CN112521545A - Ink intermediate for colored contact lenses and preparation method thereof - Google Patents

Ink intermediate for colored contact lenses and preparation method thereof Download PDF

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Publication number
CN112521545A
CN112521545A CN202011590680.9A CN202011590680A CN112521545A CN 112521545 A CN112521545 A CN 112521545A CN 202011590680 A CN202011590680 A CN 202011590680A CN 112521545 A CN112521545 A CN 112521545A
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parts
ethylene glycol
benzenediol
reaction
stirring
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Inventor
李卓
唐钰喜
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Gansu Kangshida Technologies Group Co ltd
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Gansu Kangshida Technologies Group Co ltd
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Priority to CN202011590680.9A priority Critical patent/CN112521545A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/20Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/10Printing inks based on artificial resins
    • C09D11/106Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • GPHYSICS
    • G02OPTICS
    • G02CSPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00Optical parts
    • G02C7/02Lenses; Lens systems ; Methods of designing lenses
    • G02C7/04Contact lenses for the eyes

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Ophthalmology & Optometry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses an ink intermediate for a colored contact lens and a preparation method thereof, wherein the ink intermediate comprises the following components in parts by weight: hydroxyethyl methacrylate: 20-50 parts; cyclopentanone: 10-20 parts; ethylene glycol monoethyl ether: 10-20 parts; methacrylic acid: 0.5-2 parts; methyl methacrylate: 2-4 parts; butyl acetate: 20-30 parts of a solvent; ethylene glycol: 0.2-10 parts; azobisisobutyronitrile: 0.06-10 parts; 1, 4-benzenediol: 0.003 to 0.008 portion. The preparation method comprises the steps of mixing the components except 1, 4-benzenediol according to the formula, placing the mixture into a reaction container, stirring and reacting at normal temperature for 30-60min, heating to 80-90 ℃, keeping the temperature, stirring and reacting for 1.5-2h, cooling the reaction system to normal temperature, adding the 1, 4-benzenediol according to the formula, stirring and reacting, and refrigerating at 4-8 ℃ for later use. The printing ink intermediate disclosed by the invention is simple in formula, short in process flow, free of complex reaction and investment of heating equipment, low in cost, stable in product, good in glossiness, strong in adhesive force and weather resistance.

Description

Ink intermediate for colored contact lenses and preparation method thereof
Technical Field
The invention relates to the technical field of printing ink, in particular to a printing ink intermediate for a colored contact lens, and also relates to a preparation method of the printing ink intermediate.
Background
Colored contact lenses have become the mainstay of the contact lens market because of their vision correction and decoration functions. At the present stage, the pattern styles of colored contact lenses on the market are full of porcelain, the colors of the patterns are different, and the requirements of people on beauty are greatly met. With the increasing popularity of colored contact lenses, the number of methods for producing the same is increasing. The earliest methods for producing colored contact lenses were to print colored patterns directly on a bare lens, but the colored contact lenses produced by such methods had a color layer in direct contact with the wearer's eyes, which is prone to discomfort and even risk of allergy for the wearer with a sensitive body. In order to solve this technical problem, many different color pattern printing methods have been developed.
At present, the most common way of printing color patterns is to brush a layer of lens material on a mold, then print one or more color inks on the lens material to form a desired pattern, and finally photo-cure or heat-cure the pattern on the mold surface to ensure that the pattern is not damaged in the subsequent lens production process. The patterns printed in the mode are complete in pattern and stable in pattern effect, and the patterns are located in the middle layer of the lens and are not in direct contact with eyes of a wearer, so that safety is greatly improved. However, the pattern curing process is complicated and cannot be connected with the subsequent lens production process, so that the continuous automatic production of the color contact lenses cannot be realized, and the lens yield in unit time is influenced.
Based on the above, the invention patent with publication number CN 110256900 a discloses an intermediate for color ink and a preparation method thereof, the ink intermediate can be cured by itself without the external force of light or heat, so that after the pattern is formed on the mold by the ink prepared from the ink intermediate, the injection molding process can be immediately performed, and the pattern does not generate color dissolving or blurring in the process of contacting with the injected lens material, thereby realizing the continuous automatic production of color contact lenses. However, the ink intermediate disclosed in the patent is rich in related components and long in preparation period, so that the production cost of the ink intermediate is high, the yield is low, and the ink intermediate is not suitable for short-term large-scale production of the ink intermediate.
Disclosure of Invention
The invention aims to overcome the technical problems in the prior art and provide an intermediate for the color contact lens ink, which has simple components and low production cost.
Another object of the present invention is to provide a method for preparing the above-mentioned ink intermediate with short process and high yield.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides an ink intermediate for a colored contact lens, which comprises the following components in parts by weight:
hydroxyethyl methacrylate: 20-50 parts; cyclopentanone: 10-20 parts; ethylene glycol monoethyl ether: 10-20 parts; methacrylic acid: 0.5-2 parts; methyl methacrylate: 2-4 parts; butyl acetate: 20-30 parts of a solvent; ethylene glycol: 0.2-10 parts; azobisisobutyronitrile: 0.06-5 parts; 1, 4-benzenediol: 0.003 to 0.008 portion.
Preferably, the ink intermediate comprises the following components in parts by weight:
hydroxyethyl methacrylate: 35-50 parts; cyclopentanone: 10-20 parts; ethylene glycol monoethyl ether: 10-20 parts; methacrylic acid: 0.5-2 parts; methyl methacrylate: 2-4 parts; butyl acetate: 20-30 parts of a solvent; ethylene glycol: 0.2-10 parts; azobisisobutyronitrile: 0.06-2 parts; 1, 4-benzenediol: 0.003 to 0.008 portion.
More preferably, the ink intermediate comprises the following components in parts by weight:
hydroxyethyl methacrylate: 40 parts of a mixture; cyclopentanone: 12 parts of (1); ethylene glycol monoethyl ether: 16 parts of a mixture; methacrylic acid: 1.5 parts; methyl methacrylate: 3 parts of a mixture; butyl acetate: 25 parts of (1); ethylene glycol: 3 parts of a mixture; azobisisobutyronitrile: 0.1 part; 1, 4-benzenediol: 0.005 part.
The preparation method of the ink intermediate for the colored contact lens comprises the following steps:
step one, mixing hydroxyethyl methacrylate, cyclopentanone, ethylene glycol monoethyl ether, methacrylic acid, methyl methacrylate, butyl acetate and azobisisobutyronitrile according to the formula ratio, placing the mixture into a reaction vessel, and stirring and reacting at normal temperature for 30-60 min;
step two, heating the reaction system in the step one, and then continuing to keep the temperature and stir for reaction for 1.5-2 h;
step three, adding 1,4-
Stirring the benzenediol, reacting, and refrigerating at 4-8 deg.C for use.
Further, in the first step, the stirring reaction is carried out under the protection of nitrogen.
In the second step, the end point of the temperature rise is 80-90 ℃.
In the third step, the stirring reaction time is 1 h.
Furthermore, in the first step, the reaction vessel is a reaction kettle.
The invention has the following beneficial effects:
1. according to the invention, monomers such as hydroxyethyl methacrylate, cyclopentanone, methacrylic acid, methyl methacrylate, butyl acetate, ethylene glycol, azobisisobutyronitrile and the like are mixed and then subjected to polymerization reaction to generate a polymer. Wherein, the solvent ethylene glycol monoethyl ether and butyl acetate do not participate in the reaction, the action is to reduce the concentration of the monomer to ensure that the reaction is more sufficient, and after the reaction is finished, the polymerization inhibitor 1, 4-benzenediol is added into the polymer to terminate the reaction and simultaneously prolong the storage time of the intermediate.
2. The printing ink intermediate disclosed by the invention is simple in formula, short in process flow, low in cost, high in yield and suitable for short-term large-scale production of the printing ink intermediate, and does not need complex reaction and investment of heating equipment.
3. Preparation of the ink intermediate of the present invention in N2The preparation method is carried out under protection, the product is more stable, and the product is prepared into printing ink for preparing the colored contact lenses, so that the wearing safety of the lenses can be ensured.
4. The ink intermediate disclosed by the invention is good in glossiness after film forming, and strong in adhesive force and weather resistance.
Detailed Description
The method for producing the intermediate for ink for contact lens of the present invention will be described in detail with reference to the following examples.
The adhesion and gloss detection methods of the ink intermediates in the examples are as follows:
and (3) adhesive force detection: the test sample is uniformly applied to a flat plate with a consistent surface structure, and after the coating system is dried/cured, the test column is directly bonded to the surface of the coating by using an adhesive. After the adhesive is cured, the bonded test combination is placed on a BGD 500 digital display pull-open method adhesion tester, the tester pulls the test column off from the coating at a uniform speed not exceeding 1MPa/s through a hydraulic pump, and the required force is directly displayed through a liquid crystal screen of the tester, so that the force required for damaging the adhesion between the coating and the substrate is tested (GB/T5210 color paint and varnish pull-open method adhesion test).
And (3) gloss detection: the test specimens were printed on the molds and the gloss (angle of projection 60 ℃ C.) was measured using a small-bore gloss meter SDR-B60S (GB/T8807-1988 test method for specular gloss in plastics).
Example 1
Mixing 40 parts of hydroxyethyl methacrylate, 12 parts of cyclopentanone, 16 parts of ethylene glycol monoethyl ether, 1.5 parts of methacrylic acid, 3 parts of methyl methacrylate, 25 parts of butyl acetate, 3 parts of ethylene glycol and 0.1 part of azobisisobutyronitrile, placing the mixture in a reaction kettle, and stirring the mixture at normal temperature for 40min under the protection of nitrogen. And opening a heating device of the reaction kettle, heating to 80 ℃, and continuing to keep the temperature and stir for reaction for 2 hours. After the reaction kettle is cooled to the normal temperature, 0.005 part of 1, 4-benzenediol is added, stirred for 1 hour and then refrigerated at the temperature of 4-8 ℃ for standby.
The force required to break the adhesion between the coatings was measured to be 1.14MPa using a BGD 500 digital display pull-open method adhesion tester, and the gloss (60 ℃ projection angle) was measured to be 113Gu using a small-bore gloss instrument SDR-B60S.
Example 2
Mixing 36 parts of hydroxyethyl methacrylate, 11 parts of cyclopentanone, 13 parts of ethylene glycol monoethyl ether, 0.8 part of methacrylic acid, 4 parts of methyl methacrylate, 29 parts of butyl acetate, 4 parts of ethylene glycol and 2.2 parts of azobisisobutyronitrile, placing the mixture in a reaction kettle, and stirring the mixture at normal temperature for 30min under the protection of nitrogen. And opening a heating device of the reaction kettle, heating to 80 ℃, and continuing to keep the temperature and stir for reaction for 1.5 h. After the reaction kettle is cooled to the normal temperature, 0.006 part of 1, 4-benzenediol is added, stirred for 1 hour and then refrigerated at 4-8 ℃ for later use.
A BGD 500 digital display pull-open method adhesion tester is used for measuring the force required for breaking the adhesion between the coatings, namely 1.21MPa, and a small-hole gloss instrument SDR-B60S is used for detecting that the color degree (the projection angle is 60 degrees) is 109.1 Gu.
Example 3
Mixing 45 parts of hydroxyethyl methacrylate, 10 parts of cyclopentanone, 10 parts of ethylene glycol monoethyl ether, 0.8 part of methacrylic acid, 3 parts of methyl methacrylate, 25 parts of butyl acetate, 5.2 parts of ethylene glycol and 0.9 part of azobisisobutyronitrile, placing the mixture in a reaction kettle, and stirring the mixture at normal temperature for 50min under the protection of nitrogen. And opening a heating device of the reaction kettle, heating to 85 ℃, and continuing to keep the temperature and stir for reaction for 1.5 h. After the reaction kettle is cooled to the normal temperature, 0.009 parts of 1, 4-benzenediol is added, stirred for 1 hour and then refrigerated at 4-8 ℃ for standby.
A BGD 500 digital display pull-open method adhesion tester is used for measuring the force required for breaking the adhesion between the coatings, namely 1.32MPa, and a small-hole gloss instrument SDR-B60S is used for detecting that the color degree (the projection angle is 60 degrees) is 106.2 Gu.
Example 4
Mixing 40 parts of hydroxyethyl methacrylate, 15 parts of cyclopentanone, 8 parts of ethylene glycol monoethyl ether, 0.7 part of methacrylic acid, 3 parts of methyl methacrylate, 27 parts of butyl acetate, 5 parts of ethylene glycol and 1.3 parts of azobisisobutyronitrile, placing the mixture in a reaction kettle, and stirring the mixture at normal temperature for 50min under the protection of nitrogen. And opening a heating device of the reaction kettle, heating to 90 ℃, and continuing to keep the temperature and stir for reaction for 2 hours. After the reaction kettle is cooled to the normal temperature, 0.006 part of 1, 4-benzenediol is added, stirred for 1 hour and then refrigerated at 4-8 ℃ for later use.
A BGD 500 digital display pull-open method adhesion tester is used for measuring the force required for breaking the adhesion between the coatings, namely 1.08MPa, and a small-hole gloss instrument SDR-B60S is used for detecting that the color degree (the projection angle is 60 degrees) is 103.1 Gu.
Example 5
42 parts of hydroxyethyl methacrylate, 12 parts of cyclopentanone, 11 parts of ethylene glycol monoethyl ether, 1 part of methacrylic acid, 2 parts of methyl methacrylate, 23 parts of butyl acetate, 7.4 parts of ethylene glycol and 1.6 parts of azobisisobutyronitrile are mixed and then placed in a reaction kettle, and the mixture is stirred for 40min at normal temperature under the protection of nitrogen. And opening a heating device of the reaction kettle, heating to 80 ℃, and continuing to keep the temperature and stir for reaction for 2 hours. After the reaction kettle is cooled to the normal temperature, 0.008 part of 1, 4-benzenediol is added, stirred for 1 hour and then refrigerated at 4-8 ℃ for later use.
A BGD 500 digital display pull-open method adhesion tester is used for measuring the force required for breaking the adhesion between the coatings, namely 1.31MPa, and a small-hole gloss instrument SDR-B60S is used for detecting that the color degree (the projection angle is 60 degrees) is 101.1 Gu.

Claims (8)

1. An ink intermediate for a colored contact lens, which is characterized by comprising the following components in parts by weight:
hydroxyethyl methacrylate: 20-50 parts; cyclopentanone: 10-20 parts; ethylene glycol monoethyl ether: 10-20 parts; methacrylic acid: 0.5-2 parts; methyl methacrylate: 2-4 parts; butyl acetate: 20-30 parts of a solvent; ethylene glycol: 0.2-10 parts; azobisisobutyronitrile: 0.06-5 parts; 1, 4-benzenediol: 0.003 to 0.008 portion.
2. The ink intermediate for colored contact lenses according to claim 1, comprising the following components in parts by weight:
hydroxyethyl methacrylate: 35-50 parts; cyclopentanone: 10-20 parts; ethylene glycol monoethyl ether: 10-20 parts; methacrylic acid: 0.5-2 parts; methyl methacrylate: 2-4 parts; butyl acetate: 20-30 parts of a solvent; ethylene glycol: 0.2-10 parts; azobisisobutyronitrile: 0.06-2 parts; 1, 4-benzenediol: 0.003 to 0.008 portion.
3. The ink intermediate for colored contact lenses according to claim 2, comprising the following components in parts by weight:
hydroxyethyl methacrylate: 40 parts of a mixture; cyclopentanone: 12 parts of (1); ethylene glycol monoethyl ether: 16 parts of a mixture; methacrylic acid: 1.5 parts; methyl methacrylate: 3 parts of a mixture; butyl acetate: 25 parts of (1); ethylene glycol: 3 parts of a mixture; azobisisobutyronitrile: 0.1 part; 1, 4-benzenediol: 0.005 part.
4. The method of claim 1, comprising the steps of:
step one, mixing hydroxyethyl methacrylate, cyclopentanone, ethylene glycol monoethyl ether, methacrylic acid, methyl methacrylate, butyl acetate and azobisisobutyronitrile according to the formula ratio, placing the mixture into a reaction vessel, and stirring and reacting at normal temperature for 30-60 min;
step two, heating the reaction system in the step one, and then continuing to keep the temperature and stir for reaction for 1.5-2 h;
step three, adding 1,4-
Stirring the benzenediol, reacting, and refrigerating at 4-8 deg.C for use.
5. The method of claim 4, wherein the stirring reaction in the first step is performed under a nitrogen atmosphere.
6. The method of claim 4, wherein in the second step, the end point of the temperature rise temperature is 80 to 90 ℃.
7. The method for preparing an intermediate for ink for colored contact lenses according to claim 4, wherein in the third step, the stirring reaction time is 1 h.
8. The method for preparing an intermediate for color contact lenses according to any one of claims 4 to 7, wherein in the first step, the reaction vessel is a reaction vessel.
CN202011590680.9A 2020-12-29 2020-12-29 Ink intermediate for colored contact lenses and preparation method thereof Pending CN112521545A (en)

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1035183A (en) * 1987-11-24 1989-08-30 先灵公司 Hydrophilic colored contact lenses
JPH06258605A (en) * 1993-03-05 1994-09-16 Seed:Kk Colored contact lens and its production
JPH08152582A (en) * 1994-11-30 1996-06-11 Seed:Kk Colored contact lens and its production
US20070027228A1 (en) * 2004-07-28 2007-02-01 Tucker Robert C Water-based inks for hydrogel lenses
CN101031410A (en) * 2004-09-30 2007-09-05 诺瓦提斯公司 Pad printing method for making colored contact lenses
KR100773571B1 (en) * 2007-02-09 2007-11-07 이원희 The contact lens coloring ink paste and manufacturing method of the color contact lens which it uses
US20080143003A1 (en) * 2006-12-13 2008-06-19 John Christopher Phelan Actinically curable silicone hydrogel copolymers and uses thereof
CN104371470A (en) * 2014-11-05 2015-02-25 广州福诚美化工有限公司 Self-crosslinked water-based acrylic air-drying paint and preparation method thereof
WO2015140968A1 (en) * 2014-03-19 2015-09-24 株式会社メニコン Ink composition for hydrous contact lenses
CN110256900A (en) * 2019-06-28 2019-09-20 甘肃天后光学科技有限公司 A kind of intermediate and preparation method thereof for colored ink
CN111154489A (en) * 2019-12-18 2020-05-15 东南大学 Intelligent contact lens based on up-conversion luminescent nano material and preparation method thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1035183A (en) * 1987-11-24 1989-08-30 先灵公司 Hydrophilic colored contact lenses
JPH06258605A (en) * 1993-03-05 1994-09-16 Seed:Kk Colored contact lens and its production
JPH08152582A (en) * 1994-11-30 1996-06-11 Seed:Kk Colored contact lens and its production
US20070027228A1 (en) * 2004-07-28 2007-02-01 Tucker Robert C Water-based inks for hydrogel lenses
CN101031410A (en) * 2004-09-30 2007-09-05 诺瓦提斯公司 Pad printing method for making colored contact lenses
US20080143003A1 (en) * 2006-12-13 2008-06-19 John Christopher Phelan Actinically curable silicone hydrogel copolymers and uses thereof
KR100773571B1 (en) * 2007-02-09 2007-11-07 이원희 The contact lens coloring ink paste and manufacturing method of the color contact lens which it uses
WO2015140968A1 (en) * 2014-03-19 2015-09-24 株式会社メニコン Ink composition for hydrous contact lenses
CN104371470A (en) * 2014-11-05 2015-02-25 广州福诚美化工有限公司 Self-crosslinked water-based acrylic air-drying paint and preparation method thereof
CN110256900A (en) * 2019-06-28 2019-09-20 甘肃天后光学科技有限公司 A kind of intermediate and preparation method thereof for colored ink
CN111154489A (en) * 2019-12-18 2020-05-15 东南大学 Intelligent contact lens based on up-conversion luminescent nano material and preparation method thereof

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PATRICK BOLLGRUEN,等: "Ink-jet printing of host-guest systems based on acrylates with fluorescent dopants", 《PROCEEDINGS OF SPIE》 *
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