US4157892A
Expired / Lapsed
US
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Method of coloring water-absorbable plastics and colored water-absorbable plastics
Assignee: Menicon Co Ltd
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Filing: 1976-10-12
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Granted: 1979-06-12
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Expires: 1996-10-12
Abstract
Abstract A method of coloring a water-absorbable plastic partially or totally in a single color or multiple colors in such a manner that no migration or separation of the coloring agents used can take place. A copolymer of a coupler monomer and a water-absorbable plastic monomer, a polymer of a coupler polymer and a water-absorbable plastic monomer or a polymer of a coupler monomer and a water-absorbable plastic polymer is formed into an intermediate product shaped in the form of any desired final product. The intermediate product is immersed in an aqueous solution of a developer consisting of a diazonium double salt and allowed to swell, whereby the diazo-component of the developer penetrates into the plastic. The swollen product is then immersed in an aqueous acid or alkaline solution having an optimum pH value for coupling reaction to allow formation of an azoic dye on the plastic as a result of the coupling reaction. A partially colored plastic is produced by application of ultraviolet rays to a portion or portions of the plastic on which no coloring is required, whereby the diazo-component on those portions is decomposed to leave those portions uncolored. Multiple coloring is effected by repeating the partial coloring process by changing diazonium double salts.
Inventors
- 👤 Kyoichi Tanaka
- 👤 Takeshi Mio
- 👤 Kozo Takahashi
- 👤 Toshiharu Yoshikawa
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 06:34
CPC Classifications
G; G03; G03C; G03C1/00; G03C1/52; D; D06; D06P; D06P1/00; D06P1/02; D06P1/12; D06P3/00; G02; G02B; G02B1/00; G02B1/04; G02B1/041; G02B1/043
Claims Analysis
Total Claims: 29
Claim 1
Independent Claim
187 words
A method of making a colored water-absorbable soft contact lens comprising (a) preparing a water-absorbable soft contact lens substantially composed of a material selected from the group consisting of (i) a product of copolymerization between a coupler having a polymerization radical and a water-absorbable plastic monomer capable of forming a water-absorbable soft contact lens; (ii) a product of polymerization between a coupler having a polymerization radical and a polymer of a water-absorbable plastic monomer capable of forming a water-absorbable soft contact lens; and (iii) a product of polymerization between a polymer of a coupler having a polymerization radical and a water-absorbable plastic monomer capable of forming a water-absorbable soft contact lens; said water-absorbable plastic monomer being a member selected from the group consisting of 2-hydroxyethylmethacrylate, 2-hydroxypropylmethacrylate, 2-hydroxyethylacrylate, N-methylolacrylamide, methacrylic acid, acrylic acid, N-vinyl pyrrolidone, acrylamide and vinyl acetate which is changed into a water-absorbable vinyl alcohol by hydrolysis after polymerization, and (b) immersing said water-absorbable soft contact lens in an aqueous solution of a diazonium double salt having a pH value which is suitable for causing coupling reaction to form a azoic dye within said contact lens.
Claim 2
Independent Claim
187 words
A method of making a colored water-absorbable soft contact lens comprising (a) preparing a water-absorbable soft contact lens substantially composed of a material selected from the group consisting of (i) a product of copolymerization between a coupler having a polymerization radical and a water-absorbable plastic monomer capable of forming a water-absorbable soft contact lens; (ii) a product of polymerization between a coupler having a polymerization radical and a polymer of a water-absorbable plastic monomer capable of forming a water-absorbable soft contact lens; and (iii) a product of polymerization between a polymer of a coupler having a polymerization radical and a water-absorbable plastic monomer capable of forming a water-absorbable soft contact lens; said water-absorbable plastic monomer being a member selected from the group consisting of 2-hydroxyethylmethacrylate, 2-hydroxypropylmethacrylate, 2-hydroxyethylacrylate, N-methylolacrylamide, methacrylic acid, acrylic acid, N-vinyl pyrrolidone, acrylamide and vinyl acetate which is changed into a water-absorbable vinyl alcohol by hydrolysis after polymerization, and (b) immersing said water-absorbable soft contact lens in an aqueous solution of a diazonium double salt having a pH value which is suitable for causing coupling reaction to form a azoic dye within said contact lens.
Claim 3
Dependent Claim
69 words
The method as defined in claim 1, wherein said coupler is a compound selected from the group consisting of vinyl esters of monoethylmalonate, acetoacetic acid and cyanoacetic acid having an active methylene group; acrylesters, methacryl esters, acryl amides and methacryl amides of 3-hydroxy-2-naphthoic-(m-amino) anilide, 3-hydroxy-2-naphthoic-(β-hydroxyethyl) amide, 3-hydroxy2-naphthoic-{bis-(β-hydroxyethyl)} amide, 3,5-resorcyclic(β-hydroxyethyl) amide and 2,4-resorcyclic-(β-hydroxyethyl) amide having an amino or hydroxy radical on the end of its molecule; and the polymers thereof.
Claim 4
Dependent Claim
30 words
The method as defined in claim 1, wherein said water-absorbable plastic monomer comprises at least one compound selected from the group consisting a 2-hydroxyethylmethacrylate; 2-hydroxypropylmethacrylate; 2-hydroxyethylacrylate; N-methylolacrylamide; N-vinylpyrrolidone; and acrylamide.
Claim 5
Dependent Claim
25 words
The method as defined in claim 1, wherein said water-absorbable plastic polymer is a composition selected from the group consisting of polyvinyl alchol and polyvinylpyrrolidone.
Claim 6
Dependent Claim
37 words
The method as defined in claim 1, wherein 100 parts by weight of each said product of copolymerization or polymerization contains about 0.01 to five parts by weight of said coupler or said polymer of said coupler.
Claim 7
Dependent Claim
74 words
The method as defined in claim 1, wherein said diazonium double salt is a compound selected from the group consisting of p-N,N'-dimethylaminobenzene diazonium zinc chloride; p-N,N'-diethylaminobenzene diazonium zinc chloride; 4-morpholino-2,5-dibutoxybenzene diazonium zinc chloride; p-N-ethyl-N'-hydroxyethylaminobenzene diazonium zinc chloride; 4-(p-methylbenzoylamino)-2,5-diethoxybenzene diazonium zinc chloride; 4(p-methylmercapto)-2,5-diethoxybenzene diazonium zinc chloride; 2,5-dichlorobenzene diazonium zinc chloride; 2-methoxy-5-nitrobenzene diazonium zinc chloride; 2-nitro-4-methoxybenzene diazonium zinc chloride; p-phenylaminobenzene diazonium zinc chloride; 2-chlorobenzene diazonium salt; 3-chlorobenzene diazonium salt; 4-benzoylamino-2-methoxy-5-methylbenzene diazonium salt; and p-(4'-methoxyphenylamino)-benzene diazonium salt.
Claim 8
Independent Claim
210 words
A method of making a colored soft contact lens comprising: (a) preparing a water-absorbable soft contact lens substantially composed of material selected from the group consisting of (i) a product of copolymerization between a coupler having a polymerization radical and a water-absorbable plastic monomer capable of forming a water-absorbable soft contact lens; (ii) a product of polymerization between a coupler having a polymerization radical and a polymer of a water-absorbable plastic monomer capable of forming a water-absorbable soft contact lens; and (iii) a product of polymerization between a polymer of a coupler having a polymerization radical and a water absorbable plastic monomer capable of forming a water-absorbable soft contact lens; said water-absorbable plastic monomer being a member selected from the group consisting of 2-hydroxyethylmethacrylate, 2-hydroxypropylmethacrylate, 2-hydroxyethylacrylate, N-methylolacrylamide, methacrylic acid, acrylic acid, N-vinyl pyrrolidone, acrylamide and vinyl acetate which is changed into a water-absorbable vinyl alchol by hydrolysis after polymerization; (b) immersing said water-absorbable soft contact lens in an aqueous solution of a diazonium double salt having a pH value controlled to inhibit any precoupling reaction; and (c) immersing said water-absorbable soft contact lens in an aqueous solution having a pH value which is suitable for causing coupling reaction to take place to form an azoic dye within said contact lens.
Claim 9
Independent Claim
210 words
A method of making a colored soft contact lens comprising: (a) preparing a water-absorbable soft contact lens substantially composed of material selected from the group consisting of (i) a product of copolymerization between a coupler having a polymerization radical and a water-absorbable plastic monomer capable of forming a water-absorbable soft contact lens; (ii) a product of polymerization between a coupler having a polymerization radical and a polymer of a water-absorbable plastic monomer capable of forming a water-absorbable soft contact lens; and (iii) a product of polymerization between a polymer of a coupler having a polymerization radical and a water absorbable plastic monomer capable of forming a water-absorbable soft contact lens; said water-absorbable plastic monomer being a member selected from the group consisting of 2-hydroxyethylmethacrylate, 2-hydroxypropylmethacrylate, 2-hydroxyethylacrylate, N-methylolacrylamide, methacrylic acid, acrylic acid, N-vinyl pyrrolidone, acrylamide and vinyl acetate which is changed into a water-absorbable vinyl alchol by hydrolysis after polymerization; (b) immersing said water-absorbable soft contact lens in an aqueous solution of a diazonium double salt having a pH value controlled to inhibit any precoupling reaction; and (c) immersing said water-absorbable soft contact lens in an aqueous solution having a pH value which is suitable for causing coupling reaction to take place to form an azoic dye within said contact lens.
Claim 10
Dependent Claim
70 words
The method as defined in claim 7, wherein said coupler is a compound selected from the group consisting of vinyl esters of monoethylmalonate, acetoacetic acid and cyanoacetic acid having an active methylene group; acryl esters, methacryl esters, acryl amides and methacryl amides of 3-hydroxy-2-naphthoic-(m-amino) anilide, 3-hydroxy-2-naphthoic-(β-hydroxyethyl) amide, 3-hydroxy-2-naphthoic-{bis-(β-hydroxetyl)} amide, 3,5-resorcylic-(β-hydroxyethyl) amide and 2,4-resorcylic-(β-hydroxyethyl) amide having an amino or hydroxy radical on the end of its molecule; and the polymers thereof.
Claim 11
Dependent Claim
30 words
The method as defined in claim 7, wherein said water-absorbable plastic monomer comprises at least one compound selected from the group consisting of 2-hydroxyethylmethacrylate; 2-hydroxypropylmethacrylate; 2-hydroxyethylacrylate; N-methylolacrylamide; N-vinylpyrrolidone; and acrylamide.
Claim 12
Dependent Claim
25 words
The method as defined in claim 7, wherein said water-absorbable plastic polymer is a composition selected from the group consisting of polyvinyl alcohol and polyvinylpyrrolidone.
Claim 13
Dependent Claim
37 words
The method as defined in claim 7, wherein 100 parts by weight of each said product of copolymerization or polymerization contains about 0.01 to five parts by weight of said coupler or said polymer of said coupler.
Claim 14
Dependent Claim
74 words
The method as defined in claim 7, wherein said diazonium double salt is a compound selected from the group consisting of p-N,N'-dimethylaminobenzene diazonium zinc chloride; p-N,N'-diethylaminobenzene diazonium zinc chloride; 4-morpholino-2,5-dibutoxybenzene diazonium zinc chloride; p-N-ethyl-N'-hydroxyethylaminobenzene diazonium zinc chloride; 4(p-methylbenzoylamino)-2,5-diethoxybenzene diazonium zinc chloride; 4(p-methylmercapto)-2,5-diethoxybenzene diazonium zinc chloride; 2,5-dichlorobenzene diazonium zinc chloride; 2-methoxy-5-nitrobenzene diazonium zinc chloride; 2-nitro-4-methoxybenzene diazonium zinc chloride; p-phenylaminobenzene diazonium zinc chloride; 2-chlorobenzene diazonium salt; 3-chlorobenzene diazonium salt; 4-benzoylamino-2-methoxy-5-methylbenzene diazonium salt; and p-(4'-methoxyphenylamino)-benzene diazonium salt.
Claim 15
Dependent Claim
20 words
The method as defined in claim 7, wherein said aqueous solution of a diazonium double salt is an acid solution.
Claim 16
Dependent Claim
20 words
The method as defined in claim 7, wherein said aqueous solution of a diazonium double salt is an alkaline solution.
Claim 17
Dependent Claim
29 words
The method as defined in claim 7, wherein said aqueous solution having a pH value which is suitable for causing coupling reaction to take place is an alkaline solution.
Claim 18
Dependent Claim
29 words
The method as defined in claim 7, wherein said aqueous solution having a pH value which is suitable for causing coupling reaction to take place is an acid solution.
Claim 19
Independent Claim
240 words
A method of making a partially colored water-absorbable soft contact lens comprising: (a) preparing a water-absorbable soft contact lens substantially composed of a material selected from the group consisting of (i) a product of copolymerization between a coupler having a polymerization radical and a water-absorbable plastic monomer capable of forming a water-absorbable soft contact lens; (ii) a product of polymerization between a coupler having a polymerization radical and a polymer of a water-absorbable plastic monomer capable of forming a water-absorbable soft contact lens; and (iii) a product of polymerization between a polymer of a coupler having a polymerization radical and a water-absorbable monomer capable of forming a water-absorbable soft contact lens; said water-absorbable plastic monomer being a member selected from the group consisting of 2-hydroxyethylmethacrylate, 2-hydroxypropylmethacrylate, 2-hydroxyethylacrylate, N-methylolacrylamide, methacrylic acid, acrylic acid, N-vinyl pyrrolidone, acrylamide and vinyl acetate which is changed into a water-absorbable vinyl alcohol by hydrolysis after polymerization; (b) immersing said water-absorbable soft contact lens in an aqueous solution of a sensitive diazonium double salt having a pH value controlled to inhibit any precoupling reaction; (c) applying ultraviolet rays to less than all of said contact lens to resolve the diazonium double salt in said ultraviolet ray treated portion; and (d) immersing water-absorbable soft contact lens in an aqueous solution having a pH value which is suitable for causing coupling reaction to form an azoic dye of a desired color in the remaining portion of said contact lens.
Claim 20
Independent Claim
240 words
A method of making a partially colored water-absorbable soft contact lens comprising: (a) preparing a water-absorbable soft contact lens substantially composed of a material selected from the group consisting of (i) a product of copolymerization between a coupler having a polymerization radical and a water-absorbable plastic monomer capable of forming a water-absorbable soft contact lens; (ii) a product of polymerization between a coupler having a polymerization radical and a polymer of a water-absorbable plastic monomer capable of forming a water-absorbable soft contact lens; and (iii) a product of polymerization between a polymer of a coupler having a polymerization radical and a water-absorbable monomer capable of forming a water-absorbable soft contact lens; said water-absorbable plastic monomer being a member selected from the group consisting of 2-hydroxyethylmethacrylate, 2-hydroxypropylmethacrylate, 2-hydroxyethylacrylate, N-methylolacrylamide, methacrylic acid, acrylic acid, N-vinyl pyrrolidone, acrylamide and vinyl acetate which is changed into a water-absorbable vinyl alcohol by hydrolysis after polymerization; (b) immersing said water-absorbable soft contact lens in an aqueous solution of a sensitive diazonium double salt having a pH value controlled to inhibit any precoupling reaction; (c) applying ultraviolet rays to less than all of said contact lens to resolve the diazonium double salt in said ultraviolet ray treated portion; and (d) immersing water-absorbable soft contact lens in an aqueous solution having a pH value which is suitable for causing coupling reaction to form an azoic dye of a desired color in the remaining portion of said contact lens.
Claim 21
Dependent Claim
74 words
The method as defined in claim 17, wherein said coupler is a compound selected from the group consisting of vinyl esters of monoethylmalonate, acetoacetic acid and cyanoacetic acid having an active methylene group; acryl esters, methacryl esters, acryl amides and methacryl amides of 3-hydroxy-2-naphthoic-(m-amino) anilide, 3-hydroxy-2-naphthoic-(β -hydroxyethyl) amide, 3-hydroxy-2-naphthoic-{bis-(β -hydroxyethyl)} amide, 3,5-resorcylic-(β -hydroxyethyl) amide and 2,4-resorcylic-(β -hydroxyethyl) amide having an amino or hydroxy radical on the end of its molecule; and the polymers thereof.
Claim 22
Dependent Claim
32 words
The method as defined in claim 17, wherein said water-absorbable plastic monomer comprises at least one compound selected from the group consisting of 2-hydroxyethylmethacrylate; 2-hydroxypropylmethacrylate; 2-hydroxyethylacrylate; 2-hydroxypropylmethacrylate; 2-hydroxtyethylacrylate; N-methylolacrylamide; N-vinylpyrrolidone; and acrylamide.
Claim 23
Dependent Claim
25 words
The method as defined in claim 17, wherein said water-absorbable plastic polymer is a composition selected from the group consisting of polyvinyl alcohol and polyvinylpyrrolidone.
Claim 24
Dependent Claim
37 words
The method as defined in claim 17, wherein 100 parts by weight of each said product of copolymerization or polymerization contains about 0.01 to five parts by weight of said coupler or said polymer of said coupler.
Claim 25
Dependent Claim
77 words
The method as defined in claim 17, wherein said photosensitive diazonium double salt is a compound selected from the group consisting of p-N,N'-dimethylaminobenzene diazonium zinc chloride; p-N,N'-diethylaminobenzene diazonium zinc chloride; 4-morpholine-2,5-dibutoxybenzene diazonium zinc chloride; p-N-ethyl-N'-hydroxyethylaminobenzene diazonium zinc chloride; 4(p-methyl-benzoylamino) -2,5-diethoxybenzene diazonium zinc chloride; 4(p-methylmercapto)-2,5-diethoxybenzene diazonium zinc chloride; 2,5-dichlorobenzene diazonium zinc chloride; 2-methoxy-5-nitrobenzene diazonium zinc chloride; 2-nitro-4-methoxybenzene diazonium zinc chloride; p-phenylaminobenzene diazonium zinc chloride; 2-chlorobenzene diazonium salt; 3-chlorobenzene diazonium salt; 4-benzoylamino-2-methoxy-5- methylbenzene diazonium salt; and p-(4'-methoxyphenylamino)-benzene diazonium salt.
Claim 26
Dependent Claim
20 words
The method as defined in claim 17, wherein said aqueous solution of a diazonium double salt is an acid solution.
Claim 27
Dependent Claim
20 words
The method as defined in claim 17, wherein said aqueous solution of a diazonium double salt is an alkaline solution.
Claim 28
Dependent Claim
29 words
The method as defined in claim 17, wherein said aqueous solution having a pH value which is suitable for causing coupling reaction to take place is an alkaline solution.
Claim 29
Dependent Claim
29 words
The method as defined in claim 17, wherein said aqueous solution having a pH value which is suitable for causing coupling reaction to take place is an acid solution.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1982-06-11 | 1982-12-11 | 1983-06-12 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-06-11 | 1986-12-11 | 1987-06-12 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-06-11 | 1990-12-11 | 1991-06-12 | $7700.00 | Window Closed / Lapsed |