WO2024065567A1 - 硅氧烷单体、隐形眼镜组成物及隐形眼镜 - Google Patents

硅氧烷单体、隐形眼镜组成物及隐形眼镜 Download PDF

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Publication number
WO2024065567A1
WO2024065567A1 PCT/CN2022/122963 CN2022122963W WO2024065567A1 WO 2024065567 A1 WO2024065567 A1 WO 2024065567A1 CN 2022122963 W CN2022122963 W CN 2022122963W WO 2024065567 A1 WO2024065567 A1 WO 2024065567A1
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siloxane monomer
contact lens
weight
parts
formula
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PCT/CN2022/122963
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English (en)
French (fr)
Inventor
李庭育
黄民扬
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晶硕光学股份有限公司
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Priority to PCT/CN2022/122963 priority Critical patent/WO2024065567A1/zh
Priority to CN202280086402.0A priority patent/CN118434791A/zh
Publication of WO2024065567A1 publication Critical patent/WO2024065567A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/02—Lenses; Lens systems ; Methods of designing lenses
    • G02C7/04—Contact lenses for the eyes

Definitions

  • the present invention relates to a siloxane monomer, in particular to a siloxane monomer, a contact lens composition and a contact lens.
  • silicone hydrogel contact lenses can effectively improve oxygen permeability (DK).
  • Silicone hydrogel contact lenses contain hydrophilic silicon-containing polymer materials, and then add hydrophilic monomers such as NVP, DMA, MAA, etc. to copolymerize to form silicone hydrogel contact lenses.
  • hydrophilic monomers such as NVP, DMA, MAA, etc.
  • the surface of silicone hydrogel materials has hydrophobic properties, which can easily lead to bacterial growth and cause problems such as inflammation of the lenses. Therefore, the surface of silicone hydrogel materials usually needs to be modified to improve the wettability of the material surface.
  • the technical problem to be solved by the present invention is to provide a siloxane monomer, a contact lens composition and a contact lens in view of the deficiencies of the prior art, which can effectively improve the wettability of the surface of the contact lens and do not require surface hydrophilic coating treatment.
  • siloxane monomer that can be used to make contact lenses.
  • the siloxane monomer has a chemical structure bond line formula represented by the following formula (I):
  • R 1 is H or CH 3 ; wherein R 2 is NHR 3 , N(R 3 ) 2 , OR 3 , SR 3 , or and n is not greater than 6; wherein R 3 is and n is not greater than 6; wherein R 4 is H or an alkyl group with a carbon chain length of C 1 to C 6 ; wherein x ⁇ 0, y ⁇ 1, and z ⁇ 0.
  • a weight average molecular weight or a number average molecular weight of the siloxane monomer is between 500 g/mol and 50,000 g/mol.
  • a contact lens composition which includes: a siloxane monomer, a hydrophilic monomer, a crosslinking agent, and an initiator; wherein the siloxane monomer includes a first siloxane monomer having a chemical structure bond line formula represented by the following formula (I):
  • R 1 is H or CH 3 ; wherein R 2 is NHR 3 , N(R 3 ) 2 , OR 3 , SR 3 , or and n is not greater than 6; wherein R 3 is and n is not greater than 6; wherein R 4 is H or an alkyl group with a carbon chain length of C 1 to C 6 ; wherein x ⁇ 0, y ⁇ 1, and z ⁇ 0.
  • the siloxane monomer further includes: at least one of a second siloxane monomer, a third siloxane monomer, and a fourth siloxane monomer.
  • the second siloxane monomer has a chemical structure bond line formula of formula (II):
  • the third siloxane monomer has a chemical structure bond line formula of formula (III):
  • the fourth siloxane monomer is (3-methacryloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane.
  • the amount of the first siloxane monomer is between 1 part by weight and 30 parts by weight; the amount of the second siloxane monomer is not more than 40 parts by weight; the amount of the third siloxane monomer is not more than 40 parts by weight; and the amount of the fourth siloxane monomer is not more than 30 parts by weight.
  • the hydrophilic monomer is selected from at least one of the following material groups: 2-hydroxyethyl methacrylate, methyl methacrylate, methacrylic acid, N-vinyl pyrrolidone, N,N-di(methacrylamide), 4-acryloylmorpholine, 2-hydroxyethylacrylamide, glyceryl methacrylate, glyceryl monomethacrylate, acrylic acid, N-vinyl-N-methylacetamide, glycine vinyl carbonate, 2-methacryloyloxyethyl phosphorylcholine, and 2-hydroxy-butyl methacrylate; wherein the amount of the hydrophilic monomer is between 30 parts by weight and 70 parts by weight.
  • the crosslinking agent is selected from at least one of the following material groups: poly(ethylene glycol) diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, allyl methacrylate, ethylene glycol diallyl ether, triethylene glycol diallyl ether, tetraethylene glycol diallyl ether, 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,1-tri(hydroxymethylpropane) tri(methacrylate), tri(hydroxymethylpropane) tri(acrylate), pentaerythritol tetra(acrylate), tetraethylene glycol diacrylate, ethylenebisacrylamide, 1,4-bis(acrylamide)butene, and poly(ethylene glycol) di(acrylate); wherein the amount of the crosslinking agent used is between 0.01 parts
  • the initiator is selected from at least one of the following material groups: bis(1-(2,4-difluorophenyl)-3-pyrrolyl)titanocene, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and 2-hydroxy-2-methyl-1-phenyl-1-propanone; wherein the amount of the initiator used is between 0.01 parts by weight and 2 parts by weight.
  • another technical solution adopted by the present invention is to provide a contact lens, which is made of the contact lens composition as described above; wherein, the contact lens has the following characteristics: the lens surface has a hysteresis of less than 30°, and the dyeing penetration of the lens after dyeing with Sudan black dye is greater than 70%.
  • the contact lens has (i) an oxygen permeability of 40 to 150 Barrers; (ii) an equilibrium water content of 30 to 80%; (iii) the hysteresis of 0 to 30°; (iv) the Sudan black dye penetration of 70 to 99.9%; (v) a tensile modulus of 0.1 to 0.8 MPa; and (vi) an elongation of 100 to 500%.
  • the beneficial effect of the present invention is that the siloxane monomer, contact lens composition and contact lens provided by the present invention can improve the hydrophilicity of the surface of the contact lens by introducing a siloxane monomer with a special hydrophilic structure and combining it with a special contact lens composition, and there is no need to perform surface hydrophilic coating treatment.
  • the technical solution provided by the present invention can further increase the diversity of the structure.
  • the ketone chemical structure has a resonance formula, it can cause the polarization phenomenon of charge separation, and the R2 substituent is a multi-electron atom X (such as: N, O, S), which can further promote the polarization phenomenon of charge separation, thereby increasing the ionicity of the overall molecule, which is beneficial to improving the hydrophilicity and moisture retention of the lens material.
  • the contact lens prepared by the contact lens composition of the present invention can have excellent surface hydrophilicity, and thus, no hydrophilic surface coating treatment is required.
  • the embodiment of the present invention provides a siloxane monomer that can be used to make contact lenses.
  • the siloxane monomer has a chemical structure bond line formula (skeletal formula) represented by the following formula (I):
  • R 1 is H or CH 3
  • R 2 is NHR 3 , N(R 3 ) 2 , OR 3 , SR 3 , or n is an integer of 0 to 6, and preferably an integer of 1 to 6.
  • R 3 is n is an integer of 0 to 6, and preferably an integer of 1 to 6.
  • R 4 is H or an alkyl group having a carbon chain length of C 1 to C 6 .
  • x is a positive number greater than or equal to zero (x ⁇ 0), and preferably a positive number between 50 and 100.
  • y is a positive number greater than or equal to 1 (y ⁇ 1), and preferably a positive number between 1 and 20.
  • z is a positive number greater than or equal to zero (z ⁇ 0), and preferably a positive number between 1 and 30.
  • a weight average molecular weight (weight average molecular weight, Mw) of the siloxane monomer is between 500 and 50,000, and preferably between 1,000 and 30,000.
  • a number average molecular weight (number average molecular weight, Mn) of the siloxane monomer is between 500 and 50,000, and preferably between 1,000 and 30,000.
  • a viscosity average molecular weight (viscosity average molecular weight, Mv) of the siloxane monomer is between 500 and 50,000, and preferably between 1,000 and 30,000.
  • the above molecular weight units are all grams per mole (g/mol).
  • the siloxane monomer has a hydrophilic side chain grafted onto the repeating unit of siloxane as shown below.
  • the hydrophilic side chains have repeating units based on polyethylene glycol (PEG).
  • PEG polyethylene glycol
  • the hydrophilic side chain further modifies the substituent structure of R 2 on the ketone structure, thereby increasing the diversity of the structure.
  • the substituent structure can provide aldehyde functional group characteristics.
  • the substituent structure can provide keto functional group characteristics.
  • the substituent structure can provide amide functional group characteristics.
  • R 2 is O or OH
  • the substituent structure can provide the characteristics of an ester or acid functional group.
  • the substituent structure can provide the characteristics of a thioester functional group.
  • the hydrophilic side chain of the siloxane monomer in the embodiment of the present invention is based on the ketone structure and is expanded to the characteristics of other ketone-derived functional groups, thereby increasing the diversity of the structure.
  • the siloxane monomer has a chemical structure bond line formula represented by the following formula (Ia), wherein R 2 is CH 3 , which provides ketone functional group characteristics.
  • the siloxane monomer of the embodiment of the present invention is based on polyethylene glycol, further introduces a ketone structure, and performs R2 structural modification.
  • the technical solution provided by the present invention can increase the diversity of the structure.
  • the chemical structure of ketones has a resonance formula as shown below, it can cause the polarization phenomenon of charge separation, and the R2 substituent is a multi-electron atom X (such as: N, O, S), which can further promote the polarization phenomenon of charge separation, thereby increasing the ionicity of the overall molecule, which is beneficial to improving the hydrophilicity and moisture retention of the lens material.
  • the embodiment of the present invention also provides a contact lens composition.
  • the contact lens composition comprises: a silicone monomer, a hydrophilic monomer, a crosslinking agent, an initiator, a UV absorber, a co-solvent, and a dye.
  • the siloxane monomer further includes: a first siloxane monomer, a second siloxane monomer, a third siloxane monomer, and/or a fourth siloxane monomer.
  • the first siloxane monomer is the siloxane monomer shown in formula (I) of the above embodiment.
  • R 1 is H or CH 3
  • R 2 is NHR 3 , N(R 3 ) 2 , OR 3 , SR 3 , or n is an integer of 0 to 6, and preferably an integer of 1 to 6.
  • R 3 is n is an integer from 0 to 6, and preferably an integer from 1 to 6.
  • R 4 is H or an alkyl group with a carbon chain length of C 1 to C 6.
  • x is a positive number greater than or equal to zero (x ⁇ 0), and preferably a positive number between 50 and 100.
  • y is a positive number greater than or equal to 1 (y ⁇ 1), and preferably a positive number between 1 and 20.
  • z is a positive number greater than or equal to zero (z ⁇ 0), and preferably a positive number between 1 and 30.
  • the first siloxane monomer is a siloxane monomer as shown in formula (Ia) in the above embodiment.
  • the second siloxane monomer has a chemical structure bond formula (skeletal formula) represented by the following formula (II).
  • the fourth siloxane monomer is (3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane.
  • the dosage of the first siloxane monomer is between 1 part by weight and 30 parts by weight, preferably between 5 parts by weight and 25 parts by weight, and particularly preferably between 6 parts by weight and 24 parts by weight.
  • the dosage of the second siloxane monomer is between 0 parts by weight and 40 parts by weight, and preferably between 10 parts by weight and 30 parts by weight.
  • the dosage of the third siloxane monomer is between 0 parts by weight and 40 parts by weight, and preferably between 10 parts by weight and 35 parts by weight.
  • the dosage of the fourth siloxane monomer is between 0 parts by weight and 30 parts by weight, and preferably between 3 parts by weight and 30 parts by weight.
  • the hydrophilic monomer is selected from at least one of the following materials: 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate, HEMA), methyl methacrylate (methyl methacrylate, MMA), methacrylic acid (methacrylic acid, MAA), N-vinyl pyrrolidone (N-vinyl pyrrolidone, NVP), N, N-dimethyl-acrylamide (N, N-dimethyl-acrylamide, DMA), 4-acryloylmorpholine (4-acryloylmorpholine, AcMO), 2-hydroxyethyl acrylamide (2-hydroxyethyl acryl ...
  • the dosage range of the hydrophilic monomer is preferably between 30 parts by weight and 70 parts by weight, and particularly preferably between 30 parts by weight and 65 parts by weight, but the present invention is not limited thereto.
  • the hydrophilic monomer is at least one of 2-hydroxyethyl methacrylate (HEMA), methyl methacrylate (MMA), N-vinyl pyrrolidone (NVP), N,N-di(methacrylamide) (DMA), and 4-acryloylmorpholine (AcMO), but the present invention is not limited thereto.
  • HEMA 2-hydroxyethyl methacrylate
  • MMA methyl methacrylate
  • NDP N-vinyl pyrrolidone
  • DMA N,N-di(methacrylamide)
  • AcMO 4-acryloylmorpholine
  • the crosslinking agent is at least one selected from the group consisting of the following materials: poly(ethylene glycol) diacrylate (PEGDA), ethylene glycol dimethacrylate (EGDMA), diethylene glycol dimethacrylate (DEGDMA), triethylene glycol dimethacrylate (TEGDMA), tetraethylene glycol dimethacrylate (TTEGDMA), allyl methacrylate (AMA), ethylene glycol di(allyl ether) (EGDAE), triethylene glycol di(allyl ether) (TEGDAE), tetraethylene glycol di(allyl ether) (TEGDMA), triethylene glycol di(methacrylate) (TEGDMA ...
  • PEGDA poly(ethylene glycol) diacrylate
  • EGDMA ethylene glycol dimethacrylate
  • DEGDMA diethylene glycol dimethacrylate
  • TEGDMA tetraethylene glycol dimethacrylate
  • AMA allyl methacrylate
  • EGDAE triethylene glycol di(
  • the dosage range of the crosslinking agent is preferably between 0.01 parts by weight and 5 parts by weight, and particularly preferably between 0.1 parts by weight and 3 parts by weight, but the present invention is not limited thereto.
  • the crosslinking agent is at least one of poly(ethylene glycol) diacrylate (PEGDA) and ethylene glycol dimethacrylate (EGDMA).
  • the weight average molecular weight (Mw) or number average molecular weight (Mn) of the poly(ethylene glycol) diacrylate (PEGDA) is between 500 and 800 g/mol.
  • the initiator is a photoinitiator.
  • the initiator is at least one of the group consisting of the following materials: bis(1-(2,4-difluorophenyl)-3-pyrrolyl)titanocene, phenylbis-(2,4,6-trimethylbenzoyl)-phosphine oxide, and 2-hydroxy-2-methyl-1-phenyl-1-porpanone.
  • the dosage range of the initiator is preferably between 0.01 parts by weight and 2 parts by weight, and particularly preferably between 0.05 parts by weight and 1 part by weight, but the present invention is not limited thereto.
  • the initiator is phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.
  • the contact lens composition further comprises a UV absorber.
  • the UV absorber is at least one of a material group consisting of a monomer having benzophenone and a monomer having benzotriazole.
  • the dosage range of the UV absorber is between 0.30 parts by weight and 1.80 parts by weight.
  • the UV absorber is a monomer having benzotriazole and is 2-[3-(2H-Benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate.
  • the contact lens composition further comprises a co-solvent.
  • the co-solvent is at least one of a material group selected from glycerol (GLY), isopropyl alcohol, n-butanol, t-butanol, t-amyl alcohol (AmOH) and n-hexanol.
  • GLY glycerol
  • AmOH t-amyl alcohol
  • n-hexanol n-hexanol.
  • the co-solvent is at least one of glycerol (glycerol, GLY) and t-amyl alcohol (t-amyl alcohol, AmOH).
  • the contact lens composition further comprises a dye.
  • the dye is at least one selected from the group consisting of reactive blue 19 (disodium, 1-amino-9, 10-dioxo-4-[3-(2-sulfonatooxyethylsulfonyl)anilino] anthracene-2-sulfonate), Sudan III (1-[4-(Phenylazo)phenylazo]-2-naphthol, Sudan III), indigo (2,2'-Bis(2,3-dihydro-3-oxoindolylidene), and quinoline yellow (disodium 2-(1,3-dioxo-2,3-dihydro-1H-inden-2-yl)quinolone-6,8-disul fonate, Quinoline yellow).
  • the dosage range of the dye is between 0.002 parts by weight and 0.1 parts by weight.
  • the dye is 1% (w/w) reactive blue 19 in HEMA.
  • Table 1 below shows the formula of the contact lens composition of Experimental Examples S1 to S14, including the amount of each component (such as: siloxane monomer, hydrophilic monomer, crosslinking agent, initiator, UV absorber, cosolvent, and dye). Table 1 below also shows the physical and chemical properties of the contact lenses made from the formula of Experimental Examples S1 to S14.
  • each component such as: siloxane monomer, hydrophilic monomer, crosslinking agent, initiator, UV absorber, cosolvent, and dye.
  • Experimental Examples S1 to S14 are as follows: According to the formula in Table 1, the contact lens composition is subjected to cross-linking and curing reactions to prepare the contact lens.
  • the method for manufacturing a contact lens comprises:
  • a contact lens composition (also referred to as a silicone hydrogel composition) is injected into a mold for making contact lenses.
  • a contact lens also referred to as a silicone hydrogel lens
  • a buffer solution is filled into a packaging container, and the contact lens is immersed in the buffer solution. Then, a sealing process (sealing temperature is about 125° C.) and a sterilization process (sterilization time is about 30 minutes) are performed, thereby completing the production of the contact lens product.
  • uncured water-soluble silicone macromers can be removed without extraction with an organic solvent.
  • the first siloxane monomer is the siloxane monomer shown by formula (I-a) in the above embodiment
  • the second siloxane monomer is the siloxane monomer shown by formula (II) in the above embodiment
  • the third siloxane monomer is the siloxane monomer shown by formula (III) in the above embodiment
  • the fourth siloxane monomer is (3-methacryloyloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane.
  • the hydrophilic monomer is 2-hydroxyethyl methacrylate (HEMA), methyl methacrylate (MMA), N-vinylpyrrolidone (NVP), N,N-di(methacrylamide) (DMA), and/or 4-acryloylmorpholine (AcMO).
  • the crosslinking agent is poly(ethylene glycol) diacrylate (PEGDA) and/or ethylene glycol dimethacrylate (EGDMA).
  • the initiator is phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.
  • the UV absorber is 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl] ethyl methacrylate.
  • the cosolvent is glycerol (GLY) and/or tert-amyl alcohol (AmOH).
  • the dye is 1% (w/w) reactive blue 19 in HEMA. It should be noted that the total weight of all components of the contact lens composition in Table 1 is 100 parts by weight (or 100wt%).
  • the contact lenses made from the formulations of Experimental Examples S1 to S14 were tested for physical and chemical properties, including oxygen permeability Dk (Barrer), equilibrium water content EWC (wt%), hysteresis (°), Sudan black (%) dye penetration, tensile modulus (MPa) and elongation (%).
  • oxygen permeability Dk Barrer
  • EWC equilibrium water content
  • hysteresis °
  • Sudan black % dye penetration
  • MPa tensile modulus
  • elongation %.
  • Oxygen permeability Dk (Barrer) is measured by polarographic method as described in ISO 9913-1 using an O 2 Permeometer instrument. The contact lens samples are immersed in pure water equilibrated for at least 12 hours for measurement, and then the oxygen permeability is measured in phosphate buffered saline at 35°C using an O 2 Permeometer (Model 201T) instrument (available from Rheder Development Company). The oxygen permeability is reported in Barrer units (10 -11 (cm 3 O 2 cm)/(cm 3 sec mmHg)).
  • Hysteresis (°) is measured by using a dynamic contact angle meter to measure the contact angle hysteresis of the contact lens sample, and using the captive bubble method as a method for measuring the dynamic contact angle.
  • Hysteresis (°) is calculated by measuring the difference between the advancing contact angle and the receding contact angle.
  • Sudan black (%) dye penetration was measured by preparing a 0.5% (w/w) Sudan black dye solution under stirring and leaving the solution overnight. The contact lens sample was removed from the buffer solution and gently shaken to remove most of the water remaining on the lens surface. The lens was then placed in the Sudan black dye solution prepared above for 5 minutes. Afterwards, the lens was removed from the dye bath, the excess dye solution was rinsed with warm water, and the visible light transmittance (%) of the lens was measured.
  • the tensile modulus (MPa) and elongation (%) were measured by using a tensile testing machine Zwick Z0.5.
  • the contact lens samples were cut into 2 mm width.
  • the thickness of the sample was measured using a micrometer before the test began. At the beginning of the test, the moving speed of the sample extension, the length of the sample and the distance between the jaws were kept constant. Each sample was placed in buffered saline during the measurement.
  • the modulus is recorded in MPa.
  • the elongation is recorded in %.
  • the contact lens composition formulas of Experimental Examples S3 to S14 introduce a siloxane monomer represented by Formula (I-a).
  • the hydrophilic side chain of the siloxane monomer represented by Formula (I-a) is modified with a characteristic chemical structure of ketones.
  • the contact lens made from the contact lens composition also has excellent surface hydrophilic properties. Therefore, the contact lens made from Experimental Examples S3 to S14 does not require the treatment of a hydrophilic surface coating.
  • the defining parameters of the hydrophilicity of the lens surface include hysteresis (°) and Sudan black dye (%) dye penetration.
  • hysteresis (°) angle measurement value the better the hydrophilicity, while the higher the Sudan black dye (%) dye penetration value, the better the hydrophilicity.
  • the contact lenses of Experimental Examples S3 to S14 have an oxygen permeability of 40 to 150 (preferably 45 to 75) Barrers, an equilibrium water content of 30 to 80 (preferably 37 to 57)%, a hysteresis of 0 to 30° (preferably 11 to 25°), a Sudan black dyeing penetration of 70 to 99.9 (preferably 73 to 93)%, a tensile modulus of 0.1 to 0.8 (preferably 0.26 to 0.38) MPa, and an elongation of 100 to 500 (preferably 243 to 328)%.
  • Experimental Example S9 may be considered as the best embodiment, while Experimental Example S11 is considered as the second best embodiment.
  • the reason is that Experimental Example S9 has a high oxygen permeability, and the siloxane monomer represented by Formula (I-a) has good miscibility with both long and short chain length silicon monomers, and exhibits good mechanical properties of tensile modulus and elongation.
  • Experimental Example S11 Although the tensile modulus and elongation of Experimental Example S11 are inferior to those of Experimental Example S9, this is obviously due to the increase in the amount of the siloxane monomer represented by Formula (I-a). However, Experimental Example S11 has excellent maintenance of oxygen permeability and hysteresis, which is rare in silicone hydrogel formulation systems.
  • the inventors of the present invention compared the contact lens made in Experiment S9 with the commercially available CooperVision products My Day (Stenfilcon A) and Super-Air (Fanfilcon A), and Alcon product PRECISION1 TM (Verofilcon A), and compared the average data of the surface properties of the five lenses, hysteresis (°) and Sudan black dye penetration (%).
  • the smaller the hysteresis (°) value the better the hydrophilicity of the lens surface.
  • the higher the Sudan black dye penetration (%) the less likely the dye is to be adsorbed on the lens surface, and the better the hydrophilicity of the lens surface.
  • the lens of Experimental Example S9 of the present invention without any coating process, has a hysteresis (°) data close to that of My Day (Stenfilcon A) and Super-Air (Fanfilcon A) and other products, and its Sudan Black dye penetration (%) data is better than the above products, and even close to PRECISION1 TM (Verofilcon A) product.
  • the test results are shown in Table 2 below.
  • the beneficial effect of the present invention is that the siloxane monomer, contact lens composition and contact lens provided by the present invention can improve the hydrophilicity of the surface of the contact lens by introducing a siloxane monomer with a special hydrophilic structure and combining it with a special contact lens composition, and there is no need to perform surface hydrophilic coating treatment.
  • the technical solution provided by the present invention can increase the diversity of the structure.
  • the ketone chemical structure has a resonance formula, it can cause the polarization phenomenon of charge separation, and the R2 substituent is a multi-electron atom X (such as: N, O, S), which can further promote the polarization phenomenon of charge separation, thereby increasing the ionicity of the overall molecule, which is beneficial to improving the hydrophilicity and moisture retention of the lens material.
  • the contact lens prepared by the contact lens composition of the present invention can have excellent surface hydrophilicity, and thus, no hydrophilic surface coating treatment is required.

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Abstract

一种硅氧烷单体、隐形眼镜组成物及隐形眼镜，硅氧烷单体具有如下式(Ⅰ)表示的化学结构式。其中R 1为H或CH 3，R 2为由非卤素取代的NHR 3、N(R 3) 2、OR 3、SR 3或 (aa)，R 3为 (aa)，R 4为H或具有碳链长度C1至C6的烷基，其中，n不大于6，x≥0，y≥1，z≥0；通过导入上述具有特殊亲水性结构的硅氧烷单体，且搭配于隐形眼镜组成物，使隐形眼镜的镜片表面亲水性被提升，可以不需要进行表面亲水性涂层处理。

Description

硅氧烷单体、隐形眼镜组成物及隐形眼镜 技术领域
本发明涉及一种硅氧烷单体，特别是涉及一种硅氧烷单体、隐形眼镜组成物及隐形眼镜。
背景技术
在现有技术中，硅水胶隐形眼镜可有效提高透氧率(DK)。硅水胶隐形眼镜包含亲水性含硅聚合材料，再加入亲水性单体，如：NVP、DMA、MAA等共聚合成硅水胶隐形眼镜。然而，硅氧烷水凝胶材料的表面具有疏水性的特性，其容易导致细菌滋生，而造成眼镜发炎等问题。故，聚硅氧水凝胶材料的表面通常需进行修饰，以提升材料表面的湿润性。
于是，本发明人有感上述缺陷可改善，乃特潜心研究并配合科学原理的运用，终于提出一种设计合理且有效改善上述缺陷的本发明。
发明内容
本发明所要解决的技术问题在于，针对现有技术的不足提供一种硅氧烷单体、隐形眼镜组成物及隐形眼镜，其可以使隐形眼镜镜片表面的湿润性被有效提升，且可以不需要进行表面亲水性涂层处理。
为了解决上述的技术问题，本发明所采用的其中一技术方案是，提供一种硅氧烷单体，可用于制作隐形眼镜。所述硅氧烷单体具有如下式(I)表示的化学结构键线式：
Figure PCTCN2022122963-appb-000001
优选地，R 1为H或CH 3；其中R 2为由非卤素取代的NHR 3、N(R 3) 2、OR 3、SR 3、或
Figure PCTCN2022122963-appb-000002
且n不大于6；其中R 3为
Figure PCTCN2022122963-appb-000003
且n不大于6；其中R 4为H或具碳链长度C 1至C 6的烷基；其中x≧0，y≧1、且z≧0。
优选地，所述硅氧烷单体的一重量平均分子量或一数量平均分子量是介于500克/摩尔至50,000克/摩尔之间。
为了解决上述的技术问题，本发明所采用的另外一技术方案是，提供一种隐形眼镜 组成物，其包括：硅氧烷单体、亲水性单体、交联剂、及起始剂；其中，所述硅氧烷单体包含一第一硅氧烷单体，其具有如下式(I)表示的化学结构键线式：
Figure PCTCN2022122963-appb-000004
优选地，R 1为H或CH 3；其中R 2为由非卤素取代的NHR 3、N(R 3) 2、OR 3、SR 3、或
Figure PCTCN2022122963-appb-000005
且n不大于6；其中R 3为
Figure PCTCN2022122963-appb-000006
且n不大于6；其中R 4为H或具碳链长度C 1至C 6的烷基；其中x≧0，y≧1、且z≧0。
优选地，所述硅氧烷单体进一步包含有：一第二硅氧烷单体、一第三硅氧烷单体、及一第四硅氧烷单体的至少其中之一。
优选地，所述第二硅氧烷单体具有式(II)的化学结构键线式：
Figure PCTCN2022122963-appb-000007
优选地，所述第三硅氧烷单体具有式(III)的化学结构键线式：
Figure PCTCN2022122963-appb-000008
所述式(III)中x＝8～15。
优选地，所述第四硅氧烷单体为(3-甲基丙烯酰氧基-2-羟丙氧基)丙基双(三甲基甲硅烷氧基)甲基硅烷。
优选地，基于所述隐形眼镜组成物的总重为100重量份，所述第一硅氧烷单体的用量是介于1重量份至30重量份之间；所述第二硅氧烷单体的用量不大于40重量份；所述 第三硅氧烷单体的用量不大于40重量份；所述第四硅氧烷单体的用量不大于30重量份。
优选地，所述亲水性单体选自由以下材料群组的至少其中之一：甲基丙烯酸2-羟乙酯、甲基丙烯酸甲酯、甲基丙烯酸、N-乙烯基吡咯烷酮、N,N-二(甲基丙烯酰胺)、4-丙烯酰吗啉、2-羟乙基丙烯酰胺、甲基丙烯酸甘油酯、单甲基丙烯酸甘油酯、丙烯酸、N-乙烯基-N-甲基乙酰胺、甘氨酸乙烯基碳酸酯、2-甲基丙烯酰氧基乙基磷酰胆碱、及2-羟基-甲基丙烯酸丁酯；其中，所述亲水性单体的用量介于30重量份至70重量份之间。
优选地，所述交联剂选自由以下材料群组的至少其中之一：聚(乙二醇)二丙烯酸酯、乙二醇二甲基丙烯酸酯、二乙二醇二甲基丙烯酸酯、三甘醇二甲基丙烯酸酯、四乙二醇二甲基丙烯酸酯、甲基丙烯酸烯丙酯、乙二醇二烯丙醚、三甘醇二烯丙醚、四乙二醇二烯丙醚、1,3,5-三烯丙基-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、1,1,1-三(羟甲基丙烷)三(甲基丙烯酸酯)、三(羟甲基丙烷)三(丙烯酸酯)、季戊四醇四(丙烯酸酯)、四乙二醇二丙烯酸酯、乙二丙烯酰胺、1,4-二(丙烯酰胺)丁烯、及聚(乙二醇)二(丙烯酸酯)；其中，所述交联剂的用量介于0.01重量份至5重量份之间。
优选地，所述起始剂选自由以下材料群组的至少其中之一：双(1-(2,4-二氟苯基)-3-吡咯基)二茂钛、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、及2-羟基-2-甲基-1-苯基-1-丙酮；其中，所述起始剂的用量介于0.01重量份至2重量份之间。
为了解决上述的技术问题，本发明所采用的另外一技术方案是，提供一种隐形眼镜，其是由如上所述的隐形眼镜组成物制成；其中，所述隐形眼镜具有以下特性：镜片表面具有小于30°的一滞后(Hysteresis)，并且镜片通过苏丹黑染料(Sudan black)染色后的染色穿透率大于70％。
优选地，所述隐形眼镜具有(i)40～150Barrers的一氧气渗透率；(ii)30～80％的一平衡含水量；(iii)0～30°的所述滞后；(iv)70～99.9％的所述苏丹黑染色穿透率；(v)0.1～0.8MPa的一拉伸模量；及(vi)100～500％的一伸长率。
本发明的有益效果在于，本发明所提供的硅氧烷单体、隐形眼镜组成物及隐形眼镜，其能通过导入具有特殊亲水性结构的硅氧烷单体，且搭配于特殊的隐形眼镜组成物，从而使隐形眼镜的镜片表面亲水性被提升，且可以不需要进行表面亲水性涂层处理。
本发明所提供的技术方案能更增加结构的多样性特色。此外，由于酮类化学结构具有共振式，其能造成电荷分离的极化现象，并且R 2取代基为多电子原子X(如：N、O、S)，更能够促进电荷分离的极化现象，从而使整体分子增加离子性，有利于增进镜片材料的亲水性及保湿性。
进一步地说，通过本发明隐形眼镜组成物制成的隐形眼镜镜片能具有优异的表面亲水性质，因此可以不需要亲水性表面涂层的处理。
为使能更进一步了解本发明的特征及技术内容，请参阅以下有关本发明的详细说明与化学结构，然而所提供的详细说明仅用于提供参考与说明，并非用来对本发明加以限制。
具体实施方式
以下是通过特定的具体实施例来说明本发明所公开的实施方式，本领域技术人员可由本说明书所公开的内容了解本发明的优点与效果。本发明可通过其他不同的具体实施例加以施行或应用，本说明书中的各项细节也可基于不同观点与应用，在不悖离本发明的构思下进行各种修改与变更。另外，本发明的化学结构仅为简单示意说明，并非依实际尺寸的描绘，事先声明。以下的实施方式将进一步详细说明本发明的相关技术内容，但所公开的内容并非用以限制本发明的保护范围。
应当可以理解的是，虽然本文中可能会使用到“第一”、“第二”等术语来描述各种组件或者特征化合物，但这些组件或者特征化合物不应受这些术语的限制。这些术语主要是用以区分一组件与另一组件，或者一特征化合物与另一特征化合物。另外，本文中所使用的术语“或”，应视实际情况可能包括相关联的列出项目中的任一个或者多个的组合。
在本文中，为了描述特定之数值范围，本文系采用「某一数值至另一数值」之用语，其应被解读为涵盖该数值范围内的任意数值以及由该数值范围内的任意数值界定出的较小数值范围，如同在说明书中明确记载的该任意数值和该较小数值范围。另外，为了简洁起见，本文中各化合物或者基团的结构有时会以键线式(skeletal formula)表示，而省略了实际结构内的碳原子、氢原子以及碳氢键。然而，当结构式中有明确绘示出特定的原子或原子基团时，则结构式以绘示者为主。
[硅氧烷单体]
本发明实施例提供一种可用于制作隐形眼镜的硅氧烷单体(silicone monomer)。所述硅氧烷单体具有如下式(I)表示的化学结构键线式(skeletal formula)：
Figure PCTCN2022122963-appb-000009
其中，R 1为H或CH 3。R 2为由非卤素(non-halogen)取代的NHR 3、N(R 3) 2、OR 3、SR 3、或
Figure PCTCN2022122963-appb-000010
n为0至6的整数、且优选为1至6的整数。R 3为
Figure PCTCN2022122963-appb-000011
n为0至6的整数、且优选为1至6的整数。另外，R 4为H或具碳链长度C 1至C 6的烷基(alkyl)。
其中，x为大于或等于零的正数(x≧0)、且优选为介于50至100之间的正数。y为大于或等于1的的正数(y≧1)、且优选为介于1至20的正数。再者，z为大于或等于零的正数(z≧0)、且优选为介于1至30的正数。
其中，所述硅氧烷单体的一重量平均分子量(weight average molecular weight，Mw) 介于500至50,000之间、且优选介于1,000至30,000之间。所述硅氧烷单体的一数量平均分子量(number average molecular weight，Mn)介于500至50,000之间、且优选介于1,000至30,000之间。再者，所述硅氧烷单体的一黏度平均分子量(viscosity average molecular weight，Mv)介于500至50,000之间、且优选介于1,000至30,000之间。上述分子量单位皆为克/摩尔(g/mol)。
如上述式(I)表示的化学结构键线式，所述硅氧烷单体于硅氧烷的重复单元上接枝有如下所示的亲水性侧链。
Figure PCTCN2022122963-appb-000012
所述亲水性侧链具有基于聚乙二醇(polyethylene glycol，PEG)的重复单元
Figure PCTCN2022122963-appb-000013
并且在所述聚乙二醇重复单元的末端处引进了酮类结构(ketone structure)，PEG-C(＝O)R 2。所述亲水性侧链另在酮类结构上修饰R 2的取代基结构，从而增加了结构的多样性特色。
举例而言，R 2若为H，则该取代基结构能提供醛官能基特性。
举例而言，R 2若为C，则该取代基结构能提供酮官能基特性。
举例而言，R 2若为N，则该取代基结构能提供酰胺官能基特性。
举例而言，R 2若为O或OH，则该取代基结构能提供酯类或酸类官能基的特性。
举例而言，R 2若为S，则该取代基结构能提供硫酯官能基的特性。
本发明实施例硅氧烷单体的亲水性侧链建立在酮类结构的基础上，扩充为其它酮类衍生官能基的特性，从而增加了结构的多样性特色。
在本发明的一具体应用例中，所述硅氧烷单体具有如下式(I-a)表示的化学结构键线式，其中，R 2为CH 3，其提供酮官能基特性。
Figure PCTCN2022122963-appb-000014
其中，x＝80～90，y＝3～9，并且z＝9～15。
值得一提的是，在现有技术中，许多研究机构或学者对于硅氧烷单体的亲水性改质大部分是采用聚乙二醇、聚丙二醇、甘油酯等化学结构做为亲水性侧链。
在已知的学理知识中，如同聚乙二醇、聚丙二醇、甘油酯等的化学结构，属于聚醚类多元醇(polyether polyol)。上述化合物具有亲水性的原因，是因为其结构上的氧原子(O)或羟基(OH)与水分子容易形成氢键，从而达到亲水性的目的。
不同于现有技术，本发明实施例的硅氧烷单体是在聚乙二醇的基础下，进一步引进酮类结构，并且进行R 2结构修饰。
本发明所提供的技术方案能增加了结构的多样性特色。此外，由于酮类化学结构具有如下所示的共振式，其能造成电荷分离的极化现象，并且R 2取代基为多电子原子X(如：N、O、S)，更能够促进电荷分离的极化现象，从而使整体分子增加离子性，有利于增进镜片材料的亲水性及保湿性。
以下为酮类化学结构的共振式：
Figure PCTCN2022122963-appb-000015
[隐形眼镜组成物]
本发明实施例也提供一种隐形眼镜组成物(contact lens composition)。所述隐形眼镜组成物包含：硅氧烷单体(silicone monomer)、亲水性单体(hydrophilic monomer)、交联剂(crosslinking agent)、起始剂(initiator)、UV吸收剂(UV absorber)、助溶剂(co-solvent)、及染剂(dye)。
所述硅氧烷单体进一步包含：一第一硅氧烷单体、一第二硅氧烷单体、一第三硅氧烷单体、及/或一第四硅氧烷单体。
所述第一硅氧烷单体为如上述实施例式(I)所示的硅氧烷单体。
Figure PCTCN2022122963-appb-000016
其中，R 1为H或CH 3。R 2为由非卤素(non-halogen)取代的NHR 3、N(R 3) 2、OR 3、SR 3、或
Figure PCTCN2022122963-appb-000017
n为0至6的整数、且优选为1至6的整数。R 3为
Figure PCTCN2022122963-appb-000018
n为0至6的整数、且优选为1至6的整数。另外，R 4为H或具碳链长度C 1至C 6的烷基(alkyl)。x为大于或等于零的正数(x≧0)、且优选为介于50至100之间的正数。y为大于或等于1的的正数(y≧1)、且优选为介于1至20之间的正数。再者，z为大于或等于零的正数(z≧0)、且优选为介于1至30之间的正数。在一具体应用例中，所述第一硅氧烷 单体为如上述实施例中式(I-a)所示的硅氧烷单体。
所述第二硅氧烷单体具有如以下式(II)表示的化学结构键线式(skeletal formula)。
Figure PCTCN2022122963-appb-000019
所述第三硅氧烷单体具有如以下式(III)表示的化学结构键线式(skeletal formula)，且x＝8～15。
Figure PCTCN2022122963-appb-000020
所述第四硅氧烷单体为(3-甲基丙烯酰氧基-2-羟丙氧基)丙基双(三甲基甲硅烷氧基)甲基硅烷((3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane)。
在用量范围上，基于所述隐形眼镜组成物的总重为100重量份，所述第一硅氧烷单体(具有式(I)结构的硅氧烷单体)的用量是介于1重量份至30重量份之间、优选是介于5重量份至25重量份之间、且特优选介于6重量份至24重量份之间。再者，所述第二硅氧烷单体(具有式(II)结构的硅氧烷单体)的用量介于0重量份至40重量份之间、且优选介于10重量份至30重量份之间。所述第三硅氧烷单体(具有式(III)结构的硅氧烷单体)的用量是介于0重量份至40重量份之间、且优选介于10重量份至35重量份之间。且所述第四硅氧烷单体的用量是介于0重量份至30重量份之间、且优选介于3重量份至30重量份之间。
所述亲水性单体选自由以下材料所组成群组的至少其中之一：甲基丙烯酸2-羟乙酯(2-hydroxyethyl methacrylate，HEMA)、甲基丙烯酸甲酯(methyl methacrylate，MMA)、甲基丙烯酸(methacrylic acid，MAA)、N-乙烯基吡咯烷酮(N-vinyl pyrrolidone，NVP)、N,N-二(甲基丙烯酰胺)(N,N-dimethyl-acrylamide，DMA)、4-丙烯酰吗啉(4-acryloylmorpholine，AcMO)、2-羟乙基丙烯酰胺(2-hydroxyethyl acrylamide，HEAA)、甲基丙烯酸甘油酯(glyceryl methacrylate，GMA)、单甲基丙烯酸甘油酯(glycerol mono-meth acrylate，GMMA)、丙烯酸(acrylic acid，AA)、N,N-二(甲基甲基丙烯酰胺)(N,N-di(methyl meth acryl-amide)，DMA)、N-乙烯基-N-甲基乙酰胺(N-vinyl-N-methyl acetamide)、甘氨酸乙烯基碳酸酯(glycine vinyl carbonate)、2-甲基丙烯酰氧基乙基磷酰胆碱 (2-methacryloyloxyethyl phosphorylcholine)、及2-羟基-甲基丙烯酸丁酯(2-hydroxy-butyl methacrylate)。
在用量范围上，基于所述隐形眼镜组成物的总重为100重量份，所述亲水性单体的一用量范围优选是介于30重量份至70重量份之间、且特优选是介于30重量份至65重量份之间，但本发明不受限于此。
进一步地说，在本发明的一具体应用例中，所述亲水性单体为：甲基丙烯酸2-羟乙酯(HEMA)、甲基丙烯酸甲酯(MMA)、N-乙烯基吡咯烷酮(NVP)、N,N-二(甲基丙烯酰胺)(DMA)、及4-丙烯酰吗啉(AcMO)的至少其中之一，但本发明不受限于此。
所述交联剂是选自由以下材料所组成的群组的至少其中之一：聚(乙二醇)二丙烯酸酯(poly(ethylene glycol)diacrylate，PEGDA)、乙二醇二甲基丙烯酸酯(ethylene glycol di(methacrylate)，EGDMA)、二乙二醇二甲基丙烯酸酯(di(ethylene glycol)di(methacrylate)，DEGDMA)、三甘醇二甲基丙烯酸酯(tri(ethylene glycol)di(methacrylate)，TEGDMA)、四乙二醇二甲基丙烯酸酯(tetra(ethylene glycol)di(methacrylate)，TTEGDMA)、甲基丙烯酸烯丙酯(allyl methacrylate，AMA)、乙二醇二烯丙醚(ethylene glycol di(allyl ether)，EGDAE)、三甘醇二烯丙醚(tri(ethylene glycol)di(allyl ether)，TEGDAE)、四乙二醇二烯丙醚(tetra(ethylene glycol)di(allyl ether)，TTEGDAE)、1,3,5-三烯丙基-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮(1,3,5-Triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione)、1,1,1-三(羟甲基丙烷)三(甲基丙烯酸酯)(1,1,1-tri(methylolpropane)tri(methacrylate))、三(羟甲基丙烷)三(丙烯酸酯)(tri(methylolpropane)tri(acrylate))、季戊四醇四(丙烯酸酯)(pentaerythritol tetra(acrylate))、四乙二醇二丙烯酸酯(tetra(ethylene glycol)di(acrylate))、乙二丙烯酰胺(ethylene di(acrylamide))、1,4-二(丙烯酰胺)丁烯(butylene1,4-di(acrylamide))、及聚(乙二醇)二(丙烯酸酯)(poly(ethylene glycol)di(acrylate))。
在用量范围上，基于所述隐形眼镜组成物的总重为100重量份，所述交联剂的一用量范围优选是介于0.01重量份至5重量份之间、且特优选是介于0.1重量份至3重量份之间，但本发明不受限于此。
进一步地说，在本发明的一具体应用例中，所述交联剂为：聚(乙二醇)二丙烯酸酯(PEGDA)及乙二醇二甲基丙烯酸酯(EGDMA)的至少其中之一。其中，所述聚(乙二醇)二丙烯酸酯(PEGDA)的重均分子量(Mw)或数均分子量(Mn)是介于500至800克/摩尔之间。
所述起始剂为一光起始剂。
所述起始剂是选自由以下材料所组成的群组的至少其中之一：双(1-(2,4-二氟苯基)-3-吡咯基)二茂钛(bis(2,6-difluoro-3-(1-hydropyrro-1-yl)-phenyl)titanocene)、苯基双(2,4,6-三甲基苯甲酰基)氧化膦(phenylbis-(2,4,6-trimethylbenzoyl)-phosphine oxide)、及2-羟基-2-甲基-1-苯基-1-丙酮(2-hydroxy-2-methyl-1-phenyl-1-porpanone)。
在用量范围上，基于所述隐形眼镜组成物的总重为100重量份，所述起始剂的一用量 范围优选是介于0.01重量份至2重量份之间、且特优选是介于0.05重量份至1重量份之间，但本发明不受限于此。
进一步地说，在本发明的一具体应用例中，所述起始剂为苯基双(2,4,6-三甲基苯甲酰基)氧化膦。
为了提升所述隐形眼镜组成物的紫外光阻隔能力，在本发明的一些实施方式中，所述隐形眼镜组成物进一步包含一UV吸收剂。所述UV吸收剂是选自由一具有二苯基甲酮(benzophenone)的单体及一具有苯并三唑(benzotriazole)的单体所组成的材料群组的至少其中之一。在用量范围上，基于所述隐形眼镜组成物的总重为100重量份，所述UV吸收剂的用量范围为0.30重量份至1.80重量份之间。
进一步地说，在本发明的一具体应用例中，所述UV吸收剂为具有苯并三唑的单体且为2-[3-(2H-苯并三唑-2-基)-4-羟基苯基]甲基丙烯酸乙酯(2-[3-(2H-Benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate)。
为了提升所述隐形眼镜组成物的溶解性，在本发明的一些实施方式中，所述隐形眼镜组成物进一步包含一助溶剂。所述助溶剂是选自由甘油(glycerol，GLY)、2-丙醇(isopropyl alcohol)、正丁醇(n-butanol)、叔丁醇(t-butanol)、叔戊醇(t-amyl alcohol，AmOH)及正己醇(n-hexanol)所组成的材料群组的至少其中之一。在用量范围上，基于所述隐形眼镜组成物的总重为100重量份，所述助溶剂的用量范围介于3重量份至15重量份间。
进一步地说，在本发明的一具体应用例中，所述助溶剂为甘油(glycerol，GLY)及叔戊醇(t-amyl alcohol，AmOH)的至少其中之一。
为了使所述隐形眼镜组成物具有特定颜色，在本发明的一些实施方式中，所述隐形眼镜组成物进一步包含一染剂。所述染剂是选自由活性蓝19(disodium,1-amino-9,10-dioxo-4-[3-(2-sulfonatooxyethylsulfonyl)anilino]anthracene-2-sulfonate)、苏丹三号(1-[4-(Phenylazo)phenylazo]-2-naphthol，Sudan III)、靛蓝(2,2'-Bis(2,3-dihydro-3-oxoindolylidene)，Indigo)、以及喹啉黄(disodium 2-(1,3-dioxo-2,3-dihydro-1H-inden-2-yl)quinolone-6,8-disul fonate，Quinoline yellow)所组成的材料群组的至少其中之一。
在用量范围上，基于所述隐形眼镜组成物的总重为100重量份，所述染剂的用量范围介于0.002重量份至0.1重量份之间。
进一步地说，在本发明的一具体应用例中，所述染剂为于HEMA中1％(w/w)的活性蓝19(reactive blue 19)。
[实验数据及测试结果]
以下，将参照实验例S1至实验例S14详细说明本发明之内容。然而，以下实验例仅作为帮助了解本发明，本发明的范围不限于这些实验例。在上述实验例中，S1～S2为对照组，即隐形眼镜组成物中未添加具有式(I)所示的硅氧烷单体；而S3～S14为验证本发明技术效果的实验组，即隐形眼镜组成物中有添加具有式(I)所示的硅氧烷单体。本实验数据以 具有式(I-a)所示的硅氧烷单体举例作说明，但本发明不受限于此。
下表1显示实验例S1至实验例S14隐形眼镜组成物的配方，包含各成份(如：硅氧烷单体、亲水性单体、交联剂、起始剂、UV吸收剂、助溶剂、及染剂)的用量。下表1另显示由实验例S1至实验例S14配方制作而成的隐形眼镜所具有的物化特性。
实验例S1至实验例S14的制备方式为：依据表1的配方，将隐形眼镜组成物通过交联及固化反应，以制成隐形眼镜。
更具体地说，隐形眼镜的制造方法包含：
(i)依据表1的配方，将隐形眼镜组成物(也可称为有机硅水凝胶组合物)注入一用于制作隐形眼镜的模具中。
(ii)在一光源照射下，固化并且交联该隐形眼镜组成物以形成一隐形眼镜镜片(也可称为有机硅水凝胶镜片)。
(iii)用水萃取该隐形眼镜镜片，以去除未固化的硅氧烷单体(也可称为水溶性硅酮大分子单体)。
(iv)将该隐形眼镜镜片置于酸碱值介于7.1至7.5的硼酸盐缓冲盐水中，直到该隐形眼镜的干片半成品膨润(水化程序)。
(v)将一缓冲溶液填充于一包装容器内，将该隐形眼镜浸泡于该缓冲溶液中，接着，进行一密封程序(密封温度约125℃)及一灭菌程序(灭菌时间约30分钟)，如此即完成了隐形眼镜产品的制作。
根据本发明隐形眼镜的制造方法，其无需有机溶剂萃取即可以去除未固化的水溶性硅酮大分子单体。
在表1显示的各成份中，第一硅氧烷单体为如上述实施例中式(I-a)所示的硅氧烷单体，第二硅氧烷单体为如上述实施例中式(II)所示的硅氧烷单体，第三硅氧烷单体为如上述实施例中式(III)所示的硅氧烷单体，而第四硅氧烷单体为(3-甲基丙烯酰氧基-2-羟丙氧基)丙基双(三甲基甲硅烷氧基)甲基硅烷。亲水性单体采用甲基丙烯酸2-羟乙酯(HEMA)、甲基丙烯酸甲酯(MMA)、N-乙烯基吡咯烷酮(NVP)、N,N-二(甲基丙烯酰胺)(DMA)、及/或4-丙烯酰吗啉(AcMO)。交联剂采用聚(乙二醇)二丙烯酸酯(PEGDA)及/或乙二醇二甲基丙烯酸酯(EGDMA)。起始剂采用苯基双(2,4,6-三甲基苯甲酰基)氧化膦。UV吸收剂采用2-[3-(2H-苯并三唑-2-基)-4-羟基苯基]甲基丙烯酸乙酯。助溶剂采用甘油(GLY)及/或叔戊醇(AmOH)。染剂采用HEMA中1％(w/w)的活性蓝19(reactive blue 19)。需说明的是，表1中的隐形眼镜组成物的所有成份重量加总为100重量份(或100wt％)。
由实验例S1～S14配方制作成的隐形眼镜镜片将进行物化特性测试，包含：氧气渗透率Dk(Barrer)、平衡含水量EWC(wt％)、滞后Hysteresis(°)、苏丹黑染料Sudan black(％)染色穿透率、拉伸模量Tensile Modulus(MPa)及伸长率Elongation(％)。相关测量方法说明如下，并且测试结果如表1所示。
氧气渗透率Dk(Barrer)的测量方法为：采用O 2Permeometer仪器，依据ISO 9913-1 中描述的极谱法测量氧气渗透率(Dk)。将隐形眼镜镜片的样品浸入平衡至少12小时的纯水中进行测量，然后在35℃的磷酸盐缓冲盐水中通过O 2Permeometer(Model 201T)仪器(购自Rheder Development Company)测量氧气渗透率。氧气渗透率以Barrer为单位记录(10 -11(cm 3O 2cm)/(cm 3sec mmHg))。
平衡含水量EWC(wt％)的测量方法为：用水湿润隐形眼镜镜片样品的表面后，测量该镜片的重量，以得到水合镜片重量。在烘箱中干燥该镜片，在干燥状态下测量该镜片的重量，以得到干燥镜片重量。水合镜片重量减去干燥镜片重量得到重量差。平衡含水量EWC(wt％)＝(重量差/水合重量)×100％。
滞后Hysteresis(°)的测量方法为：使用动态接触角测量仪测量隐形眼镜镜片样品的接触角滞后(Hysteresis)，并且使用捕获气泡法(captive bubble method)作为测量动态接触角的方法。通过测量前进接触角及后退接触角之间的差异来计算滞后Hysteresis(°)。
苏丹黑染料Sudan black(％)染色穿透率的测量方法为：在搅拌下制备0.5％(w/w)苏丹黑染料溶液，并将该溶液置放过夜。从缓冲溶液中取出隐形眼镜镜片样品，并轻轻摇晃，以除去大部分残留于镜片表面上的水。然后将该镜片置于上述制备的苏丹黑染料溶液中5分钟。之后，将该镜片从染浴中取出，用温水冲洗多余的染料溶液，并测量镜片的可见光透光率(％)。
拉伸模量Tensile Modulus(MPa)及伸长率Elongation(％)的测量方法为：通过使用拉伸试验机Zwick Z0.5测量拉伸模量。将隐形眼镜镜片样品切成2毫米宽。在测试开始前使用千分尺测量样品的厚度。在测试开始时，样品延伸的移动速度、样品的长度及夹爪之间的距离保持恒定。在测量期间将每个样品置于缓冲盐水中。模量以MPa为单位记录。伸长率以％为单位记录。
[表1]
Figure PCTCN2022122963-appb-000021
Figure PCTCN2022122963-appb-000022
Figure PCTCN2022122963-appb-000023
由表1可以得知，实验例S3～S14的隐形眼镜组成物配方导入了具有式(I-a)所示的硅氧烷单体。式(I-a)所示的硅氧烷单体的亲水性侧链修饰有酮类的特征化学结构。该硅氧烷单体除了具有强烈的亲水性优势外，通过该隐形眼镜组成物制作而成的隐形眼镜镜片也具有优异的表面亲水性质，因此由实验例S3～S14制作而成的隐形眼镜镜片不需要亲水性表面涂层的处理。
进一步地说，镜片表面亲水性质的界定参数包含滞后Hysteresis(°)及苏丹黑染料Sudan black(％)染色穿透率。其中滞后Hysteresis(°)的角度量测数值越低代表亲水性越好，而苏丹黑染料Sudan black(％)染色穿透率的量测数值约高代表亲水性越好。
由实验例S1～S2的测试结果可以得知，在未导入具有式(I-a)所示的硅氧烷单体的隐形眼镜组成物中，隐形眼镜镜片表现出的滞后Hysteresis约为33～34°，而苏丹黑染料Sudan black(％)染色穿透率约47～52％。
由实验例S3～S14的测试结果可以得知，在导入具有式(I-a)所示的硅氧烷单体的隐形眼镜组成物中，隐形眼镜镜片表现出的滞后Hysteresis皆是小于30°，而苏丹黑染料Sudan black(％)染色穿透率皆是大于70％，其相较于实验例1～2制作出的隐形眼镜镜片具有更优异的亲水性。
再者，由实验例S3～S14的配方制作而成的隐形眼镜镜片并未进行特殊的表面亲水性改质处理或表面亲水性涂层处理。实验例S3～S14仅是以原料配方就能达到不逊色于有进行镜片表面改质处理之镜片，表示具有式(I-a)所示的硅氧烷单体能显著提升镜片表面的亲水性。
整体而言，实验例S3～S14的隐形眼镜镜片具有40～150(优选45～75)Barrers的氧气渗透率、30～80(优选37～57)％的平衡含水量、0～30°(优选11～25°)的滞后、70～99.9(优选73～93)％的苏丹黑染色穿透率、0.1～0.8(优选0.26～0.38)MPa的拉伸模量、及100～500(优选243～328)％的伸长率。
进一步地说，在实验例S3～S14中，实验例S9可能被认为是最佳的实施例，而实验例S11被认为是次佳的实施例。理由为，实验例S9的氧气渗透率高，且具有式(I-a)所示的硅氧烷单体与长、短链长的硅单体均可以有良好的互溶性，对于拉伸模量与伸长率的机械性质呈现佳。
实验例S11虽然在拉伸模量与伸长率的表现上较实验例S9差，明显的是因为具有式(I-a)所示的硅氧烷单体的用量增加。然而，实验例S11对氧气渗透率及滞后有着极佳的维 持，此现象在硅水胶配方系统中属于少见的。
进一步地说，为了验证本发明隐形眼镜表面性质的表现，本案发明人将实验例S9制作而成的隐形眼镜镜片与与市售CooperVision产品My Day(Stenfilcon A)及Super-Air(Fanfilcon A)，以及Alcon产品PRECISION1 TM(Verofilcon A)，进行五片镜片表面性质之滞后(°)以及苏丹黑染色穿透率(％)平均值数据比较。滞后(°)数值越小表示镜片表面亲水性越好。苏丹黑染色穿透率(％)越高，表示染料不容易吸附于镜片表面，镜片表面亲水性越好。
已知PRECISION1 TM(Verofilcon A)产品镜片表面进行涂层程序处理，因此，在滞后(°)与苏丹黑染色穿透率(％)数据有优越的性能表现。
本发明实验例S9的镜片在毫无涂层程序处理下，其滞后(°)的数据与My Day(Stenfilcon A)及Super-Air(Fanfilcon A)等产品接近，并且其苏丹黑染色穿透率(％)数据比上述产品更胜一筹，甚至接近PRECISION1 TM(Verofilcon A)产品。测试结果如以下表2所示。
[表2]
Figure PCTCN2022122963-appb-000024
[实施例有益效果]
本发明的有益效果在于，本发明所提供的硅氧烷单体、隐形眼镜组成物及隐形眼镜，其能通过导入具有特殊亲水性结构的硅氧烷单体，且搭配于特殊的隐形眼镜组成物，从而使隐形眼镜的镜片表面亲水性被提升，且可以不需要进行表面亲水性涂层处理。
本发明所提供的技术方案能增加了结构的多样性特色。此外，由于酮类化学结构具有共振式，其能造成电荷分离的极化现象，并且R 2取代基为多电子原子X(如：N、O、S)，更能够促进电荷分离的极化现象，从而使整体分子增加离子性，有利于增进镜片材料的亲水性及保湿性。
进一步地说，通过本发明隐形眼镜组成物制成的隐形眼镜镜片能具有优异的表面亲水性质，因此可以不需要亲水性表面涂层的处理。
以上所公开的内容仅为本发明的优选可行实施例，并非因此局限本发明的申请专利范围，所以凡是运用本发明说明书内容所做的等效技术变化，均包含于本发明的申请专利范围之内。

Claims (10)

  1. 一种硅氧烷单体，可用于制作隐形眼镜，其特征在于，所述硅氧烷单体具有如下式(I)表示的化学结构键线式：
    Figure PCTCN2022122963-appb-100001
    其中R 1为H或CH 3；
    其中R 2为由非卤素取代的NHR 3、N(R 3) 2、OR 3、SR 3、或
    Figure PCTCN2022122963-appb-100002
    且n不大于6；
    其中R 3为
    Figure PCTCN2022122963-appb-100003
    且n不大于6；
    其中R 4为H或具碳链长度C 1至C 6的烷基；
    其中x≧0，y≧1、且z≧0。
  2. 根据权利要求1所述的硅氧烷单体，其特征在于，所述硅氧烷单体的一重量平均分子量或一数量平均分子量是介于500克/摩尔至50,000克/摩尔。
  3. 一种隐形眼镜组成物，其特征在于，所述隐形眼镜组成物包括：硅氧烷单体、亲水性单体、交联剂、及起始剂；其中，所述硅氧烷单体包含一第一硅氧烷单体，其具有如下式(I)表示的化学结构键线式：
    Figure PCTCN2022122963-appb-100004
    其中R 1为H或CH 3；R 2为由非卤素取代的NHR 3、N(R 3) 2、OR 3、SR 3、或
    Figure PCTCN2022122963-appb-100005
    n不大于6；R 3为
    Figure PCTCN2022122963-appb-100006
    n不大于6；R 4为H或C 1至C 6的烷基；x≧0，y≧1、且z≧0。
  4. 根据权利要求3所述的隐形眼镜组成物，其特征在于，所述硅氧烷单体进一步包含有：一第二硅氧烷单体、一第三硅氧烷单体、及一第四硅氧烷单体的至少其中之一；
    其中，所述第二硅氧烷单体具有式(II)的化学结构键线式：
    Figure PCTCN2022122963-appb-100007
    其中，所述第三硅氧烷单体具有式(III)的化学结构键线式：
    Figure PCTCN2022122963-appb-100008
    所述式(III)中x＝8～15；
    其中，所述第四硅氧烷单体为(3-甲基丙烯酰氧基-2-羟丙氧基)丙基双(三甲基甲硅烷氧基)甲基硅烷。
  5. 根据权利要求4所述的隐形眼镜组成物，其特征在于，基于所述隐形眼镜组成物的总重为100重量份，所述第一硅氧烷单体的用量是介于1重量份至30重量份之间；所述第二硅氧烷单体的用量不大于40重量份；所述第三硅氧烷单体的用量不大于40重量份；所述第四硅氧烷单体的用量不大于30重量份。
  6. 根据权利要求3所述的隐形眼镜组成物，其特征在于，所述亲水性单体选自由以下材料群组的至少其中之一：甲基丙烯酸2-羟乙酯、甲基丙烯酸甲酯、甲基丙烯酸、N-乙烯基吡咯烷酮、N,N-二(甲基丙烯酰胺)、4-丙烯酰吗啉、2-羟乙基丙烯酰胺、甲基丙烯酸甘油酯、单甲基丙烯酸甘油酯、丙烯酸、N-乙烯基-N-甲基乙酰胺、甘氨酸乙烯基碳酸酯、2-甲基丙烯酰氧基乙基磷酰胆碱、及2-羟基-甲基丙烯酸丁酯；其中，所述亲水性单体的用量介于30重量份至70重量份之间。
  7. 根据权利要求3所述的隐形眼镜组成物，其特征在于，所述交联剂选自由以下材料群组的至少其中之一：聚(乙二醇)二丙烯酸酯、乙二醇二甲基丙烯酸酯、二乙二醇二甲基丙烯酸酯、三甘醇二甲基丙烯酸酯、四乙二醇二甲基丙烯酸酯、甲基丙烯酸烯丙酯、乙二醇二烯丙醚、三甘醇二烯丙醚、四乙二醇二烯丙醚、1,3,5-三烯丙基-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、1,1,1-三(羟甲基丙烷)三(甲基丙烯酸酯)、三(羟甲基丙烷)三(丙烯酸酯)、季戊四醇四(丙烯酸酯)、四乙二醇二丙烯酸酯、乙二丙烯酰胺、1,4-二(丙烯酰胺)丁烯、及聚(乙二醇)二(丙烯酸酯)；其中，所述交联剂的用量介于0.01重量份至5重量份之间。
  8. 根据权利要求3所述的隐形眼镜组成物，其特征在于，所述起始剂选自由以下材料群组的至少其中之一：双(1-(2,4-二氟苯基)-3-吡咯基)二茂钛、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、及2-羟基-2-甲基-1-苯基-1-丙酮；其中，所述起始剂的用量介于0.01重量份至2重量份之间。
  9. 一种隐形眼镜，其是由根据权利要求3至根据权利要求8中任一项所述的隐形眼镜组成物制成；其特征在于，所述隐形眼镜具有以下特性：镜片表面具有小于30°的一滞后(Hysteresis)，且镜片通过苏丹黑染料(Sudan black)染色后的染色穿透率大于70％。
  10. 根据权利要求9所述的隐形眼镜，其特征在于，所述隐形眼镜具有：
    (i)40～150 Barrers的一氧气渗透率；
    (ii)30～80％的一平衡含水量；
    (iii)0～30°的所述滞后；
    (iv)70～99.9％的所述苏丹黑染色穿透率；
    (v)0.1～0.8MPa的一拉伸模量；及
    (vi)100～500％的一伸长率。
PCT/CN2022/122963 2022-09-30 2022-09-30 硅氧烷单体、隐形眼镜组成物及隐形眼镜 WO2024065567A1 (zh)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013142062A2 (en) * 2012-03-22 2013-09-26 Momentive Performance Materials Inc. Hydrophilic macromers and hydrogels comprising the same
CN103620480A (zh) * 2011-02-28 2014-03-05 库柏维景国际控股公司 具有可接受水平的能量损失的硅酮水凝胶隐形眼镜
US9056879B2 (en) * 2011-12-29 2015-06-16 Pegavision Corporation Method of manufacturing hydrophilic silicone prepolymer
US9140908B2 (en) * 2011-02-28 2015-09-22 Coopervision International Holding Company, Lp Silicone hydrogel contact lenses
CA2873437A1 (en) * 2014-12-05 2016-06-05 Pegavision Corporation Uv-blocking silicone hydrogel composition and silicone hydrogel contact lens containing thereof
CN108948282A (zh) * 2017-05-25 2018-12-07 晶硕光学股份有限公司 水溶性硅高聚物、硅水胶组成物、硅水胶镜片及制造方法
TW202233704A (zh) * 2021-02-23 2022-09-01 晶碩光學股份有限公司 隱形眼鏡材料及隱形眼鏡鏡片

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103620480A (zh) * 2011-02-28 2014-03-05 库柏维景国际控股公司 具有可接受水平的能量损失的硅酮水凝胶隐形眼镜
US9140908B2 (en) * 2011-02-28 2015-09-22 Coopervision International Holding Company, Lp Silicone hydrogel contact lenses
US9056879B2 (en) * 2011-12-29 2015-06-16 Pegavision Corporation Method of manufacturing hydrophilic silicone prepolymer
WO2013142062A2 (en) * 2012-03-22 2013-09-26 Momentive Performance Materials Inc. Hydrophilic macromers and hydrogels comprising the same
CA2873437A1 (en) * 2014-12-05 2016-06-05 Pegavision Corporation Uv-blocking silicone hydrogel composition and silicone hydrogel contact lens containing thereof
CN108948282A (zh) * 2017-05-25 2018-12-07 晶硕光学股份有限公司 水溶性硅高聚物、硅水胶组成物、硅水胶镜片及制造方法
TW202233704A (zh) * 2021-02-23 2022-09-01 晶碩光學股份有限公司 隱形眼鏡材料及隱形眼鏡鏡片

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