a mixture of at least two thereof;
(e) said lens or lens blank has a heat distortion temperature of at least 35.degree. C.;
(f) said lens or lens blank has a bleach transmission of at least 40 percent;
(g) said lens or lens blank has a refractive index at 20.degree. C. and a wavelength of 589.3 nanometers of at least 1.53; and
(h) said lens or lens blank is characterized by an absolute value of optical correction of at least 2 diopters.

### Claim 14

In a photochromic organic ophthalmic lens or lens blank comprising in combination:
(a) a thermoset organic polymeric matrix having a front surface and a rear surface; and
(b) photochromic compound;
the improvement wherein:
(c) said matrix comprises polymer formed by polymerizing polymerizable composition comprising:
(1) high refractive index imparting monomer selected from the group consisting of bisphenol A bis(methacrylate), ethoxylated bisphenol A bis(methacrylate) containing from greater than 0 to 10 ethyleneoxy groups, phenoxyethyl methacrylate, thiodiphenol bis(methacrylate), .alpha.-methylstyrene, diisopropenylbenzene, diallyl phthalate which constitutes from 0 to 40 percent by weight of the total monomer of said composition, bisphenol A bis(allyl carbonate), and a mixture of at least two thereof, wherein said diallyl phthalate is diallyl o-phthalate, diallyl m-phthalate, diallyl p-phthalate, or a mixture of two or more thereof, and
(2) aromatic ring-containing inert plasticizer selected from the group consisting of poly (ethylene glycol) dibenzoate, poly (propylene glycol) dibenzoate, 1,3-bis(phenylthio) propane, and a mixture of at least two thereof;
(d) said photochromic compound is selected from the group consisting of
1,3-dihydro-3,3-dimethyl-5-methoxy-1-propyl-spiro›2H-indol-2,3'-›3H!pyrido{ 3,2-f}(1,4) benzoxazine!;
1,3-dihydro-3,3,4,5-tetramethyl-1-propyl-spiro›2H-indole-2,3'-›3H!pyrido{3, 2-f}(1,4)benzoxazine!;
1,3-dihydro-3,3,5,6-tetramethyl-1-propyl-spiro›2H-indole-2,3'-›3H!pyrido{3, 2-f}(1,4)benzoxazine!;
3-(2,4-dimethoxy)phenyl-3-(4-methoxy)phenyl-3H-naphtho›2,1-b!pyran;
1,3,3,4,5-pentamethyl-9'-methoxycarbonyl-8'-acetoxy-spiro›indoline-2-3'-›3H !naphth›2,1,b!›1,4!oxazine!;
1,3,3,5,6-pentamethyl-9'-methoxycarbonyl-8'-acetoxy-spiro›indoline-2,3'-›3H !naphth›2,1,b!›1,4!oxazine!;
3(2-fluorophenyl)-3(4-methoxyphenyl)-8-methoxy-3H-naphtho›2,1-b!pyran;
3(2-fluorophenyl)-3(4-methoxyphenyl)-8-methoxy-9-carbomethoxy-3H-naphtho›2, 1-b!pyran; and
a mixture of at least two thereof;
(e) said lens or lens blank has a heat distortion temperature of at least 35.degree. C.;
(f) said lens or lens blank has a bleach transmission of at least 40 percent;
(g) said lens or lens blank has a refractive index at 20.degree. C. and a wavelength of 589.3 nanometers of at least 1.53; and
(h) said lens or lens blank is characterized by an absolute value of optical correction of at least 2 diopters.

### Claim 15

In a photochromic organic ophthalmic lens or lens blank comprising in combination:
(a) a thermoset organic polymeric matrix having a front surface and a rear surface; and
(b) photochromic compound imbibed into at least one of said surfaces;
the improvement wherein:
(c) said matrix comprises polymer formed by polymerizing polymerizable composition comprising:
(1) high refractive index imparting monomer selected from the group consisting of bisphenol A bis(methacrylate), ethoxylated bisphenol A bis(methacrylate) containing from greater than 0 to 10 ethyleneoxy groups, phenoxyethyl methacrylate, thiodiphenol bis(methacrylate), .alpha.-methylstyrene, diisopropenylbenzene, diallyl phthalate, bisphenol A bis(allyl carbonate), and a mixture of at least two thereof, and
(2) aromatic ring-containing inert plasticizer selected from the group consisting of poly(ethylene glycol) dibenzoate, poly(propylene glycol) dibenzoate, 1,3-bis(phenylthio)propane, and a mixture of at least two thereof;
(d) said photochromic compound is selected from the group consisting of
1,3-dihydro-3,3-dimethyl-5-methoxy-1-propyl -spiro›2H-indol-2,3'-›3H!pyrido{3,2-f}benzoxazine!;
1,3-dihydro-3,3,4,5-tetramethyl-1-propyl-spiro›2H-indole-2,3'-›3H!pyrido{3, 2-f}(1,4)benzoxazine!;
1,3-dihydro-3,3,5,6-tetramethyl-1-propyl-spiro›2H-indole-2,3'-›3H!pyrido{3, 2-f}(1,4)benzoxazine!;
3-(2,4-dimethoxy)phenyl-3-(4-methoxy)phenyl-3H-naphtho›2,1-b!pyran;
1,3,3,4,5-pentamethyl-9'-methoxycarbonyl-8'-acetoxy-spiro›indoline-2-3'-›3H !naphth›2,1,b!›1,4!oxazine!;
1,3,3,5,6-pentamethyl-9'-methoxycarbonyl-8'-acetoxy-spiro›indoline-2,3'-›3H !naphth›2,1,b!›1,4!oxazine!;
3(2-fluorophenyl)-3(4-methoxyphenyl)-8-methoxy-3H-naphtho›2,1-b!pyran;
3(2-fluorophenyl)-3(4-methoxyphenyl)-8-methoxy-9-carbomethoxy-3H-naphtho›2, 1-b!pyran; and
a mixture of at least two thereof;
(e) said lens or lens blank has a heat distortion temperature of at least 35.degree. C.;
(f) said lens or lens blank has a bleach transmission of at least 40 percent;
(g) said lens or lens blank has a refractive index at 20.degree. C. and a wavelength of 589.3 nanometers of at least 1.53; and
(h) said lens or lens blank is characterized by an absolute value of optical correction of at least 2 diopters.