CN116515300B - High oxygen permeability hard contact lens material and contact lens - Google Patents
High oxygen permeability hard contact lens material and contact lens Download PDFInfo
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- CN116515300B CN116515300B CN202310509242.2A CN202310509242A CN116515300B CN 116515300 B CN116515300 B CN 116515300B CN 202310509242 A CN202310509242 A CN 202310509242A CN 116515300 B CN116515300 B CN 116515300B
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- 239000000463 material Substances 0.000 title claims abstract description 103
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 55
- 239000001301 oxygen Substances 0.000 title claims abstract description 55
- 230000035699 permeability Effects 0.000 title claims abstract description 30
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 106
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 105
- 239000010703 silicon Substances 0.000 claims abstract description 104
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 68
- 229920002050 silicone resin Polymers 0.000 claims abstract description 60
- 239000000203 mixture Substances 0.000 claims abstract description 56
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 50
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 46
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 38
- 239000001257 hydrogen Substances 0.000 claims abstract description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000002683 reaction inhibitor Substances 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims description 38
- 239000011347 resin Substances 0.000 claims description 38
- -1 1, 1-dimethyl-2-propynyl Chemical group 0.000 claims description 27
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000007259 addition reaction Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 claims description 3
- 101100484954 Arabidopsis thaliana VQ20 gene Proteins 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 51
- 238000001723 curing Methods 0.000 description 20
- 230000003287 optical effect Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 239000007858 starting material Substances 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 8
- 238000007605 air drying Methods 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- CTPKSRZFJSJGML-UHFFFAOYSA-N sulfiram Chemical compound CCN(CC)C(=S)SC(=S)N(CC)CC CTPKSRZFJSJGML-UHFFFAOYSA-N 0.000 description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 210000004087 cornea Anatomy 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- CRJSCSRODDRNDN-UHFFFAOYSA-N methyl-tris(2-methylbut-3-yn-2-yloxy)silane Chemical compound C#CC(C)(C)O[Si](C)(OC(C)(C)C#C)OC(C)(C)C#C CRJSCSRODDRNDN-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000003961 organosilicon compounds Chemical group 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 208000003464 asthenopia Diseases 0.000 description 1
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- ARLJCLKHRZGWGL-UHFFFAOYSA-N ethenylsilicon Chemical compound [Si]C=C ARLJCLKHRZGWGL-UHFFFAOYSA-N 0.000 description 1
- 231100000040 eye damage Toxicity 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000007954 hypoxia Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—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
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Ophthalmology & Optometry (AREA)
- General Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Eyeglasses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present application relates to a high oxygen permeable rigid contact lens material made from the cured product of a curable silicone composition comprising the following components: (a) a hydrogen-containing silicone resin containing SiH groups; (b) Vinyl silicone resins containing unsaturated carbon-carbon double bonds; (c) a catalyst; and (d) a hydrosilylation reaction inhibitor. The hydrogen-containing silicone resin and the vinyl-containing silicone resin cannot simultaneously contain only the D-type silicon structural units, and at least one of the vinyl-containing silicone resin and the hydrogen-containing silicone resin contains the Q-type silicon structural units. The molar ratio of SiH groups to vinyl groups is 0.8-2.5 and the percentage of Q-type silicon structural units based on the total weight of the curable silicone composition is 27-30%. The application also relates to contact lenses made of high oxygen permeable rigid contact lens materials. Contact lenses made from the high oxygen permeability rigid contact lens materials described herein have a Shore D hardness greater than or equal to 60 and an oxygen permeability Dk greater than or equal to 200 bar without oxygen removal, and are suitable for large scale continuous production.
Description
Technical Field
The application relates to the technical field of organosilicon materials and glasses, in particular to a high oxygen permeability hard contact lens material and a contact lens made of the high oxygen permeability hard contact lens material.
Background
The oxygen permeability of the rigid keratoplasty lens material is a key factor in the ability of the wearer to wear the rigid keratoplasty lens for extended periods of time. The earliest material used for rigid contact lenses was methyl methacrylate (PMMA), which has good optical properties but lacks extreme breathability, resulting in a patient's inability to wear for extended periods of time. After finding that fluorosilicone copolymer materials have excellent effects in terms of ventilation and oxygen permeation, they began to be widely used as materials for hard contact lenses. Although hard contact lenses do have a certain degree of oxygen permeability, as the wearing time is prolonged, the wearer may suffer from eye fatigue and eye damage due to corneal hypoxia, and thus the development of a lens material with higher oxygen permeability is still an urgent need for researchers.
Commercially available hard cornea contact lenses, such as Boston XO, XO2, and Acuity 100 from Boston, are all fluorosilicone acrylate crosslinked materials prepared by a free radical curing method. Free radical curing is susceptible to oxygen inhibition, resulting in incomplete curing of the monomer, the presence of residual monomer can result in less than desired hardness of the material, and residual monomer of the material can also be biotoxic. Therefore, the preparation of the high-oxygen-permeability contact lens material by the free radical curing process needs to be assisted by a complex polymerization process, such as the improvement of the reaction temperature and the long-time curing under the nitrogen deoxidization/nitrogen atmosphere, so as to achieve the purposes of improving the conversion rate and obtaining the high-hardness material. The process of free radical curing is not friendly for the preparation of high oxygen permeability hard corneal contact lens materials for large scale continuous production.
Chinese patent application entitled "curable resin material composition, optical material, light emitting device, method of producing light emitting device, and electronic device" filed under the name "CN101591472B" discloses a curable resin material composition comprising a compound based on a SiH-group-containing siloxane containing a SiH group bonded to a silicon atom and a compound based on a c=c-bond-containing siloxane containing a carbon-carbon double bond capable of undergoing an addition reaction with the SiH group. After the hydrosilylation reaction of the two compounds, a silicone resin having a glass transition temperature of 50 ℃ or less can be obtained.
Chinese patent application publication No. CN105229783a entitled "semiconductor device and curable silicone composition for sealing semiconductor elements" discloses a hydrosilylation reaction curable silicone composition for sealing gold plated leads or substrates and semiconductor elements in a semiconductor device, the hydrosilylation reaction curable silicone composition comprising: at least (a) an organopolysiloxane having at least two alkenyl groups in a molecule; (B) An organohydrogen polysiloxane having at least two silicon atom-bonded hydrogen atoms in a molecule { in an amount of 0.1 to 10 moles per 1 mole of the alkenyl group in the component (a) }; (C) An organosilicon compound bonded to a sulfur atom and having a silicon atom-bonded hydrolyzable group (0.0001 to 2% by mass of the composition); and (D) a platinum-based hydrosilylation catalyst in an amount such that platinum atoms are in the range of 0.01 to 500ppm based on the mass unit of the composition. The cured silicone of the present application has a type a durometer hardness of 10 to 99 based on JIS K6253.
The above prior documents disclose that cured silicone resins can be prepared by hydrosilylation reaction, but function as optical materials in semiconductor devices. For this reason, there is a continuing need in the art to investigate the preparation of high oxygen permeable rigid contact lens materials by hydrosilylation reactions.
Disclosure of Invention
The object of the present application is to provide a high oxygen permeable rigid contact lens material which can be made from the cured product of a curable silicone composition. In particular, the curable silicone compositions described herein comprise (a) a hydrogen-containing silicone resin; (b) a vinyl silicone resin; (c) a catalyst; and (d) a hydrosilylation reaction inhibitor. The hydrogen-containing silicon resin comprises any one or more of a D-type silicon structural unit, a T-type silicon structural unit and a Q-type silicon structural unit. The vinyl-based silicon-containing resin comprises any one or more of a D-type silicon structural unit, a T-type silicon structural unit and a Q-type silicon structural unit. By controlling the percentage of Q-type silicon structural units in the total weight of the curable silicone composition to be 20-30% by weight, an optical material with high hardness and high oxygen permeability can be obtained.
It is also an object of the present application to provide an optical material formed after curing by the curable silicone composition as described above.
It is also an object of the present application to provide a contact lens made of the optical material as described above.
In order to solve the technical problems, the application provides the following technical scheme.
In a first aspect, the present application provides a high oxygen permeable rigid contact lens material characterized in that the high oxygen permeable rigid contact lens material is made from the cured product of a curable silicone composition, characterized in that the curable silicone composition comprises the following components:
(a) A hydrogen-containing silicone resin comprising SiH groups bonded to silicon and hydrogen atoms;
(b) A vinyl-containing silicon resin comprising a vinyl group capable of undergoing an addition reaction with the SiH group, the vinyl group comprising a carbon-carbon unsaturated double bond;
(c) A catalyst; and
(d) Hydrosilylation reaction inhibitors
Wherein the hydrogen-containing silicon resin comprises any one or more of a D-type silicon structural unit, a T-type silicon structural unit and a Q-type silicon structural unit;
wherein the vinyl-based silicon-containing resin comprises any one or more of a D-type silicon structural unit, a T-type silicon structural unit and a Q-type silicon structural unit;
wherein the hydrogen-containing silicone resin and the vinyl-containing silicone resin cannot simultaneously contain only D-type silicon structural units, and at least one of the vinyl-containing silicone resin and the hydrogen-containing silicone resin contains Q-type silicon structural units;
wherein, the ratio of SiH groups to vinyl groups is 0.8-2.5 based on the mole number;
wherein the percentage of Q-type silicon structural units based on weight is 27-30% of the total weight of the curable silicone composition;
wherein the Shore D hardness of the contact lens made of the high oxygen permeability hard contact lens material is greater than or equal to 60, and the oxygen permeability Dk is greater than or equal to 200 bar.
In a second aspect, the present application provides a contact lens made of a high oxygen permeable rigid contact lens material as described in the second aspect.
The positive effect of the present application compared to the prior art is that the curable silicone composition described herein, after curing, gives a high oxygen permeable rigid contact lens material having a Shore D hardness of greater than or equal to 60, an oxygen permeability of greater than or equal to 200 bar and a light transmittance of greater than 95% in the 380-780nm wavelength range. Contact lenses made from the high oxygen permeability rigid contact lens materials described herein have a Shore D hardness greater than or equal to 60 and an oxygen permeability Dk greater than or equal to 200 bar without oxygen removal, and are suitable for large scale continuous production.
Drawings
FIG. 1 shows a schematic representation of the reaction mechanism of a crosslinked siloxane network for the preparation of Q-containing silicone resins by hydrosilylation.
Detailed Description
Unless otherwise indicated, implied from the context, or common denominator in the art, all parts and percentages in the present application are based on weight and the test and characterization methods used are synchronized with the filing date of the present application. Where applicable, the disclosure of any patent, patent application, or publication referred to in this disclosure is incorporated herein by reference in its entirety, and the equivalent patents are incorporated herein by reference, especially with respect to the definitions of synthetic techniques, product and process designs, polymers, comonomers, initiators or catalysts, etc. in the art, as disclosed in these documents. If the definition of a particular term disclosed in the prior art is inconsistent with any definition provided in the present application, the definition of the term provided in the present application controls.
The numerical ranges in the present application are approximations, so that it may include the numerical values outside the range unless otherwise indicated. The numerical range includes all values from the lower value to the upper value that increase by 1 unit, provided that there is a spacing of at least 2 units between any lower value and any higher value. For example, if a component, physical or other property (e.g., molecular weight, melt index, etc.) is recited as being 100 to 1000, it is intended that all individual values, e.g., 100, 101,102, etc., and all subranges, e.g., 100 to 166,155 to 170,198 to 200, etc., are explicitly recited. For ranges containing values less than 1 or containing fractions greater than 1 (e.g., 1.1,1.5, etc.), then 1 unit is suitably considered to be 0.0001,0.001,0.01, or 0.1. For a range containing units of less than 10 (e.g., 1 to 5), 1 unit is generally considered to be 0.1. These are merely specific examples of what is intended to be provided, and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this disclosure. It should also be noted that the terms "first," "second," and the like herein do not limit the order of precedence, but are used merely to distinguish materials of different structures.
As used with respect to chemical compounds, the singular includes all isomeric forms and vice versa unless explicitly stated otherwise (e.g., "hexane" includes all isomers of hexane, either individually or collectively). In addition, unless explicitly stated otherwise, the use of the terms "a," "an," or "the" include plural referents.
The terms "comprises," "comprising," "including," and their derivatives do not exclude the presence of any other component, step or process, and are not related to whether or not such other component, step or process is disclosed in the present application. For the avoidance of any doubt, all use of the terms "comprising", "including" or "having" herein, unless expressly stated otherwise, may include any additional additive, adjuvant or compound. Rather, the term "consisting essentially of … …" excludes any other component, step or process from the scope of any of the terms recited below, except as necessary for operability. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. The term "or" refers to the listed individual members or any combination thereof unless explicitly stated otherwise.
In a first aspect, the present application provides a high oxygen permeable rigid contact lens material made from the cured product of a curable silicone composition. The curable silicone composition may comprise the following components: (a) A hydrogen-containing silicone resin comprising SiH groups bonded to silicon and hydrogen atoms; (b) A vinyl-based silicon-containing resin comprising a vinyl group capable of undergoing an addition reaction with the SiH group, the vinyl group comprising a carbon-carbon unsaturated double bond; and (c) a catalyst. In this embodiment, the hydrogen-containing silicon resin contains any one or more of a D-type silicon structural unit, a T-type silicon structural unit, and a Q-type silicon structural unit. In this embodiment, the vinyl-based silicon-containing resin comprises any one or more of a D-type silicon structural unit, a T-type silicon structural unit, and a Q-type silicon structural unit.
In the present application, the structural formulas of the M-type silicon structural unit, the D-type silicon structural unit, the T-type silicon structural unit, and the Q-type silicon structural unit are as follows:
the molecular formula of the M-type silicon structural unit is (CH) 3 ) 3 -Si-O 1/2 The molecular weight was 81 and the mass percentage of Si was 34.5%. The molecular formula of the D-type silicon structural unit is-Si- (CH) 3 ) 2 -O 2/2 Molecular weight was 74 and mass percent of si was 37.8%. The molecular formula of the T-shaped silicon structural unit is CH 3 -Si-O 3/2 The molecular weight was 67 and the mass percentage of Si was 41.8%. The molecular formula of the Q-type silicon structural unit is Si- (O) 1/4 ) 4 The molecular weight was 60 and the mass percentage of Si was 46.7%.
The hydrogen-containing silicone resin and the vinyl-containing silicone resin are subjected to a hydrosilylation reaction and cured in the presence of a catalyst, and the resulting cured product is a clear colorless optical material. The hydrosilylation reaction is an addition reaction of an organosilicon compound containing a silicon hydrogen bond and a compound containing an unsaturated carbon-carbon double bond under catalytic conditions such as platinum. The reaction condition is mild, the reaction efficiency is high, the conversion rate is almost 100%, and the reaction is not influenced by oxygen polymerization inhibition. The hydrosilylation reaction is known, and the reaction principle thereof can be referred to the Chalk-hard mechanism or the disclosure in the prior patent document, and is not described herein.
The inventors of the present application have found through a large number of experiments that the object of increasing the oxygen permeability of a cured product (i.e., an optical material) obtained after curing of a curable silicone composition is achieved by selectively introducing a large amount of a T/Q type silicone resin into a hydrogen-containing silicone resin and a vinyl-containing silicone resin to increase the silicon content of the curable silicone composition.
Referring to fig. 1, fig. 1 shows a schematic diagram of the reaction mechanism of a crosslinked siloxane network for preparing a Q-structure containing silicone resin by hydrosilylation reaction. Compared with the self-acceleration effect existing in the free basic body curing, the curing of hydrosilylation is a uniform process from the beginning of the reaction to the completion of the reaction. Is favorable for obtaining optical uniform material without internal stress.
Thus, in this embodiment, the hydrogen-containing silicone resin and the vinyl-containing silicone resin cannot simultaneously contain only D-type silicon structural units, and at least one of the vinyl-containing silicone resin and the hydrogen-containing silicone resin contains Q-type silicon structural units.
In one embodiment, if the Q-type silicon structural unit content is too low, the hardness of the cured product obtained after the curable silicone composition cannot meet the requirement; if the Q-type silicon structural unit content is too high, the cured product obtained after the curable silicone composition is reduced in flexibility and deteriorated in processability. In one embodiment, the percentage of Q-type silicon structural units based on the total weight of the curable silicone composition is 27-30 percent by weight. Preferably, the percentage of Q-type silicon structural units based on the total weight of the curable silicone composition is 27%, 28%, 29%, 30%, or a range or subrange between any two of these values, on a weight basis.
In one embodiment, the percentage of T-shaped silicon structural units based on the total weight of the curable silicone composition is from 5 to 15 percent by weight. Additionally or alternatively, the percentage of T-type silicon structural units and Q-type silicon structural units based on the total weight of the curable silicone composition is 20-45%.
In one embodiment, an increase in the ratio of SiH groups to vinyl groups is effective to increase the hardness of the cured product of the curable silicone composition, but too high or too low a ratio of SiH groups to vinyl groups reduces the storage stability of the hard lens material. In one embodiment, the ratio of SiH groups to vinyl groups is 0.8 to 2.5 on a molar basis. Preferably, the ratio of SiH groups to vinyl groups is 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, or a range or subrange between any two of the values thereof, on a molar basis.
In one embodiment, the hydrogen-containing silicone resin comprises Q-type silicon structural units and the vinyl-containing silicone resin comprises D-type silicon structural units or T-type silicon structural units.
In one embodiment, the vinyl-based silicon-containing resin comprises Q-type silicon structural units and the hydrogen-containing silicon resin comprises D-type silicon structural units or T-type silicon structural units.
In one embodiment, the hydrogen-containing silicone resin comprises a Q-type silicon structural unit and the vinyl-containing silicone resin comprises a Q-type silicon structural unit.
In one embodiment of the present application, in one embodiment,
the vinyl silicone resin has a structure represented by the following general formula I:
(R 1 R 2 2 SiO 1/2 )a(R 3 2 SiO 2/2 ) b (R 4 SiO 3/2 )c(SiO 4/2 ) d the general formula I is shown in the specification,
wherein R is 1 Is a long chain containing vinyl and having 2 to 12 carbon atoms; r is R 2 Saturated alkyl chain of C1-C12;
R 3 saturated alkyl chains of C1-C12 which are identical or different;
R 4 is a long chain containing vinyl and having 2 to 12 carbon atoms; or a phenyl-containing group having a total carbon number of C6-C20, and
a>0,b≥0，c≥0，d≥0，a+b+c+d＝1。
the hydrogen-containing silicone resin has at least 2SiH bonds per molecule and has a structure represented by the following formula II:
(HR 5 R 6 SiO 1/2 )e(HR 7 SiO 2/2 ) f (R 8 SiO 3/2 )g(SiO 4/2 ) h, a general formula II,
wherein R is 5 ,R 6 ，R 7 ,R 8 Independently a saturated alkyl chain of C1-C12;
and e >0, f >0, g >0, h >0, e+f+g+h=1. In one embodiment, the hydrogen-containing silicone resin is selected from one or more of the following: DC-1107, SH1310 POSS, resil 820H, and Linktech7202-2160.
In one embodiment, the vinyl silicone resin is selected from one or more of the following: vinyl MQ class: SHR-1404, VQ20, VQ2012, linktech Resil-811VS Xinjiali XJY-8206B; vinyl MT: such as Gelest SST-3PV1; linear vinyl polydimethylsiloxane RH-Vi70E.
In one embodiment, the catalyst is a platinum-based catalyst suitable for hydrosilylation reactions, preferably one or more of the following: pt-47D, pt-2000/5000 and PT-VTSC 3.0IPA catalyst.
In a specific embodiment, the hydrosilylation reaction inhibitor is selected from one or more of the following: 1-ethynyl-1-cyclohexanol and tris [ (1, 1-dimethyl-2-propynyl) oxy ] methylsilane ].
In a second aspect, the present application provides a contact lens made of a high oxygen permeable rigid contact lens material as described above. In a specific embodiment, the contact lens is a hard corneal contact lens having a Shore D hardness of greater than or equal to 60 and a Dk of greater than or equal to 200 bar.
Examples
The technical scheme of the present application will be clearly and completely described in the following in connection with the embodiments of the present application. The reagents and starting materials used were purchased commercially, unless otherwise indicated. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
The application prepares the high oxygen permeability cross-linked polysiloxane material as a hard cornea contact lens material through the hydrosilylation reaction between vinyl silicon-containing resin and hydrogen-containing silicon resin. The vinyl silicone resin can be any silicone resin with a D, T and Q structure, and the hydrogen silicone resin can be any silicone resin with a D, T and Q structure, but the vinyl silicone resin and the hydrogen silicone resin cannot be silicone resins with a D structure at the same time, and at least one of the vinyl silicone resin and the hydrogen silicone resin is silicone resin with a Q type structure.
In a preferred embodiment, the curable silicone composition described herein may comprise the following combination:
(1) Linear hydrogen-containing polysiloxanes (e.g., DC-1107) +liquid vinyl MQ resins;
(2) A hydrosilylation-POSS (T structure, silsesquioxane) +vinyl MQ resin;
(3) Linear hydrogen-containing polysiloxane + liquid vinyl MQ resin + TTMS;
(4) Hydrogen-containing MQ resin + vinyl MQ resin;
(5) Hydrogen-containing MQ resin+linear vinyl silicone oil (D structure);
(6) Vinyl MT resin + hydrogen-containing MQ resin.
In the following examples, the raw material brands or chemical structures used are as follows.
DC-1107 refers to a linear polymethylhydrosiloxane of repeat unit 50, commercially available from Dow Corning, having the structure M (D H ) 50 M. A similar commodity is Xinan (Linktech 7202-2160).
SHR-1404 refers to liquid vinyl MQ silicone resin available from Dow Corning (Dow) and has the structure M 45 M Vi 15 Q 40 . Similar liquid MQ resins have vlmer VQ20 and VQ2012.
Pt-47D refers to divinyl tetramethyl disiloxane complexed Pt (0) at a concentration of 4% and is commercially available from Dow Corning. A similar catalyst is Pt-2000/5000 of Dongguan shellfish and PT-VTSC 3.0IPA catalyst of the family of Americaceae (Umicore).
ETCH refers to 1-ethynyl-1-cyclohexanol, which is used as an inhibitor of hydrosilylation. Similar hydrosilylation inhibitors are Tris [ (1, 1-dimethyl-2-propynyl) oxy ] methylsilane ] (Tris [ (1, 1-dimethyl-2-propynyl) oxy ] methylsilane) with CAS numbers 83817-71-4.
Resil 820H (New Silicone Linktech) has the following formula:
SH1310 POSS has the structural formula shown below and is available from Hybrid Plastics, inc:
RH-Vi70E has a vinyl content of 1.45% and a viscosity of 70mPas (25 ℃) and is commercially available from Rudder, zhejiang, and has the following structural formula:
TTMS refers to styryl tris (trimethylsiloxy) silane having a weight average molecular weight Mw of 398.8 and a vinyl mass percent of 6.77%. TTMS is a highly oxygen permeable key monomer in free radical cured hard mirror formulations. However, in the curable silicone composition of the present application, the addition of TTMS adversely leads to a decrease in the hardness of the optical material.
Example 1SiHR-3
This example relates to the preparation of hard contact lenses wherein the Q silicon building blocks account for 27% by weight of the total composition material weight, the Si accounts for 37.06% by weight of the total composition material weight, and the molar ratio of SiH groups to vinyl groups is 1.10.
The experimental procedure of this example is as follows.
0.071g ETCH,0.0147g Pt-47D,11.8g DC-1107 and 88.2g SHR-1404 were weighed out sequentially in a 150mL polypropylene mixing cup. The mixture was mixed at high speed for 2 minutes at 1500rpm on a Speedmixer high speed double planetary mixer. The material was then poured into a PTFE reaction tube having a length of 20cm and a wall thickness of 2.5 mm. The reaction tube has one end with opening and bottom with screw thread sealing. The reaction tube was then placed vertically in a glass vacuum drier and evacuated for deaeration for 10 minutes. Finally, the reaction tube after deaeration was transferred to a forced air drying oven set at a temperature of 120℃and reacted overnight for 16 hours. After curing was completed, the oven was closed to allow the temperature to slowly drop to room temperature and the reaction tube was removed. The cured columnar polysiloxane resin material can be easily pushed out from one end by unscrewing the tetrafluoro threaded cap at one end, and has high optical transparency.
The Shore D hardness of the columnar material was measured and the columnar material was further machined on a lathe into a disk-like material of 12.7mm OD x 4.8mm thickness.
The disc material was further processed on a precision lathe to give hard contact lenses of a certain thickness and luminosity, and with these lenses, oxygen permeability and light transmittance were tested. The performance test data of the lenses obtained in this example are shown in table 1 below.
Example 2SiHR-4
This example relates to the preparation of hard contact lenses wherein the Q silicon building blocks account for 27.5% by weight of the total composition material, the Si accounts for 37.45% by weight of the total composition material, and the molar ratio of SiH groups to vinyl groups is 1.37.
The experimental procedure of this example is as follows.
0.071g ETCH,0.0147g Pt-47D,11.1g DC-1107,83.3g SHR-1404 and 5.6g SH1310 POSS were weighed out in order in a 150mL polypropylene mixing cup. The mixture was mixed at high speed for 2 minutes at 1500rpm on a Speedmixer high speed double planetary mixer. The material was then poured into a PTFE reaction tube having a length of 20cm and a wall thickness of 2.5 mm. The reaction tube has one end with opening and bottom with screw thread sealing. The reaction tube was then placed vertically in a glass vacuum drier and evacuated for deaeration for 10 minutes. Finally, the reaction tube after deaeration was transferred to a forced air drying oven set at a temperature of 120℃and reacted overnight for 16 hours. After curing was completed, the oven was closed to allow the temperature to slowly drop to room temperature and the reaction tube was removed. The cured columnar polysiloxane resin material can be easily pushed out from one end by unscrewing the tetrafluoro threaded cap at one end, and has high optical transparency.
The Shore D hardness of the columnar material was measured and the columnar material was further machined on a lathe into a disk-like material of 12.7mm OD x 4.8mm thickness.
The disc material was further processed on a precision lathe to give hard contact lenses of a certain thickness and luminosity, and with these lenses, oxygen permeability and light transmittance were tested. The performance test data of the lenses obtained in this example are shown in table 1 below.
Example 3SiHR-2
This example relates to the preparation of hard contact lenses wherein the Q silicon building blocks account for 23.8% by weight of the total composition material, the Si accounts for 36.0% by weight of the total composition material, and the molar ratio of SiH groups to vinyl groups is 0.95.
The experimental procedure of this example is as follows.
0.070g ETCH,0.0100g Pt-47D,10.7g DC-1107,77.32g SHR-1404 and 11.90g TTMS were weighed out sequentially in a 150mL polypropylene mixing cup. The mixture was mixed at high speed for 2 minutes at 1500rpm on a Speedmixer high speed double planetary mixer. The material was then poured into a PTFE reaction tube having a length of 20cm and a wall thickness of 2.5 mm. The reaction tube has one end with opening and bottom with screw thread sealing. The reaction tube was then placed vertically in a glass vacuum drier and evacuated for deaeration for 10 minutes. Finally, the reaction tube after deaeration was transferred to a forced air drying oven set at a temperature of 120℃and reacted overnight for 16 hours. After curing was completed, the oven was closed to allow the temperature to slowly drop to room temperature and the reaction tube was removed. The cured columnar polysiloxane resin material can be easily pushed out from one end by unscrewing the tetrafluoro threaded cap at one end, and has high optical transparency.
The Shore D hardness of the columnar material was measured and the columnar material was further machined on a lathe into a disk-like material of 12.7mm OD x 4.8mm thickness.
The disc material was further processed on a precision lathe to give hard contact lenses of a certain thickness and luminosity, and with these lenses, oxygen permeability and light transmittance were tested. The performance test data of the lenses obtained in this example are shown in table 1 below.
Example 4SiHR-8
This example relates to the preparation of hard contact lenses wherein the Q silicon building blocks comprise 28% by weight of the total weight of the composition starting materials, the Si comprises 37.4% by weight of the total weight of the composition starting materials, and the molar ratio of SiH groups to vinyl groups is 1.37.
The experimental procedure of this example is as follows.
0.060g ETCH,0.0100g Pt-47D,78.2g SHR-1404 and 21.7g Resil 820H were weighed out sequentially in a 150mL polypropylene mixing cup. The mixture was mixed at high speed for 2 minutes at 1500rpm on a Speedmixer high speed double planetary mixer. The material was then poured into a PTFE reaction tube having a length of 20cm and a wall thickness of 2.5 mm. The reaction tube has one end with opening and bottom with screw thread sealing. The reaction tube was then placed vertically in a glass vacuum drier and evacuated for deaeration for 10 minutes. Finally, the reaction tube after deaeration was transferred to a forced air drying oven set at a temperature of 120℃and reacted overnight for 16 hours. After curing was completed, the oven was closed to allow the temperature to slowly drop to room temperature and the reaction tube was removed. The cured columnar polysiloxane resin material can be easily pushed out from one end by unscrewing the tetrafluoro threaded cap at one end, and has high optical transparency.
The Shore D hardness of the columnar material was measured and the columnar material was further machined on a lathe into a disk-like material of 12.7mm OD x 4.8mm thickness.
The disc material was further processed on a precision lathe to give hard contact lenses of a certain thickness and luminosity, and with these lenses, oxygen permeability and light transmittance were tested. The performance test data of the lenses obtained in this example are shown in table 1 below.
Example 5SiHR-9
This example relates to the preparation of hard contact lenses wherein the Q silicon building blocks comprise 26.2% by weight of the total weight of the composition starting materials, the Si comprises 36.5% by weight of the total weight of the composition starting materials, and the molar ratio of SiH groups to vinyl groups is 0.84.
The experimental procedure of this example is as follows.
0.060g ETCH,0.0100g Pt-47D,55g SHR-1404, 10g Resil 820H and 35g RH-Vi70E were weighed out in sequence in a 150mL polypropylene mixing cup. The mixture was mixed at high speed for 2 minutes at 1500rpm on a Speedmixer high speed double planetary mixer. The material was then poured into a PTFE reaction tube having a length of 20cm and a wall thickness of 2.5 mm. The reaction tube has one end with opening and bottom with screw thread sealing. The reaction tube was then placed vertically in a glass vacuum drier and evacuated for deaeration for 10 minutes. Finally, the reaction tube after deaeration was transferred to a forced air drying oven set at a temperature of 120℃and reacted overnight for 16 hours. After curing was completed, the oven was closed to allow the temperature to slowly drop to room temperature and the reaction tube was removed. The cured columnar polysiloxane resin material can be easily pushed out from one end by unscrewing the tetrafluoro threaded cap at one end, and has high optical transparency.
The Shore D hardness of the columnar material was measured and the columnar material was further machined on a lathe into a disk-like material of 12.7mm OD x 4.8mm thickness.
The disc material was further processed on a precision lathe to give hard contact lenses of a certain thickness and luminosity, and with these lenses, oxygen permeability and light transmittance were tested. The performance test data of the lenses obtained in this example are shown in table 1 below.
Example 6SiHR-6
This example relates to the preparation of hard contact lenses wherein the Q-type silicon structural units comprise 27% by weight of the total composition material, the Si comprises 37.9% by weight of the total composition material, and the molar ratio of SiH groups to vinyl groups is 2.12
The experimental procedure of this example is as follows.
0.060g ETCH,0.0100g Pt-47D,70g SHR-1404 and 30g Resil 820H were weighed out sequentially in a 150mL polypropylene mixing cup. The mixture was mixed at high speed for 2 minutes at 1500rpm on a Speedmixer high speed double planetary mixer. The material was then poured into a PTFE reaction tube having a length of 20cm and a wall thickness of 2.5 mm. The reaction tube has one end with opening and bottom with screw thread sealing. The reaction tube was then placed vertically in a glass vacuum drier and evacuated for deaeration for 10 minutes. Finally, the reaction tube after deaeration was transferred to a forced air drying oven set at a temperature of 120℃and reacted overnight for 16 hours. After curing was completed, the oven was closed to allow the temperature to slowly drop to room temperature and the reaction tube was removed. The cured columnar polysiloxane resin material can be easily pushed out from one end by unscrewing the tetrafluoro threaded cap at one end, and has high optical transparency.
The Shore D hardness of the columnar material was measured and the columnar material was further machined on a lathe into a disk-like material of 12.7mm OD x 4.8mm thickness.
The disc material was further processed on a precision lathe to give hard contact lenses of a certain thickness and luminosity, and with these lenses, oxygen permeability and light transmittance were tested. The performance test data of the lenses obtained in this example are shown in table 1 below.
Comparative example 1SiHR-0
This comparative example relates to the preparation of hard contact lenses wherein the Q silicon structural units comprise 0% by weight of the total weight of the composition starting materials, the Si comprises 33.2% by weight of the total weight of the composition starting materials, and the molar ratio of SiH groups to vinyl groups is 1.55.
The experimental procedure of this example is as follows.
0.060g ETCH,0.0100g Pt-47D,5g DC-1107 and 95g RH-Vi70E were weighed out sequentially in 150mL polypropylene mixing cups. The mixture was mixed at high speed for 2 minutes at 1500rpm on a Speedmixer high speed double planetary mixer. The material was then poured into a PTFE reaction tube having a length of 20cm and a wall thickness of 2.5 mm. The reaction tube has one end with opening and bottom with screw thread sealing. The reaction tube was then placed vertically in a glass vacuum drier and evacuated for deaeration for 10 minutes. Finally, the reaction tube after deaeration was transferred to a forced air drying oven set at a temperature of 120℃and reacted overnight for 16 hours. After curing was completed, the oven was closed to allow the temperature to slowly drop to room temperature and the reaction tube was removed. The cured cylindrical silicone resin material can be pushed out from one end by unscrewing the tetrafluoro threaded cap at one end.
The columnar material obtained in this comparative example was too soft to be processed, and therefore only its Shore A hardness was measured, and its performance test data are shown in Table 1 below.
Comparative example 2SiHR-10
This comparative example relates to the preparation of hard contact lenses wherein the Q silicon structural units comprise 31.7% by weight of the total weight of the composition starting materials, the Si comprises 37.9% by weight of the total weight of the composition starting materials, and the molar ratio of SiH groups to vinyl groups is 1.36.
The experimental procedure of this example is as follows.
0.060g ETCH,0.0125g Pt-47D,75g SHR-1404, 25g SH1310 POSS were weighed in a 150mL polypropylene mixing cup and mixed at high speed for 2 minutes on a Speedmixer at 1500 rpm. The material was then poured into a PTFE reaction tube having a length of 20cm and a wall thickness of 2.5 mm. The reaction tube has one end with opening and bottom with screw thread sealing. The reaction tube was then placed vertically in a glass vacuum drier and evacuated for deaeration for 10 minutes. Finally, the reaction tube after deaeration was transferred to a forced air drying oven set at a temperature of 120℃and reacted overnight for 16 hours. After curing was completed, the oven was closed to allow the temperature to slowly drop to room temperature and the reaction tube was removed. The cured cylindrical silicone resin material can be pushed out from one end by unscrewing the tetrafluoro threaded cap at one end.
The columnar material obtained in this comparative example was too brittle to be processed, and therefore only its Shore D hardness was measured, and its performance test data are shown in Table 1 below.
The performance parameters of the polysiloxane resin materials prepared in examples 1-5 and comparative examples 1-2 are shown in Table 1.
TABLE 1 Property parameters of polysiloxane resin materials prepared in examples 1-5 and comparative examples 1-2
| Numbering device | Q％ | Si％ | Hardness of | Oxygen permeability | Transmittance of light |
| Example 1 | 27％ | 37.1％ | 60 | 227.5 | 95％ |
| Example 2 | 27.5％ | 37.5％ | 70 | 227 | 95％ |
| Example 3 | 23.8％ | 36.0％ | 50 | 224 | 95％ |
| Example 4 | 28％ | 37.4％ | 60 | 230 | 95％ |
| Example 5 | 26.2％ | 36.5％ | 55 | 200 | 95％ |
| Example 6 | 27％ | 37.9％ | 60 | 240 | 95％ |
| Comparative example 1 | 0％ | 33.4％ | 30* | / | / |
| Comparative example 2 | 31.7％ | 37.9％ | 80 | / | / |
In table 1, Q% refers to the mass percent of Q-type silicon structural units based on the total weight of the composition raw materials; si% refers to the mass percent of Si in the total weight of the composition raw materials; hardness refers to Shore D hardness; the oxygen permeability is in bar, i.e. 10 -11 (cm 2/s) [ ml O2/mmHg); the light transmittance means light transmittance in the range of 380 to 780 nm. * The polysiloxane resin material of comparative example 1 was too soft and exhibited a hardness of Shore A.
As can be seen from table 1, example 1 obtained a relatively high hardness (D60) crosslinked silicone material that was machine turned into lenses of a certain degree and measured for oxygen permeability (227.5 bar). Boston XO material prepared by a free radical curing mode has the hardness of D80 and the oxygen permeability of 100 bar.
From the data of comparative example 1, it is clear that when the mass percentage of the Q-type silicon structural units based on the total weight of the raw materials of the composition is too low, the polysiloxane resin material prepared is too soft to be processed into lenses. Meanwhile, as is clear from the data of comparative example 2, when the mass percentage of the Q-type silicon structural units based on the total weight of the raw materials of the composition is too high, the prepared polysiloxane resin material is too brittle to be processed.
The embodiments are described above in order to facilitate the understanding and application of the present application by those of ordinary skill in the art. It will be apparent to those skilled in the art that various modifications can be made to these embodiments and that the general principles described herein may be applied to other embodiments without the use of inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art, based on the present disclosure, may make improvements and modifications within the scope and spirit of the present application without departing from the scope and spirit of the present application.
Claims (9)
1. A high oxygen permeable rigid contact lens material, wherein the high oxygen permeable rigid contact lens material is made from a cured product of a curable silicone composition, wherein the curable silicone composition comprises the following components:
(a) A hydrogen-containing silicone resin comprising SiH groups bonded to silicon and hydrogen atoms;
(b) A vinyl-containing silicon resin comprising a vinyl group capable of undergoing an addition reaction with the SiH group;
(c) A catalyst; and
(d) Hydrosilylation reaction inhibitors
Wherein the hydrogen-containing silicone resin comprises any one or more of a D-type silicon structural unit, a T-type silicon structural unit and a Q-type silicon structural unit, and has a structure represented by the following general formula: (HR) 5 R 6 SiO 1/2 ) e (HR 7 SiO 2/2 ) f (R 8 SiO 3/2 ) g (SiO 4/2 ) h Wherein R is 5 ,R 6 ，R 7 ,R 8 Independently a C1-C12 saturated alkyl chain, and e>0,f≥0，g≥0，h≥0，e+f+g+h=1；
Wherein the vinyl-based silicon-containing resin comprises any one or more of a D-type silicon structural unit, a T-type silicon structural unit and a Q-type silicon structural unit, and has a structure represented by the following general formula: (R) 1 R 2 2 SiO 1/2 ) a (R 3 2 SiO 2/2 ) b (R 4 SiO 3/2 ) c (SiO 4/2 ) d Wherein R is 1 Is a long chain containing vinyl and having 2 to 12 carbon atoms; r is R 2 Saturated alkyl chain of C1-C12; r is R 3 Is the same or different C1-C12 saturationAnd an alkyl chain; r is R 4 Is a long chain containing vinyl groups having 2 to 12 carbon atoms, or a phenyl group having a total carbon number of C6 to C20, and a>0,b≥0，c≥0，d≥0，a+b+c+d=1；
Wherein the hydrogen-containing silicone resin and the vinyl-containing silicone resin cannot simultaneously contain only D-type silicon structural units, and at least one of the vinyl-containing silicone resin and the hydrogen-containing silicone resin contains Q-type silicon structural units;
wherein, the ratio of SiH groups to vinyl groups is 0.8-2.5 based on the mole number;
wherein the percentage of Q-type silicon structural units based on weight is 27-30% of the total weight of the curable silicone composition;
wherein the Shore D hardness of the contact lens made of the high oxygen permeability hard contact lens material is greater than or equal to 60, and the oxygen permeability coefficient is greater than or equal to 200 bar.
2. The high oxygen permeable rigid contact lens material of claim 1, wherein the ratio of SiH groups to vinyl groups on a molar basis is 0.8 to 2.2;
wherein the percentage of Q silicon structural units based on weight is 27-28% of the total weight of the curable silicone composition.
3. The high oxygen permeable rigid contact lens material of claim 1, wherein the T-shaped silicon structural units comprise 5-15% by weight of the total weight of the curable silicone composition;
and/or the percentage of T-type silicon structural units and Q-type silicon structural units based on weight is 20-45% of the total weight of the curable silicone composition.
4. A high oxygen permeable rigid contact lens material according to any one of claims 1 to 3, wherein the hydrogen containing silicone resin comprises Q-type silicon structural units and the vinyl containing silicone resin comprises D-type silicon structural units or T-type silicon structural units.
5. A high oxygen permeable rigid contact lens material according to any one of claims 1 to 3, wherein the vinyl-based silicon-containing resin comprises Q-type silicon structural units and the hydrogen-containing silicon resin comprises D-type silicon structural units or T-type silicon structural units.
6. A high oxygen permeable rigid contact lens material according to any one of claims 1 to 3, wherein the hydrogen containing silicone resin comprises Q-type silicon structural units and the vinyl containing silicone resin comprises Q-type silicon structural units.
7. A high oxygen permeable rigid contact lens material according to any one of claims 1 to 3, wherein the hydrogen containing silicone resin is selected from one or more of the following: DC-1107, SH1310 POSS, resil 820H, and Linktech 7202-2160;
the vinyl silicone resin is selected from one or more of the following: SHR-1404, VQ20, VQ2012, linktech Resil-811VS, xinjia XJY-8206B, gelest SST-3PV1 and RH-Vi70E;
the catalyst is a platinum catalyst suitable for hydrosilylation reaction;
the hydrosilylation reaction inhibitor is selected from one or more of the following: 1-ethynyl-1-cyclohexanol and tris [ (1, 1-dimethyl-2-propynyl) oxy ] methylsilane ].
8. The high oxygen permeable rigid contact lens material of claim 7, wherein the catalyst is selected from one or more of the following: pt-47D, pt-2000/5000 and PT-VTSC 3.0IPA catalyst.
9. Contact lens, characterized in that it is made of a high oxygen-permeable rigid contact lens material according to any one of claims 1 to 8.
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