WO2015092859A1 - 眼用レンズ - Google Patents
眼用レンズ Download PDFInfo
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- WO2015092859A1 WO2015092859A1 PCT/JP2013/083671 JP2013083671W WO2015092859A1 WO 2015092859 A1 WO2015092859 A1 WO 2015092859A1 JP 2013083671 W JP2013083671 W JP 2013083671W WO 2015092859 A1 WO2015092859 A1 WO 2015092859A1
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/14—Eye parts, e.g. lenses, corneal implants; Implanting instruments specially adapted therefor; Artificial eyes
- A61F2/16—Intraocular lenses
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/068—Polysiloxanes
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
- C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
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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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- 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
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
- C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
- G02B1/043—Contact lenses
Definitions
- the present invention relates to ophthalmic lenses such as contact lenses and intraocular lenses.
- ophthalmic lenses such as contact lenses and intraocular lenses.
- contact lenses mounted on sensitive corneas have less foreign body feeling and excellent wearing feeling. It is inherently required to demonstrate.
- intraocular lenses if the lens is made of a highly flexible lens material (polymer), the lens can be folded down and inserted into the eye with a small incision. In recent years, development of a new intraocular lens made of a lens material (polymer) having excellent flexibility has been desired.
- a silicone polymer having a siloxane main chain having a siloxane unit as a repeating unit is widely known to be excellent in flexibility and oxygen permeability.
- various ophthalmic lenses such as contact lenses are used. It is used as a material.
- a copolymer (silicone hydrogel) of a polysiloxane macromonomer in which a polymerizable group is bonded to a siloxane main chain and a hydrophilic monomer such as N-vinylpyrrolidone or dimethylacrylamide has a high water content and high oxygen permeability.
- Patent Document 1 Japanese Patent Publication No. 2008-511870
- Patent Document 2 Japanese Patent Application Laid-Open No. 2010-20330
- Patent Document 3 Japanese Patent Publication No. 2012-513042 proposes a method for producing a silicone hydrogel contact lens.
- JP-T 2008-511870 JP 2010-20330 A Special table 2012-513042 gazette Japanese Patent No. 3641110
- the present invention has been made in the background of such circumstances, and the problem to be solved is to exhibit excellent wearing feeling required as a contact lens, and an intraocular lens. It is an object of the present invention to provide an ophthalmic lens having sufficient flexibility and moderate deformation recovery required.
- the present inventor earnestly and repeatedly researched, in the ophthalmic lens composed of a polymer whose Young's modulus and relaxation rate are each within a predetermined range, The present inventors have found that the above-described problems can be solved and have completed the present invention.
- the gist of the present invention is an ophthalmic lens made of a polymer having a Young's modulus of 0.3 to 1.0 MPa and a relaxation rate of 10 to 20%.
- ⁇ calculated from the following formula (A) is 0.02 to 0.10.
- ⁇ E / r (A)
- E represents the Young's modulus (MP of the polymer constituting the ophthalmic lens).
- a) the relaxation rate (%) of the polymer.
- the polymer comprises a polysiloxane macromolecule having at least one polymerizable group and a polysiloxane chain having a siloxane unit as a repeating unit. It is a polymer of a polymerizable composition containing a monomer.
- the polysiloxane macromonomer is 1) an oxyethylene group as a repeating unit, and the repeating number is a (where a is an integer of 2 or more).
- ⁇ calculated from the following formula (B) is 0.5 to 5.0.
- ⁇ n / (a + b) (B)
- n is the total number of silicon atoms in the polysiloxane macromonomer molecule.
- the polysiloxane macromonomer has an HLB value calculated from the following formula (C) of 0.7 to 6.0.
- HLB value W E / 5 (C)
- W E is the weight fraction (% by weight) of oxyethylene groups in one molecule of the polysiloxane macromonomer.
- the number of repetitions of the oxyethylene group: a is 4-15.
- the polyoxyalkylene chain is a polyoxypropylene chain having an oxypropylene group as a structural unit.
- the number of repeating oxypropylene groups is 5-16.
- the polymerizable group is bonded to the polysiloxane chain constituting the main chain in the monomer molecule via one or more urethane bonds.
- the Young's modulus and the relaxation rate are each composed of a polymer having a predetermined range, so that the excellent wearing feeling required as a contact lens is achieved. In addition, it has sufficient flexibility and moderate deformation recovery required for an intraocular lens.
- the ophthalmic lens according to the present invention is composed of a polymer having a Young's modulus (E) of 0.3 to 1.0 MPa and a relaxation rate (r) of 10 to 20%.
- E Young's modulus
- r relaxation rate
- the Young's modulus (E) of the polymer (lens material) constituting the ophthalmic lens is often used as an index indicating the flexibility of the lens material.
- a contact lens using a lens material having a low Young's modulus is used.
- the contact lens tends to have a good wearing feeling.
- the relaxation rate (r) is found by the present inventor as an index indicating the degree of stress relaxation, and is set in the present invention. Stress relaxation means a phenomenon in which stress decreases with time when a certain strain is applied to an object. In the present invention, the relaxation rate (r) is calculated from the following formula (D).
- L 1 and L 2 are determined by a tensile test on the polymer constituting the ophthalmic lens. Specifically, using a polymer constituting an ophthalmic lens, JIS-K-7162-1994 “Plastics-Test method for tensile properties Part 2: Test conditions for mold molding, extrusion molding and cast plastic” FIG. A test piece having the shape (dumbbell shape) described in 2 is prepared, and a tensile test is performed under the condition of a tensile speed of 20 mm / min.
- the Young's modulus in the range of 0.01 to 0.10 N is defined as the Young's modulus (E) in the present invention.
- the polymer constituting the ophthalmic lens is a hydrous material such as a hydrogel constituting a hydrous soft contact lens
- the polymer is immersed in water or physiological saline to be hydrated, and in an equilibrium state.
- the polymer swollen until becomes a test piece as described above, and a tensile test is performed under the above-described conditions in water or physiological saline used for hydration.
- the obtained Young's modulus and relaxation rate are the Young's modulus and relaxation rate of the present invention.
- the polymer constituting the ophthalmic lens of the present invention has a Young's modulus and a relaxation rate within the predetermined ranges, and more preferably, ⁇ calculated from the following formula (A) is It is in the range of 0.02 to 0.10.
- ⁇ E / r (A)
- E represents the Young's modulus (MP of the polymer constituting the ophthalmic lens).
- a) is the relaxation rate (%) of the polymer.
- ⁇ is a parameter found as a result of the present inventors diligently researching ophthalmic lenses such as contact lenses and intraocular lenses, and in particular, wearing feeling as a contact lens and intraocular lens It is an index showing the flexibility and deformation recovery property.
- the ophthalmic lens composed of a polymer having an ⁇ in the range of 0.02 to 0.10, the ophthalmic lens exhibits better wearing feeling as a contact lens, and is sufficient as an intraocular lens. This means that flexibility and appropriate deformation recovery properties are more effectively expressed.
- the ophthalmic lens according to the present invention is composed of a polymer having Young's modulus and relaxation rate each within a predetermined range.
- a polymer at least one polymerizable group
- a polymer of a polymerizable composition containing a polysiloxane macromonomer having a siloxane unit as a repeating unit is preferable.
- any polymer can be used as long as the Young's modulus and relaxation rate of the finally obtained polymer can be within the above-mentioned predetermined ranges. It is.
- a polyoxyethylene chain having an oxyethylene group as a repeating unit and a repeating number of a (where a is an integer of 2 or more)
- a polysiloxane macromonomer of 0.0 is particularly advantageously used.
- ⁇ n / (a + b) (B)
- n is the total number of silicon atoms in the polysiloxane macromonomer molecule.
- the above-mentioned polysiloxane macromonomer has a characteristic structure, it can be used for both hydrophobic monomers and hydrophilic monomers generally used in the production of ophthalmic lenses. Therefore, good compatibility can be ensured. That is, when manufacturing various ophthalmic lenses such as contact lenses, the conventional polysiloxane macromonomer has poor compatibility with other components (for example, hydrophilic monomer), and the resulting lens becomes cloudy.
- the polysiloxane macromonomer having a characteristic structure as described above is also used in a compounding composition that has been difficult to adopt due to the possibility of generating grease when used as an intraocular lens. Can be used. Therefore, the ophthalmic lens of the present invention has various characteristics such as oxygen permeability due to the increased degree of freedom of the composition compared to conventional ophthalmic lenses using polysiloxane macromonomers. It is possible to improve.
- the polysiloxane macromonomer advantageously used in the present invention has the same polymerizable group as the conventional polysiloxane macromonomer.
- a polymerizable group examples include an acryloyloxy group, a methacryloyloxy group, a vinyl group, and an allyl group.
- the polysiloxane macromonomer advantageously used in the present invention has a polyoxyethylene chain in which the number of repeating oxyethylene groups is 2 or more, but the number of repeating oxyethylene groups is too large (many If the macromonomer has a polyoxyethylene chain in which the number of repeating oxyethylene groups is too large (too many), it is difficult to produce a macromonomer. There is a risk that the strength of the lens decreases and becomes brittle. Therefore, when the ophthalmic lens of the present invention is produced, the number of repeating oxyethylene groups constituting the polyoxyethylene chain is suitably selected within the range of preferably 4 to 15, more preferably 4 to 10. Polysiloxane-based macromonomers are used.
- a polysiloxane macromonomer advantageously used in the present invention together with a polyoxyethylene chain having a repeating number of oxyethylene groups of 2 or more is a polyoxyethylene group having a repeating unit of an oxyalkylene group different from the oxyethylene group. It has an alkylene chain.
- the oxyalkylene group constituting the polyoxyalkylene chain any of various conventionally known oxyalkylene groups can be used as long as they do not inhibit the effects of the present invention.
- oxybutylene groups preferably has a polyoxypropylene chain having an oxypropylene group (—CH (CH 3 ) CH 2 O—) as a repeating unit.
- the number of repeating oxyalkylene groups different from the oxyethylene group is appropriately determined according to the type of oxyalkylene group constituting the polyoxyalkylene chain.
- the number of repeating oxypropylene groups is preferably in the range of 5 to 16.
- the polysiloxane macromonomer advantageously used in the present invention has a polyoxyethylene chain and a polyoxyalkylene chain different from the polyoxyethylene chain as described above, and from the above formula (B).
- the calculated ⁇ is configured to be in the range of 0.5 to 5.0.
- ⁇ is a parameter found as a result of the present inventors diligently researching the polysiloxane macromonomer used for the ophthalmic lens, and a hydrophobic component such as a hydrophobic monomer, and It is a parameter
- polysiloxane macromonomer having ⁇ of 0.5 to 5.0 is superior to both the hydrophobic component and the hydrophilic component used in producing an ophthalmic lens.
- polysiloxane macromonomers having a ⁇ of less than 0.5 or ⁇ of more than 5.0 exhibit poor compatibility with hydrophobic components and / or hydrophilic components. The effects of the invention cannot be enjoyed more advantageously.
- the polysiloxane macromonomer described above preferably has an HLB value calculated from the following formula (C) of 0.7 to 6.0.
- HLB value W E / 5 (C)
- W E is the weight fraction (% by weight) of oxyethylene groups in one molecule of the polysiloxane macromonomer.
- the polysiloxane macromonomer used in the present invention has a polysiloxane chain having a siloxane unit as a repeating unit in the molecular chain
- the present invention using such a polysiloxane macromonomer is used.
- the ophthalmic lens according to the above exhibits excellent oxygen permeability.
- an ophthalmic lens is manufactured using a polysiloxane macromonomer having a structure in which a polymerizable group is bonded to a polysiloxane chain constituting a main chain in a monomer molecule through one or more urethane bonds.
- the polysiloxane macromonomer advantageously used in the ophthalmic lens according to the present invention has the above-described structural characteristics, so that the raw material for the ophthalmic lens according to the present invention is used. Any monomer can be used.
- Examples of the polysiloxane macromonomer advantageously used in the production of the ophthalmic lens of the present invention include those represented by the following general formula (I).
- a 1 and A 2 are groups represented by the following general formulas (II) and (III), respectively.
- Y 21 and Y 22 are all polymerizable groups, and each independently represents an acryloyloxy group, a methacryloyloxy group, a vinyl group or an allyl group.
- R 21 and R 22 each independently represents a direct bond or an alkylene group having a straight chain or branched chain having 2 to 6 carbon atoms.
- the alkylene group is preferably an ethylene group, a propylene group or a butylene. It is a group.
- Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 are each independently a polyoxyalkylene chain having a direct bond or an oxyalkylene group as a repeating unit. is there. However, at least one or more of Z 1 to Z 6 is a polyoxyethylene chain in which the number of repeating oxyethylene groups is 2 or more, and at least one or more of Z 1 to Z 6 that are not polyoxyethylene chains. Is a polyoxyalkylene chain having an oxyalkylene group different from the oxyethylene group as a repeating unit.
- the number of repeating oxyethylene groups is preferably 4 to 15, more preferably 4 to 10, and the polyoxyethylene group having an oxyalkylene group different from the oxyethylene group as a repeating unit.
- the alkylene chain is preferably a polyoxypropylene chain having 5 to 16 repeating oxypropylene groups.
- U 1 is a group represented by the following general formula (IV), and includes a urethane bond in the molecular chain of the polysiloxane macromonomer.
- E 21 is a —NHCO— group (in this case, E 21 forms a urethane bond with X 21 ), or a saturated or unsaturated aliphatic system, alicyclic system and aromatic Represents a divalent group derived from a diisocyanate selected from the group of the group (in this case, E 21 forms a urethane bond between Z 1 and X 21 ), and X 21 represents an oxygen atom .
- U 2 is a group represented by the following general formula (VI), and includes a urethane bond in the molecular chain of the polysiloxane macromonomer.
- -R 41 -X 41 -E 41 -X 42 -R 42 - ⁇ (VI)
- R 41 and R 42 each independently represent an alkylene group having a linear or branched chain having 2 to 6 carbon atoms
- X 41 and X 42 are each independently Represents an oxygen atom or an alkylene glycol group
- E 41 is a divalent group derived from a diisocyanate selected from the group consisting of saturated or unsaturated aliphatic, alicyclic and aromatic groups (in this case, E 41 is X 41 and X 42 form a urethane bond).
- U 3 is a group represented by the following general formula (VII), and contains a urethane bond in the molecular chain of the polysiloxane macromonomer. : -X 22 -E 22 - ⁇ (VII )
- X 22 represents an oxygen atom
- E 22 represents a —NHCO— group (in this case, E 22 forms a urethane bond with X 22 ), or is saturated or unsaturated.
- divalent group derived from a diisocyanate selected from the group of aliphatic groups include divalent groups derived from saturated aliphatic diisocyanates such as ethylene diisocyanate, 1,3-diisocyanate propane, hexamethylene diisocyanate; A divalent group derived from an alicyclic diisocyanate such as diisocyanate cyclohexane, bis (4-isocyanatocyclohexyl) methane, isophorone diisocyanate; a divalent group derived from an aromatic diisocyanate such as tolylene diisocyanate or 1,5-diisocyanate naphthalene Unsaturated fatty systems such as 2,2'-diisocyanate diethyl fumarate
- a divalent group derived from hexamethylene diisocyanate and a divalent group derived from isophorone diisocyanate are relatively easily available, and can ultimately impart high strength to the target ophthalmic lens. Therefore, it is advantageously employed in the present invention.
- S 1 and S 2 are each independently a group represented by the following general formula (V).
- R 31 and R 38 are each independently an alkylene group having a linear or branched chain having 2 to 6 carbon atoms
- R 32 , R 33 , R 34 , R 35 , R 36 and R 37 are each independently an alkyl group having 1 to 6 carbon atoms, a fluorine-substituted alkyl group, or a phenyl group.
- the above-described alkyl group substituted with fluorine includes 3,3,3-trifluoro-n-propyl group, 2,2,2-trifluoroisopropyl group, 4,4,4-trifluoro-n- Butyl group, 3,3,3-trifluoroisobutyl group, 3,3,3-trifluoro-sec-butyl group, 2,2,2-trifluoro-tert-butyl group, 5,5,5-trifluoro Examples include -n-pentyl group, 4,4,4-trifluoroisopentyl group, 3,3,3-trifluoroneopentyl group, 6,6,6-trifluorohexyl group and the like.
- K is an integer of 1 to 1500
- L is 0 or an integer of 1 to 1500
- the sum of K and L: “K + L” is an integer of 1 to 1500.
- the value of “K + L” is 0, not only the oxygen permeability of the ophthalmic lens material obtained using such a monomer is lowered, but also the flexibility tends to be lowered.
- the value of “K + L” is preferably an integer of 2 to 1000, more preferably an integer of 3 to 500.
- n represents 0 or an integer of 1 to 10.
- n in the general formula (I) is 0 or an integer of 1 to 5.
- polysiloxane macromonomer used in producing the ophthalmic lens of the present invention preferred embodiments thereof include those represented by the following general formula (VIII) and the following general formula (IX). .
- the polysiloxane macromonomer used in producing the ophthalmic lens of the present invention is not limited to those represented by the following general formula (VIII) and the following general formula (IX). Needless to say.
- R 51 represents a hydrogen atom or a methyl group
- a is an integer of 2 or more
- b is an integer of 2 or more
- n is an integer of 1 to 1500.
- R 52 and R 5 3 is a hydrogen atom or a methyl group.
- a ′ is an integer of 2 or more
- b ′ is an integer of 2 or more
- n ′ is 1. It is an integer of ⁇ 1500.
- R 61 and R 62 are a hydrogen atom or a methyl group. When R 61 is a hydrogen atom, R 62 is a methyl group, and when R 61 is a methyl group, R 62 is It is a hydrogen atom.
- the above-mentioned polysiloxane macromonomer is produced by using various known compounds as starting materials (raw materials) and reacting them continuously or stepwise according to known methods. Is possible.
- the ophthalmic lens according to the present invention is formed using a polysiloxane macromonomer having a specific structure as described above as one of the raw material monomers.
- a polysiloxane macromonomer having a specific structure as described above as one of the raw material monomers.
- the polysiloxane macromonomer means a polysiloxane macromonomer having a specific structure as described above.
- components used in producing the ophthalmic lens of the present invention include hydrophilic monomers, hydrophobic monomers, cross-linking agents, reinforcing agents, hydrophilizing agents, ultraviolet absorbers and dyes. .
- hydrophilic monomers include N-vinylpyrrolidone (NVP); acrylamide, N, N-dimethylacrylamide (DMAA), N, N-diethylacrylamide, N, N-dimethylaminopropylacrylamide, and N-isopropylacrylamide.
- NVP N-vinylpyrrolidone
- DMAA N-dimethylacrylamide
- DMAA N-dimethylacrylamide
- N-diethylacrylamide N, N-dimethylaminopropylacrylamide
- N-isopropylacrylamide N-isopropylacrylamide
- Acrylamide monomers such as acryloylmorpholine; hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxybutyl acrylate; (alkyl) aminoalkyl acrylates such as 2-dimethylaminoethyl acrylate and 2-butylaminoethyl acrylate; Alkylene glycol monoacrylates such as ethylene glycol monoacrylate and propylene glycol monoacrylate; ethylene glycol Ethylene glycol vinyl ether; acrylic acid; aminostyrene; hydroxystyrene; vinyl acetate; glycidyl acrylate; allyl glycidyl ether; vinyl propionate; N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-4-methyl- 2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-6-methyl-2-pyrrolidone, N-
- examples of the hydrophobic monomer include silicon-containing monomers and fluorine-containing alkyl (meth) acrylates conventionally used for ophthalmic lenses. These hydrophobic monomers are used as an auxiliary component of the polysiloxane macromonomer.
- the molecular weight is higher than that of the polysiloxane macromonomer. Since it is small, there is an advantage that the compatibility of the polymerizable composition can be improved by adding such a silicon-containing monomer.
- fluorine-containing alkyl (meth) acrylates improve the solubility of oxygen in the lens (polymer), which is one factor in oxygen permeability in contact lenses, and reduce the tackiness of the lens surface.
- the hydrophobicity and oleophobicity effectively prevent adhesion of lipids and the like, and improve the stain resistance of the lens.
- ⁇ (meth) acrylate in this specification is used as a general term including “ ⁇ acrylate” and “ ⁇ methacrylate”.
- silicon-containing monomer examples include pentamethyldisiloxymethyl group, bis (trimethylsiloxy) (methyl) silylmethyl group, bis (trimethylsiloxy) (methyl) silylpropyl group, tris (trimethylsiloxy) silylmethyl group, and tris (trimethylsiloxy).
- silicon-containing monomers such as siloxanyl (meth) acrylate and siloxanylstyrene in which a silylpropyl group or the like is introduced into (meth) acrylate or styrene.
- bis (trimethylsiloxy) (methyl) silylpropyl (meth) acrylate and tris (trimethylsiloxy) silylpropyl (meth) acrylate are easy to purify, oxygen-permeable, readily available, and compatible. From the point of view, it is particularly preferably used.
- fluorine-containing alkyl (meth) acrylate examples include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, and (perfluorobutyl) ethyl.
- Method Method
- fluorine-containing alkyl (meth) acrylates in particular, the larger the fluorine portion is, the more convenient it is to ensure better oxygen permeability, and the lens can be made moderately soft. Therefore, it can be more suitably employed.
- fluorine-containing acrylic (meth) acrylates having a large fluorine moiety include (perfluorohexyl) ethyl (meth) acrylate, (perfluorooctyl) ethyl (meth) acrylate, (perfluorodecyl) ethyl (meth) acrylate, and the like.
- (perfluorooctyl) ethyl (meth) acrylate is the most desirable because it is commercially available and can be easily purified by distillation under reduced pressure.
- the crosslinking agent is added as necessary for the purpose of improving the mechanical strength, shape stability, etc. of the ophthalmic lens, and is appropriately used according to the polysiloxane macromonomer. is there.
- a crosslinking agent is rarely required, but when using a macromonomer with a small polymerizable group or
- the amount of the above-mentioned hydrophobic monomer is small, it is desirable to use an appropriate crosslinking agent because the shape stability, strength, durability and the like of the ophthalmic lens may be problematic.
- any known crosslinking agent having two or more polymerizable groups and conventionally used in ophthalmic lenses can be used.
- (meth) acrylates of polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol; adipic acid Divinyl, diallyl adipate, allyl adipate vinyl ester, divinyl sebacate, diallyl sebacate, allyl sebacate vinyl ester, oxalic acid, malonic acid, maleic acid, methylmalonic acid, succinic acid, dimethylmalonic acid, ethyl Malonic acid, methyl succinic acid, glutaric acid, dimethyl succinic acid, isopropyl malonic acid, methyl glutaric acid, methyl adipic acid,
- the crosslinking agent as described above is in a quantitative ratio of 0.0005 to 10 parts by weight with respect to 100 parts by weight of the total of the above-mentioned monomer components (polysiloxane macromonomer, hydrophilic monomer and hydrophobic monomer).
- a crosslinking agent is required, if the blending amount of the crosslinking agent is too small, a sufficient effect due to the crosslinking agent cannot be obtained, and the shape retention property such as a circle required for an ophthalmic lens after hydration or There is a possibility that moderate elasticity or the like cannot be obtained.
- the amount is too large, the polymer has too many cross-linking points, and the ophthalmic lens becomes brittle and may be easily damaged. It is.
- the reinforcing agent is added to adjust the mechanical strength of the ophthalmic lens.
- the polysiloxane macromonomer has a large number of polymerizable groups in one molecule, the polysiloxane macromonomer itself has a crosslinking effect, and the macromonomer provides excellent resilience.
- a reinforcing agent should be used. Is desirable.
- any of various known reinforcing agents conventionally used for ophthalmic lenses can be used.
- Specific examples include vinyl esters and allyl esters of organic carboxylic acids such as vinyl acetate and allyl propionate, (meth) acrylic acid esters and macromonomers thereof, styrene derivatives, and the like. At least one of such conventionally known reinforcing agents is appropriately selected and used.
- the blending ratio of the reinforcing agent as described above is 1 to 20 parts by weight with respect to 100 parts by weight of the total of the monomer components (polysiloxane macromonomer, hydrophilic monomer and hydrophobic monomer) described above. It is preferable to mix
- the blending ratio is less than 1 part by weight with respect to 100 parts by weight of the monomer component, there is a possibility that a sufficient reinforcing effect cannot be obtained.
- it exceeds 20 parts by weight the desired oxygen permeability may be difficult to obtain, or a sufficient water content may not be obtained.
- the hydrophilizing agent is a component for imparting hydrophilicity to the ophthalmic lens.
- an ophthalmic lens obtained by copolymerizing a polymerizable composition containing the monomer component described above is desired.
- the hydrophilicity or water wettability of the surface is insufficient, the compatibility between the polymerizable monomers is insufficient, the elasticity of the ophthalmic lens is too large, or the polymerization container material Or it is desirable to use suitably, when affinity with a molding container material is too large.
- hydrophilizing agent conventionally used in ophthalmic lenses can be used as such a hydrophilizing agent.
- mono (meth) acrylates of polyhydric alcohols such as ethylene glycol, propylene glycol and 1,6-hexanediol
- N- (meth) acryloylmorpholine such as ethylene glycol, propylene glycol and 1,6-hexanediol
- N- (meth) acryloylmorpholine such as ethylene glycol, propylene glycol and 1,6-hexanediol
- N- (meth) acryloylmorpholine such as N- (meth) acryloylpiperidine
- N-vinylpiperidone N Examples include -vinyl-N-methylacetamide; N-vinyl-N-ethylacetamide; N-vinyl-N-methylformamide; N-methyl- ⁇ -methylene-2-pyrrolidone and the like.
- the blending ratio of the hydrophilizing agent as described above is 1 to 30 parts by weight with respect to 100 parts by weight of the total of the monomer components (polysiloxane macromonomer, hydrophilic monomer and hydrophobic monomer) described above. It is blended in the polymerizable composition in a proper quantitative ratio.
- the blending ratio is less than 1 part by weight with respect to 100 parts by weight of the monomer component described above, sufficient hydrophilicity is obtained in the finally obtained ophthalmic lens.
- the blending ratio exceeds 30 parts by weight, the compatibility between the monomers may deteriorate or the desired oxygen permeability may not be obtained. is there.
- ophthalmic lens according to the present invention in addition to the above-described components, if necessary, various compounding agents generally used in the production of ophthalmic lenses conventionally. It is also possible to use additives.
- a polymerizable ultraviolet absorber for imparting ultraviolet absorption to the contact lens a polymerizable dye for coloring the contact lens, and an ultraviolet absorption in the contact lens
- examples thereof include polymerizable ultraviolet-absorbing dyes for imparting properties and coloring lenses.
- the polymerizable ultraviolet absorber for example, 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- (meth) acryloyloxy-5-t-butylbenzophenone, 2-hydroxy-4 A benzophenone-based polymerizable UV absorber such as (meth) acryloyloxy-2 ′, 4′-dichlorobenzophenone, 2-hydroxy-4- (2′-hydroxy-3 ′-(meth) acryloyloxypropoxy) benzophenone; 2 -(2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl) -2H-benzotriazole [HMEPBT], 2- (2'-hydroxy-5'-(meth) acryloyloxyethylphenyl) -5-chloro -2H-benzotriazole, 2- (2'-hydroxy-5'- (Meth) acryloyloxypropylphenyl) -2H-benzotriazole
- the polymerizable dye first, 1-phenylazo-4- (meth) acryloyloxynaphthalene, 1-phenylazo-2-hydroxy-3- (meth) acryloyloxynaphthalene, 1-naphthylazo-2-hydroxy-3- (Meth) acryloyloxynaphthalene, 1- ( ⁇ -anthrylazo) -2-hydroxy-3- (meth) acryloyloxynaphthalene, 1-((4 ′-(phenylazo) -phenyl) azo) -2-hydroxy-3- (Meth) acryloyloxynaphthalene, 1- (2 ′, 4′-xylylazo) -2- (meth) acryloyloxynaphthalene, 1- (o-tolylazo) -2- (meth) acryloyloxynaphthalene, 2- (m- (Meth) acryloylamide-anilino) -4,6-bis (1 ′-
- Examples of the polymerizable dye further include 1,5-bis ((meth) acryloylamino) -9,10-anthraquinone, 1- (4′-vinylbenzoylamide) -9,10-anthraquinone, 4-amino-1- (4′-vinylbenzoylamide) -9,10-anthraquinone, 5-amino-1- (4′-vinylbenzoylamide) -9,10-anthraquinone, 8-amino-1- (4′-vinylbenzoylamide) -9,10-anthraquinone, 4-nitro-1- (4'-vinylbenzoylamide) -9,10-anthraquinone, 4-hydroxy-1- (4'-vinylbenzoylamide) -9,10-anthraquinone, -(3'-vinylbenzoylamide) -9,10-anthraquinone, 1- (2'-vinylbenzo
- examples of polymerizable ultraviolet absorbing dyes include 2,4-dihydroxy-3 (p-styrenoazo) benzophenone, 2,4-dihydroxy-5- (p-styrenoazo) benzophenone, 2,4-dihydroxy-3- (p -(Meth) acryloyloxymethylphenylazo) benzophenone, 2,4-dihydroxy-5- (p- (meth) acryloyloxymethylphenylazo) benzophenone, 2,4-dihydroxy-3- (p- (meth) acryloyloxy Ethylphenylazo) benzophenone, 2,4-dihydroxy-5- (p- (meth) acryloyloxyethylphenylazo) benzophenone, 2,4-dihydroxy-3- (p- (meth) acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy-5- (p (Meth) acryloyloxypropylphenylazo)
- the polymerizable ultraviolet absorbent, the polymerizable dye and the polymerizable ultraviolet absorbent dye as described above are based on 100 parts by weight of the total of the monomer components (polysiloxane macromonomer, hydrophilic monomer and hydrophobic monomer) described above. It is preferably blended into the polymerizable composition at a quantitative ratio of 3 parts by mass or less, more preferably blended into the polymerizable composition at a quantitative ratio of 0.01 to 2 parts by mass. Is done. When the blending ratio of these polymerizable ultraviolet absorbers exceeds 3 parts by mass, the mechanical strength of the obtained contact lens tends to decrease, and the above-mentioned polymerization is considered in consideration of the toxicity of the ultraviolet absorber and the dye. This is because it is preferable that the amount of the active ultraviolet absorber or the like is small.
- the water content of the contact lens finally obtained is 10 to 60%. It is preferable that the blending ratio of each component in the polymerizable composition is determined. If the moisture content of the contact lens is less than 10%, even if a tear film exists between the lens and the cornea, the lens is pressed against the cornea by blinking, and the distance between the lens and the cornea is reduced. Eventually, there is a risk that the lens sticks to the cornea like a suction cup. On the other hand, if the water content exceeds 60%, the oxygen permeability may be lowered. More preferably, the blending ratio of each component in the polymerizable composition is determined so that the water content is particularly 12 to 55% within the range of 10 to 60%.
- a polymerizable composition containing each of these components is appropriately selected from the above-described components according to the target ophthalmic lens.
- the target ophthalmic lens is obtained by copolymerizing the prepared polymerizable composition in accordance with various conventionally known polymerization methods.
- a hydrous contact lens can be manufactured by the following method.
- a thermal polymerization initiator is added to the polymerizable composition, and then gradually or stepwise in a temperature range of room temperature to about 150 ° C. After adding a polymerization method by heating (polymerization method) or photopolymerization initiator (and photosensitizer) to the polymerizable composition, it is irradiated with an appropriate light beam (for example, ultraviolet ray or electron beam).
- an appropriate light beam for example, ultraviolet ray or electron beam.
- Examples of the polymerization method (photopolymerization method) and a method of performing polymerization by combining the thermal polymerization method and the photopolymerization method can be given.
- the polymerization method include a bulk polymerization method and a solution polymerization method, but other known methods may be used.
- the method (processing method) for molding the contact lens is not particularly limited, and the polymerizable composition is accommodated in a suitable polymerization mold or polymerization container, and the polymerization mold or polymerization container is accommodated.
- a contact lens material ophthalmic lens material
- a polymerization method that gives a desired shape of a contact lens or a cutting method for forming the shape into a shape of a predetermined shape is prepared.
- a predetermined polymerizable monomer composition is accommodated in a molding cavity of the polymerization die, and is described above in the die.
- the molding method is preferably employed because it can effectively reduce the production cost.
- the thermal polymerization initiator used is 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvalero). Nitrile), benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, lauroyl peroxide, t-butyl peroxyhexanoate, 3,5,5-trimethylhexanoyl peroxide, etc. I can do it.
- These thermal polymerization initiators can be used alone or in admixture of two or more.
- the amount of the thermal polymerization initiator used is preferably 0.001 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of all the monomer components of the polymerizable composition.
- the heating temperature of the polymerizable composition is preferably 50 to 150 ° C., more preferably 60 to 140 ° C.
- the heating time of the polymerizable composition is preferably 10 to 120 minutes, more preferably 20 to 60 minutes.
- the photopolymerization initiator used is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), bis (2,4,6-trimethyl).
- Phosphine oxide photopolymerization initiators such as benzoyl) -phenylphosphine oxide; benzoins such as methyl orthobenzoyl benzoate, methyl benzoyl formate, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin-n-butyl ether Photopolymerization initiator: 2-hydroxy-2-methyl-1-phenylpropan-1-one (HMPPO), p-isopropyl- ⁇ -hydroxyisobutylphenone, pt-butyltrichloroa Phenone-based photopolymerization initiators such as tophenone, 2,2-dimethoxy-2-phenylacetophenone, ⁇ , ⁇ -dichloro-4-phenoxyacetophenone, N, N-tetraethyl-4,4-diaminobenzophenone; 1-hydroxycyclohexylphen
- photopolymerization initiators can be used alone or in admixture of two or more. Moreover, you may use a photosensitizer with a photoinitiator.
- the ratio of these photopolymerization initiator and photosensitizer used is preferably 0.001 to 2 parts by mass, more preferably 0.01 to 1 part per 100 parts by mass of all the monomer components of the polymerizable composition. Part by mass.
- the type of a photopolymerization initiator when polymerizing a polymerizable composition by a photopolymerization method, it is necessary to select the type of a photopolymerization initiator to be used according to the wavelength range of light to be irradiated.
- the light illuminance is preferably in the range of 0.1 to 100 mW / cm 2 .
- light with different illuminances may be irradiated stepwise, and the light irradiation time is preferably 1 minute or longer.
- the polymerizable composition may be heated simultaneously with the light irradiation, whereby the polymerization reaction is promoted, and it is possible to easily form a copolymer.
- the template or polymerization vessel used for photopolymerization is not particularly limited as long as it is a material that can transmit light necessary for polymerization (curing) of the polymerizable composition, but polypropylene, polystyrene, nylon, polyester What consists of general purpose resin, such as these, is preferable.
- the copolymer obtained as described above is usually subjected to a treatment for removing residues in the copolymer.
- a treatment for removing residues in the copolymer is because, for example, in the bulk polymerization method, the viscosity of the system increases with the progress of the polymerization reaction, the monomer component cannot diffuse in the high viscosity system, and the monomer that cannot participate in the polymerization reaction is co-polymerized in an unpolymerized state.
- a solvent that does not participate in the polymerization reaction often remains in the copolymer in the solution polymerization method, and such a residue is a contact lens that is a medical device. This is because it is necessary to reduce the weight as much as possible.
- the copolymer is immersed in water, an organic solvent, or a mixed solvent thereof, and the residue is eluted from the polymer by preferably repeating this.
- a solvent for such treatment an aqueous solution in which an inorganic compound is dissolved, such as physiological saline, or a mixed solution of such an aqueous solution and an organic solvent can be used.
- the copolymer that has been subjected to the removal process of the residue is subjected to a hydration process by being immersed in water, whereby a desired hydrous contact lens is manufactured.
- the contact lens is appropriately sterilized so as to ensure sufficient safety with respect to a living body.
- various treatments for improving the surface characteristics are performed on the contact lens in a dry state or a water-containing state after molding by the molding method or the cutting method as described above.
- Examples of such treatment include low temperature plasma treatment, atmospheric pressure plasma treatment, and corona discharge.
- the low temperature plasma treatment is performed in a dilute gas atmosphere such as an alkane having 1 to 6 carbon atoms and a fluorine-substituted alkane, nitrogen, oxygen, carbon dioxide, argon, hydrogen, air, water, silane, or a mixture thereof.
- a dilute gas atmosphere such as an alkane having 1 to 6 carbon atoms and a fluorine-substituted alkane, nitrogen, oxygen, carbon dioxide, argon, hydrogen, air, water, silane, or a mixture thereof.
- the low temperature plasma treatment in a dilute gas atmosphere of a mixture of organic silane, methane, nitrogen and the like.
- the low temperature plasma treatment can be performed under reduced pressure and atmospheric pressure.
- the output, processing time, and gas concentration are appropriately set using high frequency RF (for example, 13.65 MHz), low frequency AF (for example, 15.0 to 40.0 KHz), and microwave (for example, 2.45 GHz). It is possible to control the surface modification effect by adjusting.
- hydrophilic agents such as 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid, methoxytriethylene glycol (meth) acrylate, dimethylacrylamide, etc. It is also effective to make the surface of the contact lens hydrophilic so as to impart more excellent water wettability.
- TRIS 3-tris (trimethylsiloxy) silylpropyl methacrylate
- DMAA dimethylacrylamide
- N-MMP 1-methyl-3-methylene-2-pyrrolidinone
- TPO diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide
- HMEPBT 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethyl phenyl) -2H-benzotriazole
- HMPPO 2-hydroxy-2-methyl-1-phenylpropan-1-one
- EDMA Ethylene glycol dimethacrylate
- MTA 2-methoxyethyl acrylate
- AMA allyl methacrylate
- the reaction solution was dissolved in 800 mL of acetonitrile and transferred to a separatory funnel. Next, 800 mL of hexane was added to the separatory funnel to separate the layers. Of the three separated layers, the bottom layer was discarded. Furthermore, 200 mL of acetonitrile was added and the liquids were separated again. Of the three separated layers, the bottom layer was discarded. Furthermore, 200 mL of acetonitrile was added and the liquids were separated again. Of the three separated layers, the bottom layer was discarded.
- the HLB value is 2.72.
- the reaction solution was dissolved in 600 mL of acetonitrile and transferred to a separatory funnel. Next, 600 mL of hexane was added to the separatory funnel to separate the layers. Of the three separated layers, the bottom layer was discarded. Furthermore, 300 mL of acetonitrile was added and the liquids were separated again. Of the three separated layers, the bottom layer was discarded. Furthermore, 150 mL of acetonitrile was added and the liquids were separated again. Of the three separated layers, the bottom layer was discarded.
- the reaction solution was dissolved in 800 mL of acetonitrile and transferred to a separatory funnel. Next, 800 mL of hexane was added to the separatory funnel to separate the layers. Of the three separated layers, the bottom layer was discarded. Furthermore, 400 mL of acetonitrile was added and the liquids were separated again. Of the three separated layers, the bottom layer was discarded. Furthermore, 200 mL of acetonitrile was added and the liquids were separated again. Of the three separated layers, the bottom layer was discarded. The remaining layer was recovered, 0.0122 g of 4-methoxy-1-naphthol (MNT) was added, and the solvent was distilled off under reduced pressure to obtain 67.67 g of a highly viscous light yellow liquid.
- MNT 4-methoxy-1-naphthol
- the HLB value is 2.30.
- the reaction solution was dissolved in 1000 mL of acetonitrile and transferred to a separatory funnel. Next, 1000 mL of hexane was added to the separatory funnel to separate the layers. Of the two separated layers, the lower layer (acetonitrile layer) was discarded. Furthermore, 400 mL of acetonitrile was added and the liquids were separated again. Of the two separated layers, the lower layer was discarded. Furthermore, 400 mL of acetonitrile was added and the liquids were separated again. Of the two separated layers, the lower layer was discarded.
- the HLB value is 1.74.
- the reaction solution was dissolved in 800 mL of acetonitrile and transferred to a separatory funnel. Next, 800 mL of hexane was added to the separatory funnel to separate the layers. Of the two separated layers, the lower layer (acetonitrile layer) was discarded. Furthermore, 400 mL of acetonitrile was added and the liquids were separated again. Of the two separated layers, the lower layer was discarded. Furthermore, 400 mL of acetonitrile was added and the liquids were separated again. Of the two separated layers, the lower layer was discarded.
- the reaction solution was dissolved in 800 mL of acetonitrile and transferred to a separatory funnel. Next, 800 mL of hexane was added to the separatory funnel to separate the layers. Of the two separated layers, the lower layer (acetonitrile layer) was discarded. Furthermore, 400 mL of acetonitrile was added and the liquids were separated again. Of the two separated layers, the lower layer was discarded. Furthermore, 400 mL of acetonitrile was added and the liquids were separated again. Of the two separated layers, the lower layer was discarded.
- the HLB value is 1.97.
- the reaction solution was dissolved in 800 mL of acetonitrile and transferred to a separatory funnel. Next, 800 mL of hexane was added to the separatory funnel to separate the layers. Of the two separated layers, the lower layer (acetonitrile layer) was discarded. Furthermore, 400 mL of acetonitrile was added and the liquids were separated again. Of the two separated layers, the lower layer was discarded. Furthermore, 400 mL of acetonitrile was added and the liquids were separated again. Of the two separated layers, the lower layer was discarded.
- the HLB value is 1.54.
- the reaction solution was dissolved in 800 mL of acetonitrile and transferred to a separatory funnel. Next, 800 mL of hexane was added to the separatory funnel to separate the layers. Of the two separated layers, the lower layer (acetonitrile layer) was discarded. Furthermore, 400 mL of acetonitrile was added and the liquids were separated again. Of the two separated layers, the lower layer was discarded. Furthermore, 400 mL of acetonitrile was added and the liquids were separated again. Of the two separated layers, the lower layer was discarded.
- the reaction solution was dissolved in 800 mL of acetonitrile and transferred to a separatory funnel. Next, 800 mL of hexane was added to the separatory funnel to separate the layers. Of the two separated layers, the lower layer (acetonitrile layer) was discarded. Furthermore, 400 mL of acetonitrile was added and the liquids were separated again. Of the two separated layers, the lower layer was discarded. Furthermore, 400 mL of acetonitrile was added and the liquids were separated again. Of the two separated layers, the lower layer was discarded.
- the HLB value is 4.81.
- the acryloylethyl isocyanate remaining in the reaction solution is deactivated with methanol, and the obtained silicone solution is dissolved in the same amount of hexane, and then the hexane solution is the same as the hexane used previously. Wash 3 times with an amount of acetonitrile. Then, 0.03 g of dibutylhydroxytoluene (BHT) is added to the upper layer (hexane layer) of the washed reaction solution, and the hexane is distilled off under reduced pressure, whereby a colorless and transparent liquid polysiloxane macromonomer ( 203 g of macromonomer J) were obtained.
- the reaction solution was dissolved in 800 mL of acetonitrile and transferred to a separatory funnel. Next, 800 mL of hexane was added to the separatory funnel to separate the layers. Of the two separated layers, the lower layer (acetonitrile layer) was discarded. Furthermore, 400 mL of acetonitrile was added and the liquids were separated again. Of the two separated layers, the lower layer was discarded. Furthermore, 400 mL of acetonitrile was added and the liquids were separated again. Of the two separated layers, the lower layer was discarded.
- the reaction solution was dissolved in 800 mL of acetonitrile and transferred to a separatory funnel. Next, 800 mL of hexane was added to the separatory funnel to separate the layers. Of the two separated layers, the lower layer was discarded. Furthermore, 400 mL of acetonitrile was added and the liquids were separated again. Of the two separated layers, the lower layer was discarded. Furthermore, 400 mL of acetonitrile was added and the liquids were separated again. Of the two separated layers, the lower layer was discarded.
- comparative macromonomer b- A polysiloxane macromonomer (comparative macromonomer c) represented by the following structural formula (X) was synthesized according to the same production method as in Example 1 disclosed in JP-A-2001-72739.
- the comparative macromonomer c has an HLB value calculated from the above formula of 0.46.
- an ultraviolet irradiation device (ultraviolet effect device manufactured by Eye Graphics Co., Ltd .: UBX0302-03) equipped with an ultraviolet lamp having a dominant wavelength at 365 nm is used.
- the polymerization was carried out by irradiating with UV light at an irradiation intensity of about 10 mW / cm 2 for about 20 minutes.
- Example 1 to Example 13 Comparative Example 1 to Comparative Example 7
- Example 6 Each polymer was transparent enough to be used as an ophthalmic lens.
- the polymers according to Comparative Examples 1 to 5 and Comparative Example 7 were white turbid or slightly turbid, and were found to be inappropriate as ophthalmic lenses.
- Fig. A The sample after hydration and sterilization is shown in Fig. A. of JIS-K-7162-1994, “Plastics-Test method for tensile properties, Part 2: Molding, extrusion and cast plastic test conditions”. It was processed into the shape described in 2 (dumbbell shape). In addition, the thickness of the obtained dumbbell-shaped sample was about 0.34 mm.
- the Young's modulus and relaxation rate of the polymer are within a predetermined range.
- a wide range of blending compositions can be assembled.
- the polymer using a polysiloxane macromonomer different from such a predetermined polysiloxane macromonomer even if the same blending composition is adopted, the polymer becomes cloudy. Even when a blending composition that is transparent to the extent that it can be used as an ophthalmic lens is employed, it may be difficult to keep the Young's modulus and relaxation rate of the polymer within an appropriate range for an ophthalmic lens. It is recognized.
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Abstract
Description
α=E/r ・・・ (A)
式(A)中、Eは、眼用レンズを構成する重合体のヤング率(MP
a)であり、rは、同重合体の緩和率(%)である。
β=n/(a+b) ・・・ (B)
式(B)中、nは、ポリシロキサン系マクロモノマー分子中のケイ
素原子の総数である。
[HLB値]=WE /5 ・・・(C)
式(C)中、WE は、ポリシロキサン系マクロモノマーの一分子内に
おける、オキシエチレン基の重量分率(重量%)である。
式(D):
[緩和率:r(%)]=[(L1 -L2 )/L1 ]×100
かかる式(D)において、L1 及びL2 は、眼用レンズを構成する重合体についての引張試験によって求められるものである。具体的には、眼用レンズを構成する重合体を用いて、JIS-K-7162-1994 『プラスチック-引張特性の試験方法 第2部:型成形、押出成形及び注型プラスチックの試験条件』の図A.2に記載の形状(ダンベル状)の試験片を準備し、引張速度:20mm/minの条件にて引張試験を実施する。測定される応力が0.1Nとなった時点で直ちに引張を停止し、その停止直後の応力を測定してL1 とすると共に、引張停止から30秒経過後の応力を測定し、これをL2 とする。また、引張試験において、応力が0.01~0.10Nの範囲におけるヤング率を、本発明でのヤング率(E)とする。尚、眼用レンズを構成する重合体が、例えば含水性ソフトコンタクトレンズを構成するハイドロゲルの如き、含水性材料である場合には、水又は生理食塩水に浸漬せしめて水和させ、平衡状態となるまで膨潤させた重合体を、上記の形状に加工して試験片とし、水和の際に用いた水又は生理食塩水中において上記した条件の下に引張試験を実施し、その測定結果より得られるヤング率及び緩和率を、本発明のヤング率及び緩和率とする。
α=E/r ・・・ (A)
式(A)中、Eは、眼用レンズを構成する重合体のヤング率(MP
a)であり、rは、同重合体の緩和率(%)である。
β=n/(a+b) ・・・ (B)
式(B)中、nは、ポリシロキサン系マクロモノマー分子中のケイ
素原子の総数である。
[HLB値]=WE /5 ・・・(C)
式(C)中、WE は、ポリシロキサン系マクロモノマーの一分子内に
おける、オキシエチレン基の重量分率(重量%)である。
Y21-R21- ・・・(II)
-R22-Y22 ・・・(III )
それら一般式(II)及び一般式(III )中、Y21及びY22は、何れも重合性基であり、それぞれ独立に、アクリロイルオキシ基、メタクリロイルオキシ基、ビニル基又はアリル基を示している。一方、R21及びR22は、それぞれ独立に、直接結合又は炭素数2~6の直鎖状又は分岐鎖を有するアルキレン基を示し、このアルキレン基としては、好ましくはエチレン基、プロピレン基又はブチレン基である。
-E21-X21- ・・・(IV)
かかる一般式(IV)において、E21は-NHCO-基(この場合、E21はX21とウレタン結合を形成している)、又は、飽和若しくは不飽和脂肪族系、脂環式系及び芳香族系の群から選ばれたジイソシアネート由来の2価の基(この場合、E21はZ1 及びX21の間でウレタン結合を形成している)を示し、X21は酸素原子を示している。
-R41-X41-E41-X42-R42- ・・・(VI)
かかる一般式(VI)において、R41及びR42は、それぞれ独立して、炭素数2~6の直鎖状若しくは分岐鎖を有するアルキレン基を示し、X41及びX42は、それぞれ独立して、酸素原子又はアルキレングリコール基を示し、E41は、飽和若しくは不飽和脂肪族系、脂環式系及び芳香族系の群から選ばれたジイソシアネート由来の2価の基(この場合、E41はX41及びX42の間でウレタン結合を形成している)を示すものである。
-X22-E22- ・・・(VII )
かかる一般式(VII )において、X22は酸素原子を示し、E22は-NHCO-基(この場合、E22はX22との間でウレタン結合を形成している)、又は、飽和若しくは不飽和脂肪族系、脂環式系及び芳香族系の群から選ばれたジイソシアネート由来の2価の基(この場合、E22はZ5 及びX22の間でウレタン結合を形成している)を示している。
、bは2以上の整数、nは1~1500の整数である。また、R52及びR5
3は水素原子又はメチル基であり、R52が水素原子である場合には、R53は
メチル基であり、R52がメチル基である場合には、R53は水素原子である
。)
~1500の整数である。また、R61及びR62は水素原子又はメチル基で
あり、R61が水素原子である場合には、R62はメチル基であり、R61がメチ
ル基である場合には、R62は水素原子である。)
含水率(重量%)=[(W1 -W2 )/W1 ]×100
・TRIS:3-トリス(トリメチルシロキシ)シリルプロピルメタクリレート
・DMAA:ジメチルアクリルアミド
・N-MMP:1-メチル-3-メチレン-2-ピロリジノン
・TPO:ジフェニル(2,4,6-トリメチルベンゾイル)ホスフィンオキサイド
・HMEPBT:2-(2’-ヒドロキシ-5’-(メタ)アクリロイルオキシエチルフ ェニル)-2H-ベンゾトリアゾール
・HMPPO:2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン
・EDMA:エチレングリコールジメタクリレート
・MTA:2-メトキシエチルアクリレート
・AMA:アリルメタクリレート
500mLナスフラスコに、信越化学株式会社製の両末端ポリプロピレンオキサイド変性シリコーン(商品名:X-22-4952 、オキシプロピレン基の繰り返し数:10、ジメチルシロキサンの繰り返し数:20)の107.48g(官能基当量が1120g/molであることから、95.96mmol)と、イソホロンジイソシアネートの26.64g(119.85mmol)とを投入し、スターラーを用いて室温下で撹拌し、X-22-4952 をイソホロンジイソシアネートに溶解させた。次いで、同フラスコに、テトラキス(2,4-ペンタンジオナト)ジルコニウム(IV)の0.1427gをアセトニトリルの1.8248gに溶解させてなる溶液を加え、室温下で30分間、撹拌した。さらに、X-22-4952 の26.78g(官能基当量が1120g/molであることから、23.91mmol)を加え、フラスコにジムロート冷却管を装着し、オイルバス中において、70℃で2時間、撹拌した。
500mLナスフラスコに、両末端ポリプロピレンオキサイド変性シリコーン(オキシプロピレン基の繰り返し数:5、ジメチルシロキサンの繰り返し数:20)の88.30g(官能基当量が974g/molであることから、90.66mmol)と、イソホロンジイソシアネートの50.37g(226.61mmol)とを投入し、スターラーを用いて室温下で撹拌し、シリコーンをイソホロンジイソシアネートに溶解させた。次いで、同フラスコに、テトラキス(2,4-ペンタンジオナト)ジルコニウム(IV)の0.1750gをアセトニトリルの2.1474gに溶解させてなる溶液を加え、フラスコにジムロート冷却管を装着し、オイルバス中において、70℃で1.5時間、撹拌した。
500mLナスフラスコに、両末端ポリプロピレンオキサイド変性シリコーン(オキシプロピレン基の繰り返し数:16、ジメチルシロキサンの繰り返し数:20)の163.39g(官能基当量が1355g/molであることから、120.58mmol)と、イソホロンジイソシアネートの67.01g(301.47mmol)とを投入し、スターラーを用いて室温下で撹拌し、シリコーンをイソホロンジイソシアネートに溶解させた。次いで、同フラスコに、テトラキス(2,4-ペンタンジオナト)ジルコニウム(IV)の0.3147gをアセトニトリルの3.1922gに溶解させてなる溶液を加え、フラスコにジムロート冷却管を装着し、オイルバス中において、70℃で1.5時間、撹拌した。
500mLナスフラスコに、両末端ポリプロピレンオキサイド変性シリコーン(オキシプロピレン基の繰り返し数:16、ジメチルシロキサンの繰り返し数:40)の152.56g(官能基当量が1905g/molであることから、80.08mmol)と、イソホロンジイソシアネートの44.53g(200.33mmol)とを投入し、スターラーを用いて室温下で撹拌し、シリコーンをイソホロンジイソシアネートに溶解させた。次いで、同フラスコに、テトラキス(2,4-ペンタンジオナト)ジルコニウム(IV)の0.2989gをアセトニトリルの3.1234gに溶解させてなる溶液を加え、フラスコにジムロート冷却管を装着し、オイルバス中において、70℃で1.5時間、撹拌した。
500mLナスフラスコに、両末端ポリプロピレンオキサイド変性シリコーン(オキシプロピレン基の繰り返し数:5、ジメチルシロキサンの繰り返し数:40)の112.30g(官能基当量が1522g/molであることから、73.78mmol)と、イソホロンジイソシアネートの41.01g(184.50mmol)とを投入し、スターラーを用いて室温下で撹拌し、シリコーンをイソホロンジイソシアネートに溶解させた。次いで、同フラスコに、テトラキス(2,4-ペンタンジオナト)ジルコニウム(IV)の0.2009gをアセトニトリルの1.9901gに溶解させてなる溶液を加え、フラスコにジムロート冷却管を装着し、オイルバス中において、70℃で1.5時間、撹拌した。
500mLナスフラスコに、両末端ポリプロピレンオキサイド変性シリコーン(オキシプロピレン基の繰り返し数:10、ジメチルシロキサンの繰り返し数:40)の115.53g(官能基当量が1711g/molであることから、67.52mmol)と、イソホロンジイソシアネートの37.52g(168.80mmol)とを投入し、スターラーを用いて室温下で撹拌し、シリコーンをイソホロンジイソシアネートに溶解させた。次いで、同フラスコに、テトラキス(2,4-ペンタンジオナト)ジルコニウム(IV)の0.2035gをアセトニトリルの2.5868gに溶解させてなる溶液を加え、フラスコにジムロート冷却管を装着し、オイルバス中において、70℃で1.5時間、撹拌した。
500mLナスフラスコに、両末端ポリプロピレンオキサイド変性シリコーン(オキシプロピレン基の繰り返し数:10、ジメチルシロキサンの繰り返し数:60)の121.95g(官能基当量が2257g/molであることから、54.03mmol)と、イソホロンジイソシアネートの30.10g(135.41mmol)とを投入し、スターラーを用いて室温下で撹拌し、シリコーンをイソホロンジイソシアネートに溶解させた。次いで、同フラスコに、テトラキス(2,4-ペンタンジオナト)ジルコニウム(IV)の0.2130gをアセトニトリルの2.6731gに溶解させてなる溶液を加え、フラスコにジムロート冷却管を装着し、オイルバス中において、70℃で1.5時間、撹拌した。
500mLナスフラスコに、両末端ポリプロピレンオキサイド変性シリコーン(オキシプロピレン基の繰り返し数:10、ジメチルシロキサンの繰り返し数:40)の115.11g(官能基当量が1711g/molであることから、67.27mmol)と、イソホロンジイソシアネートの37.38g(168.17mmol)とを投入し、スターラーを用いて室温下で撹拌し、シリコーンをイソホロンジイソシアネートに溶解させた。次いで、同フラスコに、テトラキス(2,4-ペンタンジオナト)ジルコニウム(IV)の0.2001gをアセトニトリルの2.5765gに溶解させてなる溶液を加え、フラスコにジムロート冷却管を装着し、オイルバス中において、70℃で1.5時間、撹拌した。
500mLナスフラスコに、両末端ポリプロピレンオキサイド変性シリコーン(オキシプロピレン基の繰り返し数:5、ジメチルシロキサンの繰り返し数:20)の98.20g(官能基当量が974g/molであることから、100.82mmol)と、イソホロンジイソシアネートの56.03g(252.07mmol)とを投入し、スターラーを用いて室温下で撹拌し、シリコーンをイソホロンジイソシアネートに溶解させた。次いで、同フラスコに、テトラキス(2,4-ペンタンジオナト)ジルコニウム(IV)の0.1730gをアセトニトリルの2.2347gに溶解させてなる溶液を加え、フラスコにジムロート冷却管を装着し、オイルバス中において、70℃で1.5時間、撹拌した。
両末端SiH基含有ジメチルポリシロキサン(Si原子数:40)の294.6g(0.1mol)と、末端アリルデカプロピレンオキサイド-ヘキサエチレンオキサイドの216.5g(0.24mol)と、イソプロピルアルコールの200gとを、1Lフラスコに投入し、塩化白金酸中和物ビニルシロキサン錯体3%エタノール溶液の0.03gを触媒として用いて、イソプロピルアルコール還流下、4時間、反応を実施した。なお、かかる反応の後、ジメチルポリシロキサンのSiH基は完全に消失していることを確認した。
500mLナスフラスコに、両末端ポリプロピレンオキサイド変性シリコーン(オキシプロピレン基の繰り返し数:10、ジメチルシロキサンの繰り返し数:40)の122.97g(官能基当量が1711g/molであることから、71.87mmol)と、イソホロンジイソシアネートの39.94g(179.68mmol)とを投入し、スターラーを用いて室温下で撹拌し、シリコーンをイソホロンジイソシアネートに溶解させた。次いで、同フラスコに、テトラキス(2,4-ペンタンジオナト)ジルコニウム(IV)の0.2113gをアセトニトリルの3.1027gに溶解させてなる溶液を加え、フラスコにジムロート冷却管を装着し、オイルバス中において、70℃で1.5時間、撹拌した。
500mLナスフラスコに、信越化学株式会社製の両末端ポリプロピレンオキサイド変性シリコーン(商品名:X-22-4952 、オキシプロピレン基の繰り返し数:10、ジメチルシロキサンの繰り返し数:20)の110.79g(官能基当量が1120g/molであることから、98.91mmol)と、イソホロンジイソシアネートの33.08g(148.8mmol)とを投入し、スターラーを用いて室温下で撹拌し、X-22-4952 をイソホロンジイソシアネートに溶解させた。次いで、同フラスコに、テトラキス(2,4-ペンタンジオナト)ジルコニウム(IV)の0.1799gをアセトニトリルの1.74gに溶解させてなる溶液を加え、室温下で30分間、撹拌した。さらに、X-22-4952 の33.55g(官能基当量が1120g/molであることから、29.96mmol)を加え、室温下で25分間、撹拌した後、フラスコにジムロート冷却管を装着し、オイルバス中において、70℃で2時間、撹拌した。その後、フラスコ内より少量の反応液を採取し、1HNMR を測定したところ、イソホロンジイソシアネートの1級NCO基に隣接するCH2 のシグナル(3.1ppm付近)がほぼ消失していることを確認した。
特開2001-72739号公報に示される実施例1と同様の製法に従って、下記構造式(X)にて表わされるポリシロキサン系マクロモノマー(比較マクロモノマーc)を合成した。この比較マクロモノマーcの、上記式より算出されるHLB値は0.46である。
両末端SiH基含有ジメチルポリシロキサン(Si原子数:20)の146.6g(0.1mol)と、末端アリルデカプロピレンオキサイド(オキシプロピレン基の繰り返し数:10)の153.1g(0.24mol)と、イソプロピルアルコールの150gとを、1Lフラスコに投入し、塩化白金酸中和物ビニルシロキサン錯体3%エタノール溶液の0.03gを触媒として用いて、イソプロピルアルコール還流下、4時間、反応を実施した。なお、かかる反応の後、ジメチルポリシロキサンのSiH基は完全に消失していることを確認した。
原子である場合には、R72はメチル基であり、R71がメチル基である場合
には、R72は水素原子である。)
1,1,3,3-テトラメチル-1,3-メタクリロキサプロピル-ジシロキサンの193g(0.5mol)と、オクタメチルシクロテトラシロキサンの1480g(5mol)と、トリフロロメタンスルホン酸の0.28gを、3Lフラスコに投入し、室温下で5時間、反応させた。その後、フラスコに56gの重曹を加え、室温下で2時間、中和した後、反応液を濾過、精製した。
Claims (9)
- ヤング率が0.3~1.0MPaであり、且つ緩和率が10~20%である重合体よりなる眼用レンズ。
- 下記式(A)より算出されるαが0.02~0.10である請求項1に記載の眼用レンズ。
α=E/r ・・・ (A)
式(A)中、Eは、眼用レンズを構成する重合体のヤング率
(MPa)であり、rは、同重合体の緩和率(%)である。 - 前記重合体が、少なくとも一つ以上の重合性基と、シロキサン単位を繰り返し単位とするポリシロキサン鎖とを有するポリシロキサン系マクロモノマーを含む重合性組成物の重合体である請求項1又は請求項2に記載の眼用レンズ。
- 前記ポリシロキサン系マクロモノマーが、1)オキシエチレン基を繰り返し単位とし、繰り返し数がa(但し、aは2以上の整数である)であるポリオキシエチレン鎖と、2)オキシエチレン基とは異なるオキシアルキレン基を繰り返し単位とし、繰り返し数がb(但し、bは2以上の整数である)であるポリオキシアルキレン鎖とを有しており、下記式(B)より算出されるβが0.5~5.0である請求項3に記載の眼用レンズ。
β=n/(a+b) ・・・ (B)
式(B)中、nは、ポリシロキサン系マクロモノマー分子中
のケイ素原子の総数である。 - 前記ポリシロキサン系マクロモノマーの、下記式(C)より算出されるHLB値が0.7~6.0である請求項4に記載の眼用レンズ。
[HLB値]=WE /5 ・・・(C)
式(C)中、WE は、ポリシロキサン系マクロモノマーの一
分子内における、オキシエチレン基の重量分率(重量%)であ
る。 - 前記オキシエチレン基の繰り返し数:aが4~15である請求項4又は請求項5に記載の眼用レンズ。
- 前記ポリオキシアルキレン鎖が、オキシプロピレン基を構成単位とするポリオキシプロピレン鎖である請求項4乃至請求項6の何れか1項に記載の眼用レンズ。
- 前記オキシプロピレン基の繰り返し数が5~16である請求項7に記載の眼用レンズ。
- 前記重合性基が、一つ以上のウレタン結合を介して、モノマー分子において主鎖を構成する前記ポリシロキサン鎖に結合している請求項3乃至請求項8の何れか1項に記載の眼用レンズ。
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EP13899516.2A EP3086162B1 (en) | 2013-12-16 | 2013-12-16 | Ocular lens |
US15/177,781 US9657131B2 (en) | 2013-12-16 | 2016-06-09 | Ophthalmic lens |
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EP3290462A1 (en) * | 2016-08-30 | 2018-03-07 | Shin-Etsu Chemical Co., Ltd. | Both-terminal modified polysiloxane macromonomer and a method for preparing the same |
WO2018056472A1 (en) | 2016-09-23 | 2018-03-29 | Menicon Co., Ltd. | Cosmetic composition for nails, method of using same, and cosmetic resin for nails |
JP7179729B2 (ja) | 2016-12-16 | 2022-11-29 | クーパーヴィジョン インターナショナル リミテッド | 組込み構成要素を有するコンタクトレンズ |
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EP3822296A4 (en) * | 2019-02-26 | 2022-07-06 | Menicon Co., Ltd. | POLYMER MATERIAL |
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US20160289368A1 (en) | 2016-10-06 |
EP3086162A1 (en) | 2016-10-26 |
JPWO2015092859A1 (ja) | 2017-03-16 |
JP6023899B2 (ja) | 2016-11-09 |
EP3086162B1 (en) | 2019-04-17 |
EP3086162A4 (en) | 2017-08-09 |
US9657131B2 (en) | 2017-05-23 |
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