WO2023033012A1 - ホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー - Google Patents
ホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー Download PDFInfo
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- WO2023033012A1 WO2023033012A1 PCT/JP2022/032689 JP2022032689W WO2023033012A1 WO 2023033012 A1 WO2023033012 A1 WO 2023033012A1 JP 2022032689 W JP2022032689 W JP 2022032689W WO 2023033012 A1 WO2023033012 A1 WO 2023033012A1
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- divalent group
- group
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- alkylene divalent
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- 239000000178 monomer Substances 0.000 title claims abstract description 172
- -1 Polydimethylsiloxane Polymers 0.000 title claims abstract description 154
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 76
- 239000004205 dimethyl polysiloxane Substances 0.000 title claims abstract description 72
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 title claims abstract description 72
- 239000000203 mixture Substances 0.000 claims abstract description 133
- 229920000642 polymer Polymers 0.000 claims abstract description 77
- 229920001477 hydrophilic polymer Polymers 0.000 claims abstract description 43
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 112
- 125000002947 alkylene group Chemical group 0.000 claims description 101
- 150000001875 compounds Chemical class 0.000 claims description 88
- 238000006243 chemical reaction Methods 0.000 claims description 42
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 31
- 125000003700 epoxy group Chemical group 0.000 claims description 27
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- 238000004519 manufacturing process Methods 0.000 claims description 17
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- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims description 10
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- 229910019142 PO4 Inorganic materials 0.000 claims description 8
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- 150000004692 metal hydroxides Chemical class 0.000 claims description 7
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- 230000002194 synthesizing effect Effects 0.000 claims description 6
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- 230000000052 comparative effect Effects 0.000 description 32
- 238000011156 evaluation Methods 0.000 description 31
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 28
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- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
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- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- PNLUGRYDUHRLOF-UHFFFAOYSA-N n-ethenyl-n-methylacetamide Chemical compound C=CN(C)C(C)=O PNLUGRYDUHRLOF-UHFFFAOYSA-N 0.000 description 7
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
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Images
Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/395—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing phosphorus
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- 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
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
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- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/30—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen phosphorus-containing groups
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- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
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- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
- G02C7/02—Lenses; Lens systems ; Methods of designing lenses
- G02C7/04—Contact lenses for the eyes
Definitions
- the present disclosure includes a polydimethylsiloxane-containing monomer having a phosphorylcholine group and a hydroxyl group, a method for producing the monomer, a composition containing the monomer, a polymer obtained by polymerizing the composition, an ophthalmic device containing the polymer, It also relates to a method for producing a polydimethylsiloxane-containing monomer having a hydrosilane at its end.
- contact lenses which are ophthalmic devices, must receive oxygen from the air and require oxygen permeability.
- contact lenses made from siloxane monomers have been developed in order to improve oxygen permeability.
- Contact lenses require wettability in addition to oxygen permeability. Contact lenses with high wettability are said to be comfortable to wear and comfortable to wear for a long time. In order to improve the wettability of contact lenses, it is common to include hydrophilic monomers in raw materials.
- siloxane monomers are generally highly hydrophobic and have poor compatibility with hydrophilic monomers. Therefore, phase separation is likely to occur, making it difficult to produce a transparent contact lens.
- a good contact lens also needs to satisfy multiple factors such as adequate mechanical strength. In order to satisfy these factors at the same time, various types and compounding ratios of siloxane monomers and hydrophilic monomers have been studied, and formulation optimization has been planned.
- Patent Document 1 a contact lens produced using a composition in which a hydrophilic polymer such as polyvinylpyrrolidone (PVP) is mixed in addition to a siloxane monomer and a hydrophilic monomer exhibits good wearing comfort due to high wettability. rice field.
- a hydrophilic polymer such as polyvinylpyrrolidone (PVP)
- PVP polyvinylpyrrolidone
- the hydrophilic polymer like the hydrophilic monomer, also has poor compatibility with the siloxane monomer, and there is a problem that phase separation tends to occur.
- Patent Documents 2 and 3 disclose contact lenses manufactured from polydimethylsiloxane-containing monomers having hydrophilic groups.
- a polyether group, a hydroxyl group, an amide group, etc. are selected. It was necessary to introduce a functional group, and there was a concern that other elements required for excellent contact lenses would be adversely affected.
- contact lenses made from siloxane monomers exhibit high oxygen permeability, they tend to adhere to lipids due to the hydrophobic nature of the siloxane monomers, and one of the problems is that the lipids adhere to the lenses and reduce wearing comfort. .
- Techniques such as surface modification are used to suppress lipid adhesion.
- plasma treatment is included as part of the manufacturing process for contact lenses.
- the plasma treatment requires dedicated equipment, and a simpler surface modification method is desired from the viewpoint of cost.
- the present disclosure provides a polydimethylsiloxane-containing monomer that exhibits good compatibility with hydrophilic monomers and hydrophilic polymers, and a hydrous polymer obtained by polymerizing a composition containing the polydimethylsiloxane-containing monomer and a hydrophilic monomer.
- the contact lens obtained by the method has excellent surface hydrophilicity and coatability, and furthermore, the contact lens obtained by adding water to the polymer obtained by polymerizing the composition containing the polydimethylsiloxane-containing monomer, the hydrophilic monomer and the hydrophilic polymer.
- An object of the present invention is to provide a lens having anti-lipid adhesion properties.
- the present disclosure was completed by confirming that a polydimethylsiloxane-containing monomer having a phosphorylcholine group and a hydroxyl group represented by the following formula (1A) can solve the problems. That is, the present disclosure is as follows.
- a polydimethylsiloxane-containing monomer represented by formula (1A) having a phosphorylcholine group and a hydroxyl group (compound represented by formula (1A)).
- R 1 is H or CH 3
- W 1 is O or NR 4 , where R 4 is H or an alkyl group having 1 to 4 carbon atoms, and a is an integer of 1 to 100;
- a 0 are represented by equation (2).
- X 1 is an alkylene divalent group having 3 to 8 carbon atoms or a divalent group of -R 6 -OR 7 -, where R 6 is an alkylene divalent group having 3 to 6 carbon atoms.
- R 7 is a C 1-6 alkylene divalent group
- Y is a C 1-8 alkylene divalent group or a -R 8 -OR 9 - divalent group
- R 8 and R 9 is each independently an alkylene divalent group having 1 to 6 carbon atoms
- Y is represented by formula (3) or formula (4)
- Z is a phosphorylcholine group.
- a production method comprising the step of synthesizing formula (1A).
- R 1 is H or CH 3
- W 1 is O or NR 4 , where R 4 is H or an alkyl group having 1 to 4 carbon atoms, and a is an integer of 1 to 100;
- a 0 are represented by equation (2).
- X 1 is an alkylene divalent group having 3 to 8 carbon atoms or a divalent group of -R 6 -OR 7 -, where R 6 is an alkylene divalent group having 3 to 6 carbon atoms.
- R 7 is a C 1-6 alkylene divalent group
- Y is a C 1-8 alkylene divalent group or a -R 8 -OR 9 - divalent group
- R 8 and R 9 is each independently an alkylene divalent group having 1 to 6 carbon atoms
- Y is represented by formula (3) or formula (4)
- Z is a phosphorylcholine group.
- R 3 is H or CH 3
- X 2 is an alkylene divalent group having 1 to 10 carbon atoms or a -R 10 -OR 11 - divalent group, where R 10 and R 11 are each independently an alkylene divalent group having 1 to 6 carbon atoms.
- R 1 is H or CH 3 , W 1 is O or NR 4 , where R 4 is H or an alkyl group having 1 to 4 carbon atoms, and a is an integer of 1 to 100 .
- R 1 is H or CH 3 and W 1 is O or NR 4 , where R 4 is H or an alkyl group having 1 to 4 carbon atoms.
- R 1 is H or CH 3 and W 1 is O or NR 4 , where R 4 is H or an alkyl group having 1 to 4 carbon atoms.
- a composition comprising a compound represented by the following formula (1A) and one or more hydrophilic monomers.
- R 1 is H or CH 3
- W 1 is O or NR 4 , where R 4 is H or an alkyl group having 1 to 4 carbon atoms, and a is an integer of 1 to 100;
- a 0 are represented by equation (2).
- X 1 is an alkylene divalent group having 3 to 8 carbon atoms or a divalent group of -R 6 -OR 7 -, where R 6 is an alkylene divalent group having 3 to 6 carbon atoms.
- R 7 is a C 1-6 alkylene divalent group
- Y is a C 1-8 alkylene divalent group or a -R 8 -OR 9 - divalent group
- R 8 and R 9 is each independently an alkylene divalent group having 1 to 6 carbon atoms
- Y is represented by formula (3) or formula (4)
- Z is a phosphorylcholine group.
- R 3 is H or CH 3
- X 2 is an alkylene divalent group having 1 to 10 carbon atoms or a -R 10 -OR 11 - divalent group, where R 10 and R 11 are each independently an alkylene divalent group having 1 to 6 carbon atoms.
- a composition comprising at least one compound represented by formula (1A) below, at least one hydrophilic monomer, and at least one hydrophilic polymer.
- R 1 is H or CH 3
- W 1 is O or NR 4 , where R 4 is H or an alkyl group having 1 to 4 carbon atoms, and a is an integer of 1 to 100;
- a 0 are represented by equation (2).
- X 1 is an alkylene divalent group having 3 to 8 carbon atoms or a divalent group of -R 6 -OR 7 -, where R 6 is an alkylene divalent group having 3 to 6 carbon atoms.
- R 7 is a C 1-6 alkylene divalent group
- Y is a C 1-8 alkylene divalent group or a -R 8 -OR 9 - divalent group
- R 8 and R 9 is each independently an alkylene divalent group having 1 to 6 carbon atoms
- Y is represented by formula (3) or formula (4)
- Z is a phosphorylcholine group.
- R 3 is H or CH 3
- X 2 is an alkylene divalent group having 1 to 10 carbon atoms or a -R 10 -OR 11 - divalent group, where R 10 and R 11 are each independently an alkylene divalent group having 1 to 6 carbon atoms.
- a composition comprising a compound represented by formula (1A) below, one or more hydrophilic monomers, and one or more siloxane monomers.
- R 1 is H or CH 3
- W 1 is O or NR 4 , where R 4 is H or an alkyl group having 1 to 4 carbon atoms, and a is an integer of 1 to 100;
- a 0 are represented by equation (2).
- X 1 is an alkylene divalent group having 3 to 8 carbon atoms or a divalent group of -R 6 -OR 7 -, where R 6 is an alkylene divalent group having 3 to 6 carbon atoms.
- R 7 is a C 1-6 alkylene divalent group
- Y is a C 1-8 alkylene divalent group or a -R 8 -OR 9 - divalent group
- R 8 and R 9 is each independently an alkylene divalent group having 1 to 6 carbon atoms
- Y is represented by formula (3) or formula (4)
- Z is a phosphorylcholine group.
- R 3 is H or CH 3
- X 2 is an alkylene divalent group having 1 to 10 carbon atoms or a -R 10 -OR 11 - divalent group, where R 10 and R 11 are each independently an alkylene divalent group having 1 to 6 carbon atoms.
- 7. 7 7.
- composition comprising a compound represented by the following formula (1A), one or more hydrophilic monomers, one or more hydroxyl group-containing siloxane monomers, and one or more hydrophilic polymers.
- R 1 is H or CH 3
- W 1 is O or NR 4
- R 4 is H or an alkyl group having 1 to 4 carbon atoms
- a is an integer of 1 to 100
- a 0 are represented by equation (2).
- X 1 is an alkylene divalent group having 3 to 8 carbon atoms or a divalent group of -R 6 -OR 7 -, where R 6 is an alkylene divalent group having 3 to 6 carbon atoms. and R 7 is a C 1-6 alkylene divalent group, Y is a C 1-8 alkylene divalent group or a -R 8 -OR 9 - divalent group, where R 8 and R 9 is each independently an alkylene divalent group having 1 to 6 carbon atoms, or Y is represented by formula (3) or formula (4), and Z is a phosphorylcholine group.
- An ophthalmic device comprising the polymer according to 11 above. 13. Said R 1 is CH 3 , said W 1 is O, X 1 of said A 0 is CH 2 CH 2 CH 2 -O-CH 2 or CH 2 CH 2 CH 2 CH 2 , Y is the formula (3), a compound represented by formula (1A) according to the preceding item 1, which is formula (4) (wherein R 3 is CH 3 and X 2 is CH 3 ) or CH 2 ; 14.
- R 1 is CH 3
- said W 1 is O
- X 1 of said A 0 is CH 2 CH 2 CH 2 -O-CH 2 or CH 2 CH 2 CH 2 CH 2
- Y is the formula (3)
- formula (4) (wherein R 3 is CH 3 and X 2 is CH 3 ) or CH 2 , the composition according to any one of the preceding items 4 to 8. 15. Use of the composition according to any one of 4 to 8 above for manufacturing an ophthalmic device.
- the polydimethylsiloxane-containing monomer having a phosphorylcholine group and a hydroxyl group of the present disclosure has a phosphorylcholine group and a hydroxyl group, and therefore has good compatibility with hydrophilic monomers and hydrophilic polymers.
- a contact lens obtained by hydrating a polymer obtained by polymerizing a composition containing said polydimethylsiloxane-containing monomer and a hydrophilic monomer has excellent surface hydrophilicity and coatability, and said polydimethylsiloxane-containing monomer and hydrophilic monomer.
- a contact lens obtained by hydrating a polymer obtained by polymerizing a composition containing a hydrophilic polymer has transparency and anti-lipid adhesion.
- the present disclosure relates to polydimethylsiloxane-containing monomers having phosphorylcholine groups and hydroxyl groups. More specifically, the polydimethylsiloxane-containing monomer having a phosphorylcholine group and a hydroxyl group of the present disclosure is represented by the following formula (1A), contains a polydimethylsiloxane moiety, further has a phosphorylcholine group and a hydroxyl group in the molecule, and further has a vinyl terminal group. , preferably polymerizable polydimethylsiloxane compounds.
- the polydimethylsiloxane-containing monomer having a phosphorylcholine group and a hydroxyl group of the present disclosure has a phosphorylcholine group and a hydroxyl group in the molecule, and therefore exhibits good compatibility with hydrophilic monomers and hydrophilic polymers.
- a transparent polymer is obtained when the composition of the polydimethylsiloxane-containing monomer and the hydrophilic monomer is polymerized. Further, the contact lens obtained by hydrating the polymer exhibits excellent surface hydrophilicity and coatability.
- a transparent polymer is obtained when the composition of the polydimethylsiloxane-containing monomer, hydrophilic monomer and hydrophilic polymer is polymerized. Furthermore, contact lenses obtained by hydrating the polymer exhibit excellent anti-lipid adhesion properties.
- the polydimethylsiloxane-containing monomers contain vinyl end groups to facilitate polymerization with other compositions (including monomers).
- the polydimethylsiloxane-containing monomer having a phosphorylcholine group and a hydroxyl group of the present disclosure is a polydimethylsiloxane-containing monomer represented by formula (1A).
- R 1 is H or CH 3
- W 1 is O or NR 4
- R 4 is H or an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group);
- a is an integer from 1 to 100
- a 0 is represented by formula (2).
- a is not particularly limited as long as it is within the above range, a is 1 to 100, preferably 2 to 50, more preferably 2 to 30, still more preferably 2 to 15, and particularly preferably 2 to 10.
- X 1 is a C 3-8 alkylene divalent group or a -R 6 -OR 7 - divalent group, where R 6 is a C 3-6 alkylene divalent group.
- R 7 is an alkylene divalent group having 1 to 6 carbon atoms
- Y is an alkylene divalent group having 1 to 8 carbon atoms or a divalent group of —R 8 —OR 9 —, where R 8 and R 9 are each independently an alkylene divalent group having 1 to 6 carbon atoms, or Y is represented by formula (3) or formula (4), and Z is a phosphorylcholine group.
- C2-C6 alkylene refers to a divalent group obtained by removing two hydrogen atoms from a C2-C6 alkyl. The same applies to other similar terms. Alkylene groups form two bonds with other groups in organic compounds.
- R 3 is H or CH 3 and X 2 is an alkylene divalent group having 1 to 10 carbon atoms or a divalent group of -R 10 -OR 11 -, where R 10 and R 11 are each independently an alkylene divalent group having 1 to 6 carbon atoms.
- Z is a phosphorylcholine group, and the following formula (5) can be exemplified.
- a polydimethylsiloxane-containing monomer having a phosphorylcholine group and a hydroxyl group represented by formula (1A) of the present disclosure is synthesized by the following method.
- a hydrosilylation reaction between the compound represented by formula (6A) and a vinyl compound having an epoxy group and further a reaction between the epoxy group of the compound after the reaction and a carboxylic acid of a carboxylic acid compound having a phosphorylcholine group
- a reaction between an epoxy group of a vinyl compound having an epoxy group and a carboxylic acid of a carboxylic acid compound having a phosphorylcholine group, and a vinyl compound having a phosphorylcholine group and a hydroxyl group after the reaction and a compound represented by formula (6A) is prepared from the step of synthesizing formula (1A) by the hydrosilylation reaction of
- R 1 is H or CH 3 and W 1 is O or NR 4 where R 4 is H or C 1-4 alkyl.
- R 1 is H or CH 3 and W 1 is O or NR 4 where R 4 is H or C 1-4 alkyl.
- R 1 is H or CH 3
- W 1 is O or NR 4
- R 4 is H or an alkyl group having 1-4 carbon atoms, and a is an integer of 1-100;
- a compound represented by formula (6A) is synthesized by the following method.
- a chlorosilane compound represented by the formula (7) is dissolved in a solvent, and a metal hydroxide is added to convert it into a silanol compound represented by the formula (7A).
- a poor solvent is added and the precipitated metal salt is removed by filtration.
- a cyclic siloxane is mixed, an organic base catalyst is added to initiate the reaction, and a chlorosilane compound is used to terminate the reaction.
- a desired value of a in formula (6A) can be obtained by controlling the molar ratio of the silanol compound and the cyclic siloxane to be mixed.
- metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, and potassium hydroxide. Lithium oxide is preferred.
- the metal hydroxide is usually added in an amount of 1.0 mol equivalent to 4.0 mol equivalents, preferably 1.5 mol equivalents to 2.5 mol equivalents, relative to the chlorosilane compound.
- Solvents include, for example, dichloromethane, tetrahydrofuran, dimethylsulfoxide, dimethylformamide, and mixed solvents thereof, and tetrahydrofuran is preferred from the viewpoint of solubility.
- the solvent is usually used in an amount of 5 to 50 equivalents, preferably 10 to 30 equivalents, relative to the metal hydroxide.
- Poor solvents include, for example, hexane, heptane, cyclohexane, 2-methylpentane, 3-methylpentane, benzene, toluene, or mixed poor solvents thereof, with hexane and heptane being particularly preferred.
- the poor solvent is generally used in an amount of 0.5 to 1.5 equivalents, preferably 0.8 to 1.2 equivalents, relative to the solvent.
- cyclic siloxane 6-, 8-, or 10-membered cyclic siloxanes are used, and from the viewpoint of reactivity, 6-membered cyclic siloxane (hexamethylcyclotrisiloxane) is preferable.
- a solvent may be added when mixing the cyclic siloxane. Examples of the solvent to be added at this time include the above-described solvents, and it is preferable to use the same solvent.
- the amount of the solvent to be added is not particularly limited, but is preferably 1.0 to 10 equivalents, preferably 1.5 to 5 equivalents, relative to the cyclic siloxane.
- the organic base catalyst is an organic amine having an amidine structure, a guanidine structure, a phosphazene structure, a proazaphosphatrane structure, etc., such as 1,5-diazabicyclo[4.3.0]non-5-ene (DBN).
- DBN 1,5-diazabicyclo[4.3.0]non-5-ene
- 1,8-diazabicyclo[5.4.0]undec-7-ene (diazabicycloundecene, DBU), 7-methyl-1,5,7-triazabicyclo[4.4.0]deca- 5-ene (MTBD), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), t-butylimino-tris(dimethylamino)phosphorane (BEMP), phosphazene base P1- tBu-tris(tetramethylene) (tBu-P1(Pyrr)), phosphazene base P2-Et (P2-Et)), 2,8,9-triisobutyl-2,5,8,9-tetraaza-1-phos fabicyclo[3.3.3]undecane (TiBP) and the like.
- DBU 1,8-diazabicyclo[5.4.0]undec-7-ene
- MTBD 7-methyl-1,5,7-triazabicyclo
- the organic base catalyst exerts its effect when added in a catalytic amount, it is usually 0.01 to 0.5 mol %, preferably 0.05 to 0.5 mol %, relative to the silanol group-containing compound represented by formula (7A). Add 2 mol %.
- the organic base catalyst can be removed by liquid separation purification after the reaction.
- a chlorosilane compound having hydrosilane is used as the chlorosilane compound.
- 5-hexamethyltrisiloxane, 1-chloro-1,1,3,3,5,5,7,7-octamethyltetrasiloxane, etc. can be mentioned, but chlorodimethylsilane is preferred from the standpoint of availability.
- the silanol group-containing compound represented by the formula (7A) When terminating the reaction with a chlorosilane compound, it is necessary to add the chlorosilane compound in an equimolar amount or more to the silanol compound represented by the formula (7A), so the silanol group-containing compound represented by the formula (7A) , usually 1.0 mol% to 5.0 mol%, preferably 1.1 mol% to 2.5 mol%.
- a base may be added for the purpose of capturing hydrogen chloride.
- the base include pyridine, diisopropylamine, triethylamine, trioctylamine, etc. Triethylamine is preferred because of ease of handling.
- the base is preferably added in an equimolar amount or more than the chlorosilane compound.
- (meth)acrylate means “acrylate or methacrylate”, and the same applies to other similar terms.
- R 1 is H or CH 3 and W 1 is O or NR 4 where R 4 is H or C 1-4 alkyl.
- R 1 is H or CH 3 and W 1 is O or NR 4 where R 4 is H or C 1-4 alkyl.
- R 1 is H or CH 3
- W 1 is O or NR 4
- R 4 is H or an alkyl group having 1-4 carbon atoms, and a is an integer of 1-100;
- a hydrosilylation reaction is a reaction known to those skilled in the art and refers to a reaction in which a hydrosilane having a silicon-hydrogen bond adds to an unsaturated bond to form a silicon-carbon bond in the presence of a metal catalyst.
- metal catalysts examples include rhodium catalysts typified by Wilkinson catalysts, and platinum catalysts typified by platinum chloride catalysts and Karstedt catalysts. Platinum chloride catalysts and Karstedt catalysts are preferred.
- reaction between an epoxy group and a carboxylic acid is a reaction known to those skilled in the art, and refers to a reaction to form a bond of formula (8) accompanied by ring opening of the epoxy group in the presence of a base catalyst.
- base catalysts include, but are not limited to, triethylamine, dimethylamine, diisopropylethylamine, diisopropylamine, sodium hydroxide, and potassium hydroxide. Preferred are triethylamine and sodium hydroxide.
- the compound represented by formula (1A) is synthesized from the compound represented by formula (6A) by combining a hydrosilylation reaction and a reaction between an epoxy group and a carboxylic acid.
- a method for producing the compound represented by Formula (1A) is shown below.
- a compound represented by the formula (6A) and an excess amount of a vinyl compound having an epoxy group represented by the formula (9) are mixed and subjected to a hydrosilylation reaction to convert the hydrosilane in the formula (6A) to the formula A compound added to the vinyl group of (9) is obtained.
- Unreacted compound of formula (9) may be removed by concentration operation using an evaporator or the like.
- a carboxylic acid compound having a phosphorylcholine group represented by formula (10) is added to react the epoxy group with the carboxylic acid.
- the reaction between the epoxy group and the carboxylic acid forms the bond represented by formula (8), yielding a polydimethylsiloxane-containing monomer having a phosphorylcholine group and a hydroxyl group represented by formula (1A).
- An unreacted carboxylic acid compound having a phosphorylcholine group represented by formula (10) can be removed by liquid separation purification.
- Another method for producing the compound represented by formula (1A) includes the following method. Excess amounts of the vinyl compound having an epoxy group represented by the formula (9) and the carboxylic acid compound having a phosphorylcholine group represented by the formula (10) are reacted with the epoxy group and the carboxylic acid to obtain the compound represented by the formula (11). A vinyl compound having the represented phosphorylcholine group and hydroxyl group is synthesized. At this time, the unreacted compound of formula (9) may be removed by a concentration operation using an evaporator or the like.
- formula (6A) is added to carry out a hydrosilylation reaction between the compound represented by formula (6A) and an excess amount of the vinyl compound having a phosphorylcholine group and a hydroxyl group represented by formula (11).
- Polydimethylsiloxane having a phosphorylcholine group and a hydroxyl group represented by the formula (1A) is obtained by adding the hydrosilane in the formula (6A) to the vinyl group of the vinyl compound having a phosphorylcholine group and a hydroxyl group represented by the formula (11).
- a content monomer is obtained.
- the unreacted vinyl compound having a phosphorylcholine group and a hydroxyl group represented by formula (11) can be removed by a liquid separation operation.
- X 3 is an alkyl group having 1 to 6 carbon atoms or a divalent group of —R 12 —OR 13 —, where R 12 is an alkylene divalent group having 1 to 4 carbon atoms, and R 13 is an alkylene divalent group having 1 to 6 carbon atoms.
- Y is an alkylene divalent group having 1 to 8 carbon atoms or a divalent group of —R 8 —OR 9 —, where R 8 and R 9 are independently each other an alkylene divalent group having 1 to 6 carbon atoms.
- R 8 and R 9 are independently each other an alkylene divalent group having 1 to 6 carbon atoms.
- Y is represented by formula (3) or formula (4), and Z is a phosphorylcholine group.
- X 3 is an alkyl group having 1 to 6 carbon atoms or a divalent group of —R 12 —OR 13 —, where R 12 is an alkylene divalent group having 1 to 4 carbon atoms, and R 13 is an alkylene divalent group having 1 to 6 carbon atoms, Y is an alkylene divalent group having 1 to 8 carbon atoms or a divalent group of -R 8 -OR 9 -, where R 8 and R 9 are , are each independently an alkylene divalent group having 1 to 6 carbon atoms, or Y is represented by formula (3) or formula (4), and Z is a phosphorylcholine group.
- Examples of compounds of formula (9) include 3,4-epoxy-1-butene, 1,2-epoxy-5-hexene, allyl glycidyl ether, 1,2-epoxy-9-decene, and the like.
- X 3 is an alkyl group having 1 to 6 carbon atoms or a divalent group of —R 12 —OR 13 —, where R 12 is an alkylene divalent group having 1 to 4 carbon atoms, and R 13 is an alkylene divalent group having 1 to 6 carbon atoms.
- a carboxylic acid compound having a phosphorylcholine group used for synthesis of formula (1A) is represented by formula (10).
- Y is an alkylene divalent group having 1 to 8 carbon atoms or a divalent group of —R 8 —OR 9 —, where R 8 and R 9 are independently each other an alkylene divalent group having 1 to 6 carbon atoms.
- R 8 and R 9 are independently each other an alkylene divalent group having 1 to 6 carbon atoms.
- Y is represented by formula (3) or formula (4), and Z is a phosphorylcholine group.
- the vinyl compound having a phosphorylcholine group and a hydroxyl group represented by formula (11), which is used in the synthesis of formula (1A), is a vinyl compound having an epoxy group represented by formula (9) and a vinyl compound represented by formula (10). It is synthesized by reacting an epoxy group and a carboxylic acid with a carboxylic acid compound having a phosphorylcholine group.
- a vinyl compound having a phosphorylcholine group and a hydroxyl group represented by the formula (11) is converted into a poly(poly) having a phosphorylcholine group and a hydroxyl group represented by the formula (1A) by hydrosilylation reaction with a compound represented by the formula (6A). Used in the synthesis of dimethylsiloxane-containing monomers.
- X 3 is an alkyl group having 1 to 6 carbon atoms or a divalent group of —R 12 —OR 13 —, where R 12 is an alkylene divalent group having 1 to 4 carbon atoms, and R 13 is an alkylene divalent group having 1 to 6 carbon atoms, Y is an alkylene divalent group having 1 to 8 carbon atoms or a divalent group of -R 8 -OR 9 -, where R 8 and R 9 are , are each independently an alkylene divalent group having 1 to 6 carbon atoms, or Y is represented by formula (3) or formula (4), and Z is a phosphorylcholine group.
- Example 1 of the composition of the present disclosure contains at least one polydimethylsiloxane-containing monomer having a phosphorylcholine group and a hydroxyl group represented by formula (1A) and at least one hydrophilic monomer.
- the compositions of the present disclosure can be polymerized using catalysts or initiators known to those skilled in the art.
- the total amount of the polydimethylsiloxane-containing monomer having a phosphorylcholine group and a hydroxyl group represented by formula (1A) is 10 to 60 parts by mass, preferably 15 to 55 parts by mass. Yes, more preferably 25 to 45 parts by mass.
- the hydrophilic monomer is 20 to 80 parts by weight, preferably 25 to 70 parts by weight, more preferably 30 to 60 parts by weight, based on the total amount. If it is less than 20 parts by mass, the hydrophilicity of the contact lens may decrease. If it exceeds 80 parts by mass, sufficient oxygen permeability may not be obtained.
- a hydrophilic monomer is a compound having a hydrophilic functional group and a polymerizable vinyl group.
- Hydrophilic monomers are, for example, 2-(methacryloyloxyethyl)-2-(trimethylammonioethyl)phosphate, 2-hydroxyethyl (meth)acrylate, N-vinylpyrrolidone, N,N-dimethylacrylamide, 2-hydroxypropyl selected from the group consisting of (meth)acrylates, 2-hydroxybutyl (meth)acrylate, N-methyl-N-vinylacetamide, 2-hydroxyethyl (meth)acrylamide, ethylene glycol monovinyl ether, diethylene glycol monovinyl ether and mixtures thereof can be used, but is not particularly limited.
- Example 1 of the composition of the present disclosure components other than the polydimethylsiloxane-containing monomer having a phosphorylcholine group and a hydroxyl group represented by formula (1A) and the hydrophilic monomer may be included.
- Other components of the compositions of the present disclosure include, for example, siloxane monomers. By adding a siloxane monomer to the composition, it is possible to improve the oxygen permeability and mechanical properties of the polymerized composition.
- the siloxane monomer is not particularly limited as long as it is a compound containing siloxane and a vinyl group.
- siloxane monomer is usually contained in an amount of 5 to 40 parts by mass, preferably 8 to 30 parts by mass, more preferably 10 to 25 parts by mass, based on the total amount of monomers.
- Other components of the compositions of the present disclosure include, for example, crosslinkers.
- Cross-linking agents are known to those skilled in the art, for example tetra(ethylene glycol) di(meth)acrylate, tri(ethylene glycol) di(meth)acrylate, ethylene glycol di(meth)acrylate, di(ethylene glycol) di( meth)acrylate, glycerol dimethacrylate, allyl (meth)acrylate, N,N'-methylenebis(meth)acrylamide, N,N'-ethylenebis(meth)acrylamide, N,N'-dihydroxyethylenebis(meth)acrylamide, selected from the group consisting of triallyl isocyanurate, tetraethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether, ethylene glycol divinyl ether, trimethylolpropane tri(meth)acrylate, and combinations thereof.
- the cross-linking agent is usually contained in an amount of 0.1 to 5 parts by mass, preferably 0.3 to 3 parts by mass, more preferably 0.5 to 2 parts by mass based on the total amount of the composition.
- the polydimethylsiloxane-containing monomer having a phosphorylcholine group and a hydroxyl group represented by formula (1A) is 100 parts by mass, 33 to 800 parts by mass of one or more hydrophilic monomers,
- One or more siloxane monomers can be from 8 to 400 parts by weight.
- Example 2 of the composition of the present disclosure contains at least one polydimethylsiloxane-containing monomer having a phosphorylcholine group and a hydroxyl group represented by formula (1A), at least one hydrophilic monomer, and at least one hydrophilic polymer. Includes more than one type.
- Example 2 of the composition of the present disclosure includes at least one polydimethylsiloxane-containing monomer having a phosphorylcholine group and a hydroxyl group represented by formula (1A), at least one hydrophilic monomer, and a hydrophilic polymer and at least one hydroxyl group-containing siloxane monomer.
- Example 2 of the composition of the present disclosure can be polymerized using catalysts or initiators known to those skilled in the art.
- Example 2 of the composition of the present disclosure the polydimethylsiloxane-containing monomer having a phosphorylcholine group and a hydroxyl group represented by formula (1A) is contained, based on the total amount of the monomer, from 5 parts by mass to 50 parts by mass, preferably 10 parts by mass. part to 40 parts by mass, more preferably 15 to 35 parts by mass. If it is less than 5 parts by mass, the transparency of the polymer obtained by polymerization is lowered, and if it exceeds 50 parts by mass, the surface wettability of the polymer is lowered.
- the hydrophilic monomer is usually contained in an amount of 20 to 90 parts by weight, preferably 40 to 80 parts by weight, based on the total amount of monomers.
- the hydroxyl group-containing siloxane monomer is usually contained in an amount of 20 to 90 parts by weight, preferably 40 to 80 parts by weight, based on the total amount of monomers.
- the hydrophilic polymer is contained in an amount of 0.1 to 15 parts by mass, preferably 1 to 10 parts by mass, based on the total amount of the composition.
- a hydrophilic monomer is a compound having a hydrophilic functional group and a polymerizable vinyl group.
- Hydrophilic monomers are, for example, 2-hydroxyethyl (meth)acrylate, N-vinylpyrrolidone, N,N-dimethylacrylamide, 2-(methacryloyloxyethyl)-2-(trimethylammonioethyl)phosphate, 2-hydroxypropyl It can be selected from the group consisting of (meth)acrylate, 2-hydroxybutyl (meth)acrylate, N-methyl-N-vinylacetamide, and mixtures thereof, but is not particularly limited.
- Hydrophilic polymers can be exemplified by polyamides, polylactams, polyimides and polylactones. Preferably, they are hydrogen bond acceptors that effectively become more hydrophilic by hydrogen bonding to water in an aqueous environment.
- the hydrophilic polymer is a linear polymer having cyclic moieties contained within its polymer backbone. More preferably, the cyclic moiety is a cyclic moiety in a cyclic amide or imide.
- Polymers of this type preferably include, for example, polyvinylpyrrolidone and polyvinylimidazole, but polymers such as polydimethylacrylamide are also useful in that capacity. Polyvinylpyrrolidone is the most preferred hydrophilic polymer.
- the molecular weight of the hydrophilic polymer is not particularly limited, it is generally 100,000 to 500,000, more preferably 300,000 to 500,000.
- Example 2 of the composition of the present disclosure components other than the polydimethylsiloxane-containing monomer having a phosphorylcholine group and a hydroxyl group represented by formula (1A), the hydrophilic monomer and the hydrophilic polymer may be included.
- Example 2 of the composition of the present disclosure include, for example, siloxane monomers.
- siloxane monomers By adding a siloxane monomer to the composition, it is possible to improve the oxygen permeability and mechanical properties of the polymerized composition.
- the siloxane monomer is not particularly limited as long as it is a compound containing siloxane and a vinyl group, but from the viewpoint of compatibility of the composition, a hydroxyl group-containing siloxane monomer is preferred.
- the siloxane monomer or hydroxyl group-containing siloxane monomer is usually contained in an amount of 5 to 50 parts by mass, preferably 10 to 40 parts by mass, more preferably 15 to 30 parts by mass, based on the total amount of monomers.
- Example 2 of the composition of the present disclosure include, for example, a crosslinker.
- Cross-linking agents are known to those skilled in the art, for example tetra(ethylene glycol) di(meth)acrylate, tri(ethylene glycol) di(meth)acrylate, ethylene glycol di(meth)acrylate, di(ethylene glycol) di( meth)acrylate, glycerol dimethacrylate, allyl (meth)acrylate, N,N'-methylenebis(meth)acrylamide, N,N'-ethylenebis(meth)acrylamide, N,N'-dihydroxyethylenebis(meth)acrylamide, selected from the group consisting of triallyl isocyanurate, tetraethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether, ethylene glycol divinyl ether, and combinations thereof.
- the cross-linking agent is usually contained in an amount of 0.1 to 5 parts by mass, preferably 0.3 to 3 parts by mass, more preferably 0.5 to 2 parts by mass based on the total amount of the composition.
- the polydimethylsiloxane-containing monomer having a phosphorylcholine group and a hydroxyl group represented by formula (1A) is 100 parts by mass, 40 to 1800 parts by mass of one or more hydrophilic monomers, It is also possible to use 0.2 to 300 parts by weight of one or more hydrophilic polymers and 40 to 1800 parts by weight of one or more siloxane monomers.
- the combination of the polydimethylsiloxane-containing monomer having a phosphorylcholine group and a hydroxyl group represented by formula (1A), the hydrophilic monomer and the hydrophilic polymer contained in Example 2 of the composition of the present disclosure is not particularly limited, but preferred combinations are as follows. is mentioned.
- Example 1 of the composition of the present disclosure is not particularly limited, but preferred combinations are as follows. mentioned.
- the polymer of the present disclosure can be obtained by polymerization of the composition of the present disclosure, in which any solvent, any thermal initiator or photoinitiator as a radical initiator for polymerization is used. be able to.
- the polymerization method is not particularly limited, and various methods known to those skilled in the art can be used.
- the composition is mixed and uniformly dissolved, a thermal polymerization initiator represented by a peroxide, an azo compound, or a photopolymerization initiator is added as appropriate, and the composition is dispensed into a contact lens mold. , heating, UV irradiation, or other known methods.
- the polymerization may be carried out in the air, or may be carried out in an atmosphere of an inert gas such as nitrogen or argon for the purpose of improving the polymerization rate.
- the pressure in the polymerization system is desirably 1 kgf/cm 2 or less.
- suitable solvents when a solvent is used include, but are not limited to, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2- pentanol, tert-amyl alcohol, 1-hexanol, 1-octanol, 1-decanol, 1-dodecanol, glycolic acid, lactic acid, acetic acid and the like. Any one of these solvents may be used, or a mixture of two or more thereof may be used. At least one selected from ethanol, 1-propanol, 2-propanol and 1-hexanol is preferred in terms of availability and pH stability. For Example 1 of the composition of the present disclosure, more preferably no solvent is included.
- Suitable thermal polymerization initiators include, for example, peroxides, hydroperoxides, azo-bis(alkyl- or cycloalkylnitriles), persulfates, percarbonates or mixtures thereof.
- Examples are benzoyl peroxide, tert-butyl peroxide, di-tert-butyl-diperoxyphthalate, tert-butyl hydroperoxide, azo-bis(isobutyronitrile) (AIBN), 1,1-azodiisobutylamidine, 1 , 1′-azo-bis(1-cyclohexanecarbonitrile), 2,2′-azo-bis(2,4-dimethylvaleronitrile), and the like.
- the polymerization is conveniently carried out at elevated temperature, for example at a temperature of 25-140° C., preferably 40-120° C., in the solvent mentioned above.
- the reaction time can vary within wide limits, but is conveniently, for example, 1 to 24 hours or preferably 1.5 to 12 hours.
- the components and solvents used in the polymerization reaction are previously degassed and the copolymerization reaction is carried out under an inert atmosphere, for example under a nitrogen or argon atmosphere.
- Suitable photoinitiators are benzoin methyl ether, diethoxyacetophenone, benzoylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, preferably Darocur® 1173 and Darocur® 2959, Irgacure® 819, It is a Germanic Norrish type I photoinitiator.
- benzoylphosphine oxide initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide; bis-(2,6-dichlorobenzoyl)-4-N-propylphenylphosphine oxide; and bis-(2,6- dichlorobenzoyl)-4-N-butylphenylphosphine oxide.
- reactive photoinitiators which can be incorporated into macromers or used as specialized monomers, for example.
- the polymer After polymerization, it can be separated from the mold by a known method and the polymer can be taken out in a dry state. Also, the polymer can be immersed in a solvent (eg, water, ethanol, 1-propanol, 2-propanol, and a mixed solution thereof) together with the mold to swell the polymer and peel it off. Furthermore, washing is carried out by repeatedly immersing the polymer in these solvents to remove residues, residuals, by-products, etc. of each component, and a polymer can be obtained.
- a solvent eg, water, ethanol, 1-propanol, 2-propanol, and a mixed solution thereof
- Solvents used for washing include water, ethanol, 1-propanol, 2-propanol, and mixtures thereof.
- the polymer can be immersed in an alcoholic solvent at a temperature of 10° C. to 40° C. for 10 minutes to 10 hours. After washing with an alcohol-based solvent, it may be washed by immersing it in an aqueous solution with an alcohol concentration of 20 to 50% by mass for 10 minutes to 10 hours. Any solvent can be used for washing as long as it has quality for pharmaceuticals, quasi-drugs, and medical devices.
- An ophthalmic device of the present disclosure consists essentially of or comprises a polymer of the present disclosure.
- the ophthalmic device in the present disclosure includes, but is not particularly limited to, contact lenses, soft contact lenses, hard contact lenses, intraocular lenses, and artificial corneas.
- Example 1-1 Synthesis of compound represented by formula (1A) ⁇ after dissolving 3.00 g of the compound represented by and 0.81 g of allyl glycidyl ether in 7.07 g of toluene, 18 ⁇ L of Karstedt catalyst (manufactured by Tokyo Chemical Industry Co., Ltd.) adjusted to a 10% by weight xylene solution was added overnight. The hydrosilylation reaction was carried out at 0.01 g of activated carbon was added and stirred for 30 minutes, the activated carbon was removed by pressure filtration, and the mixture was concentrated by an evaporator.
- Karstedt catalyst manufactured by Tokyo Chemical Industry Co., Ltd.
- Example 1-1 The assigned results of 1 H NMR analysis of Example 1-1 are shown below (FIG. 1).
- 1 H NMR (DMSO-d6): ⁇ 0.0 ppm (i), 0.5 ppm (h, j), 1.6-1.7 ppm (g, k), 1.9 ppm (e), 3.2 ppm (t), 3.3-3.8 ppm (l, m, o, s), 4.0-4.5 ppm (f, n, r), 5.6 ppm, 6.1 ppm (d), 5.8 ppm (u), 7.3 ppm (q), 8.0 ppm (p)
- Example 1-2 Synthesis of compound represented by formula (1A) ), R 3 : —CH 3 , X 2 : —CH 3 , Z: Formula (5) ⁇ compound 3.67 g, allyl glycidyl ether 1.21 g, methanol 3.76 g, 2-propanol 3.76 g, triethylamine 0. After adding 29 g, the temperature was raised and the reaction was carried out overnight under reflux. After the reaction, an insoluble portion was removed by pressure filtration, and concentration was performed using an evaporator.
- Example 1-2 The assigned results of 1 H NMR analysis of Example 1-2 are shown below (FIG. 2).
- 1 H NMR (DMSO-d6): ⁇ 0.0 ppm (i), 0.5-0.6 ppm (h, j), 1.2 ppm (s), 1.6-1.7 ppm (g, k), 1.9 ppm (e), 2.6-2.9 ppm (q, r), 3.2 ppm (x), 3.3-3.8 ppm (l, m, o, p, w), 3 .9 to 4.7 ppm (f, n, t, u, v), 5.6 ppm, 6.1 ppm (d), 5.8 ppm (y)
- Example 1-3 Synthesis of Compound Represented by Formula (1A)
- a carboxylic acid compound having a phosphorylcholine group represented by Formula (10) was prepared in JP-A-2005-187956.
- Formula ( 1A ) ⁇ R 1 :-CH 3 , W 1 :- O—, a: 6, X 1 : —CH 2 CH 2 CH 2 —O—CH 2 — in A 0 , Y: —CH 2 —, Z: formula (5) ⁇ was obtained.
- Table 1 shows the synthesis results of Examples 1-3.
- Example 1-4 Synthesis of compound represented by formula (1A) In the same manner as in Example 1-1, the compound of formula (6A) obtained in Synthesis Example 1-2 and , 1,2-epoxy-5-hexene to give the formula (1A) ⁇ R 1 : —CH 3 , W 1 : —O—, a: 12, X 1 in A 0 :—CH 2 CH 2 CH 2 CH 2 —, Y: Formula (3), Z: Formula (5) ⁇ .
- Table 1 shows the synthesis results of Examples 1-4.
- Example 1-5 Synthesis of compound represented by formula (1A)
- the compound of formula (6A) obtained in Synthesis Example 1-3 was used in the same reaction.
- formula (1A) ⁇ R 1 : -CH 3 , W 1 : -O-, a: 19, A 0 , X 1 : -CH 2 CH 2 CH 2 -O-CH 2 -, Y: Equation (3), Z: Equation (5) ⁇ were obtained.
- Table 1 shows the synthesis results of Examples 1-5.
- Example 1-6 Synthesis of compound represented by formula (1A)
- the compound of formula (6A) obtained in Synthesis Example 1-4 was used in the same reaction.
- formula (1A) ⁇ R 1 : -CH 3 , W 1 : -O-, a: 48, A 0 , X 1 : -CH 2 CH 2 CH 2 -O-CH 2 -, Y: Equation (3), Z: Equation (5) ⁇ were obtained.
- Table 1 shows the synthesis results of Examples 1-6.
- DMAA N,N-dimethylacrylamide
- HEMA 2-hydroxyethyl methacrylate
- HPMA 2-hydroxypropyl methacrylate (2-hydroxypropyl ester, 2-hydroxy-1-methylethyl ester mixture)
- HBMA 2-hydroxybutyl methacrylate
- NVP N-vinylpyrrolidone
- MVA N-methyl-N-vinylacetamide
- MPC 2-(methacryloyloxyethyl)-2-(trimethylammonioethyl) phosphate
- PVP K90 Polyvinylpyrrolidone K90 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
- TEGDMA Tetraethylene glycol dimethacrylate
- composition uniformity The uniformity of the composition before polymerization was evaluated by the following method.
- the prepared composition was placed in a colorless and transparent container and visually evaluated by giving a score according to the following criteria. 1: The composition is uniform and transparent.
- the coating property was evaluated according to the procedure shown below.
- the contact lens-shaped polymer of the example was taken out from the glass vial, the water on the surface of the lens was wiped off, and the contact lens was immersed in 1 mL of dyeing solution for 5 minutes. The polymer was removed and excess dye was removed with saline and a clean cloth moistened with saline.
- the contact lens-shaped polymer of the example dyed with the staining solution was immersed in 1.5 mL of physiological saline, and the absorbance at 600 nm was measured.
- the absorbance of the contact lens-shaped polymer of the example before dyeing is A 0
- the absorbance of the contact lens-shaped polymer of the example after dyeing is A 1 .
- the absorbance increased by staining was calculated according to the following formula (1), and scored and evaluated according to the following criteria.
- Absorbance A 1 - A 0
- Example 2-1 Formula (1A) compound obtained in Example 1-1 20.0 parts by weight, DMAA 10.0 parts by weight, HBMA 10.0 parts by weight, NVP 30.0 parts by weight, SiGMA 30.0 parts by weight, PVP K90 5.00 parts by weight, 1.00 parts by weight TEGDMA, and 30.0 parts by weight HexOH were mixed. Subsequently, 0.50 parts by mass of AIBN was added and mixed to prepare a composition. The resulting composition was evaluated for composition uniformity and was given a score of "1". The composition was then dispensed into contact lens molds and placed in an oven. After the inside of the oven was replaced with nitrogen, the temperature was raised to 100° C.
- Example 2 shows the results of Example 2-1.
- Example 2-2 to 2-6 were carried out in the same manner as in Example 2-1 except that the composition shown in Table 2 was followed. Evaluation of composition uniformity, polymer transparency, and lipid adhesion resistance was performed in the same manner as in Example 2-1. Table 2 shows the evaluation results of Examples 2-2 to 2-6.
- Comparative Example 2-1 According to the composition shown in Table 2, instead of 20.0 parts by mass of the compound represented by formula (1A), 20.0 parts by mass of the comparative compound of formula (1A) prepared in Synthesis Example 1-5 was used. Comparative Example 2-1 was performed in the same manner as Example 2-1. Composition uniformity, polymer transparency, and anti-lipid adhesion were evaluated in the same manner as in Example 2-1. Gender was given a score of "5". Table 2 shows the evaluation results of Comparative Example 2-1.
- Comparative Example 2-2 According to the composition shown in Table 2, instead of 20.0 parts by mass of the compound represented by formula (1A), 20.0 parts by mass of the comparative compound of formula (1A) synthesized in Synthesis Example 1-6 was used. A composition was prepared in the same manner as in Example 2-1. The resulting composition was evaluated for composition uniformity and given a score of "2". Therefore, the subsequent polymerization steps and the evaluation of polymer transparency and anti-lipid adhesion properties were not carried out. Table 2 shows the evaluation results of Comparative Example 2-2.
- Comparative Example 2-3 According to the composition shown in Table 2, instead of 20.0 parts by mass of the compound represented by formula (1A), 20.0 parts by mass of the comparative compound of formula (1A) synthesized in Synthesis Example 1-7 was used. Comparative Example 2-3 was performed in the same manner as Example 2-1. Composition uniformity, polymer transparency, and anti-lipid adhesion were evaluated in the same manner as in Example 2-1. Gender was given a score of "4". Table 2 shows the evaluation results of Comparative Example 2-3.
- Examples 2-1 to 2-3 were all given a score of "1" for composition uniformity and "1" for polymer transparency, so hydrophilic monomers and hydrophilic polymers were given. showed very good compatibility with Examples 2-4 to 2-6 were all given a score of "1" for composition uniformity and "2” for polymer transparency, so that hydrophilic monomers and hydrophilic polymers showed sufficiently good compatibility with All of Examples 2-1 to 2-4 were given a score of "1" for the anti-lipid adhesion property, thus exhibiting extremely high anti-lipid adhesion property. Examples 2-5 were given a score of "2" for anti-lipid adhesion, thus exhibiting high anti-lipid adhesion.
- Examples 2-6 demonstrated anti-lipid adhesion by being given a score of "3" for anti-lipid adhesion. From the above results, the compound represented by formula (1A) used in Examples 2-1 to 2-6 has good compatibility with hydrophilic monomers and hydrophilic polymers and resistance to polymers. It was confirmed that the lipid-adhesive conferment was shown at the same time.
- Comparative Example 2-1 was given a score of "1" for composition uniformity and "1" for polymer transparency, showing very good compatibility with hydrophilic monomers and hydrophilic polymers. . On the other hand, it did not exhibit anti-lipid adhesion, as it was given a score of "5" for anti-lipid adhesion. Comparative Example 2-2 was given a score of "2" for composition uniformity and did not exhibit good compatibility with hydrophilic monomers or hydrophilic polymers. Comparative Example 2-3 was given a score of "1” for the composition uniformity, but was given a score of "4" for the transparency of the polymer. No compatibility was shown. It also did not exhibit anti-lipid adhesion, as it was given a score of "4" for anti-lipid adhesion. From the above results, the comparative compound of formula (1A) used in Comparative Examples 2-1 to 2-3 did not simultaneously exhibit good compatibility with hydrophilic monomers and hydrophilic polymers and anti-lipid adhesion properties. rice field.
- a polydimethylsiloxane-containing monomer having a phosphorylcholine group and a hydroxyl group represented by formula (1A) exhibits good compatibility with a hydrophilic monomer or a hydrophilic polymer, and a composition with a hydrophilic monomer or a hydrophilic polymer. It was confirmed that when polymerized, it imparts anti-lipid adhesion properties to the polymer.
- Example 3-1 Formula (1A) compound obtained in Example 1-1 2.00 g (40.0 parts by mass), TRIS 1.00 g (20.0 parts by mass), MPC 0.50 g (10.0 parts by mass), HBMA 1.10 g (22.0 parts by mass) were mixed in a container and stirred at room temperature until the MPC was dissolved. Furthermore, 0.4 g (8.0 parts by mass) of NVP, 0.05 g (1.0 parts by mass) of TEGDMA, and 0.025 g (0.5 parts by mass) of AIBN are added to the container, and the mixture becomes uniform at room temperature. to obtain a composition. The resulting composition was evaluated for composition uniformity and given a score of "1". The composition was then dispensed into contact lens molds and placed in an oven.
- the inside of the oven was replaced with nitrogen, the inside of the oven was heated to 80° C. and maintained at 80° C. for 12 hours to polymerize the composition and obtain a polymer. Each polymer was taken out from the cell to obtain a polymer. After the polymer was immersed in 100 mL of a 50% by mass 2-propanol aqueous solution for 4 hours, it was immersed in 100 mL of deionized water for 4 hours to remove unreacted substances and the like for purification. The purified polymer was immersed in a physiological saline solution described in ISO-18369-3 to swell (hydrate) to obtain a contact lens-like polymer. Each evaluation was performed on the contact lens-shaped polymer. Table 3 shows the blending ratio of each component in the composition, polymerization conditions, and each evaluation result.
- Example 3-2 to 3-4 A contact lens-like polymer was obtained in the same manner as in Example 1, except that the blending ratio of each component in the composition and the polymerization conditions were as shown in Table 3. Each evaluation was performed in the same manner as in Example 3-1. Table 3 shows the results.
- Example 3-2 the composition was polymerized by UV irradiation for 30 minutes at room temperature with a UV-LED irradiator (irradiation light wavelength: 405 nm) at an irradiance of 1.5 mW/cm 2 to obtain a polymer. rice field.
- Example 3-3 A polymer in the form of a contact lens was obtained in the same manner as in Example 1, except that the mixing ratio of each component in the composition and the polymerization conditions were as shown in Table 3. Each evaluation was performed in the same manner as in Example 3-1. Table 3 shows the results. Regarding Comparative Example 3-1, the obtained composition was evaluated for composition uniformity and was given a score of "2". Therefore, the subsequent polymerization steps and each evaluation were not performed. Regarding Comparative Example 3-3, the obtained polymer was evaluated for polymer transparency, and a score of "2" was given. Therefore, each subsequent evaluation was not implemented.
- TRIS 3-[tris(trimethylsiloxy)silyl]propyl methacrylate
- I-189 Bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide EtOH: ethanol
- NPA 1-propanol (normal propyl alcohol)
- Examples 3-1 to 3-4 were all given a score of "1" for composition uniformity and "1" for polymer transparency. Good compatibility was shown. All of Examples 3-1 to 3-4 were given a score of "1” in the wettability evaluation (hydrophilicity evaluation), and thus showed extremely high hydrophilicity. All of Examples 3-1 to 3-3 were given a score of "1” in the evaluation of antifouling property (evaluation of coating property), and thus exhibited extremely high coatability. Example 3-4 was given a score of "2" in the antifouling property evaluation (coating property evaluation), indicating high coatability.
- a polydimethylsiloxane-containing monomer having a phosphorylcholine group and a hydroxyl group represented by formula (1A) exhibits good compatibility with a hydrophilic monomer or a hydrophilic polymer, and a composition with a hydrophilic monomer or a hydrophilic polymer. It was found to impart anti-lipid adhesion, hydrophilicity and coating properties to the polymer when polymerized.
- the present disclosure can provide polydimethylsiloxane-containing monomers having phosphorylcholine groups and hydroxyl groups with the following properties.
- (2) A polymer obtained by polymerizing a composition containing the present monomer, hydrophilic monomer and hydrophilic polymer has transparency and antilipidity.
- (3) A polymer obtained by polymerizing a composition containing the present monomer and a hydrophilic monomer has transparency and excellent surface hydrophilicity and coatability without surface treatment.
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Abstract
Description
本出願は、参照によりここに援用されるところの日本出願特願2021-141694号優先権を請求する。
特許文献1において、シロキサンモノマーと親水性モノマーに加えて、ポリビニルピロリドン(PVP)などの親水性ポリマーを混合した組成物を用いて作製されたコンタクトレンズは、高い湿潤性により良好な装用感を示した。一方で、親水性ポリマーも親水性モノマーと同様にシロキサンモノマーとの相溶性が悪く、相分離が生じやすいという問題があった。
そこで、本開示は、親水性モノマーや親水性ポリマーと良好な相溶性を示すポリジメチルシロキサン含有モノマーの提供、該ポリジメチルシロキサン含有モノマーと親水性モノマーを含む組成物を重合した重合物を含水して得られるコンタクトレンズが優れた表面親水性、コーティング性を有すること、さらに、該ポリジメチルシロキサン含有モノマーと親水性モノマーおよび親水性ポリマーを含む組成物を重合した重合物を含水して得られるコンタクトレンズが抗脂質付着性を有することを課題とする。
すなわち、本開示は下記の通りである。
2.式(1A)で表される化合物の製造方法であって、
式(6A)で表される化合物とエポキシ基を有するビニル化合物とのヒドロシリル化反応、さらに該反応後の化合物のエポキシ基とホスホリルコリン基を有するカルボン酸化合物のカルボン酸との反応、または、
エポキシ基を有するビニル化合物のエポキシ基とホスホリルコリン基を有するカルボン酸化合物のカルボン酸との反応、さらに該反応後のホスホリルコリン基と水酸基を有するビニル化合物と式(6A)で表される化合物とのヒドロシリル化反応により、
式(1A)を合成する工程を含む製造方法。
3.式(6A)で表される、末端にヒドロシランを有するポリジメチルシロキサン含有モノマーの製造方法であって、
式(7)で表されるクロロシラン化合物を金属水酸化物により式(7A)で表されるシラノール化合物に変換し、次に、
有機塩基存在下、環状シロキサンおよびクロロシラン化合物の反応により、式(6A)で表される末端にヒドロシランを有するポリジメチルシロキサン含有モノマーを合成する工程を含む製造方法。
4.以下式(1A)で表される化合物と、親水性モノマーを1種類以上含む組成物。
5.以下式(1A)で表される化合物、親水性モノマーを1種類以上、親水性ポリマーを1種類以上含む組成物。
6.以下式(1A)で表される化合物、親水性モノマーを1種類以上、シロキサンモノマーを1種類以上含む組成物。
7.前記親水性モノマーが2-(メタクリロイルオキシエチル)-2-(トリメチルアンモニオエチル)ホスフェートであることを特徴とする、前項4~6のいずれか1に記載の組成物。
8.以下式(1A)で表される化合物、親水性モノマーを1種類以上、水酸基含有シロキサンモノマーを1種類以上、親水性ポリマーを1種類以上含む組成物。
9.前記親水性ポリマーがポリアミド、ポリラクタム、ポリイミド、ポリラクトン、およびポリデキストランから成る群から1以上選択される、前項5又は8のいずれか1に記載の組成物。
10.前記親水性ポリマーがポリビニルピロリドンである、前項5又は8のいずれか1に記載の組成物。
11.前項4~6及び8のいずれか1に記載の組成物を重合して得られた重合物。
12.前項11に記載の重合物を含む眼科デバイス。
13.前記R1はCH3であり、前記W1はOであり、前記A0のX1はCH2CH2CH2-O-CH2若しくはCH2CH2CH2CH2であり、Yは式(3)、式(4)(ここで、R3はCH3であり、X2はCH3である)若しくはCH2である、前項1に記載の式(1A)で表される化合物。
14.前記R1はCH3であり、前記W1はOであり、前記A0のX1はCH2CH2CH2-O-CH2若しくはCH2CH2CH2CH2であり、Yは式(3)、式(4)(ここで、R3はCH3であり、X2はCH3である)若しくはCH2である、前項4~8のいずれか1に記載の組成物。
15.前項4~8のいずれか1に記載の組成物を眼科デバイス製造のための使用。
該ポリジメチルシロキサン含有モノマーと親水性モノマーの組成物を重合したときに透明な重合物が得られる。さらに、該重合物を含水して得られるコンタクトレンズは優れた表面親水性、コーティング性を示す。
該ポリジメチルシロキサン含有モノマー、親水性モノマーおよび親水性ポリマーの組成物を重合したときに透明な重合物が得られる。さらに、該重合物を含水して得られるコンタクトレンズは優れた抗脂質付着性を示す。加えて、該ポリジメチルシロキサン含有モノマーは、ビニル末端基を含むことにより、他の組成物(モノマーを含む)と重合が容易になる。
本開示のホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマーは、式(1A)で表されるポリジメチルシロキサン含有モノマーである。
なお、本明細書において、「炭素数2~6のアルキレン」という用語は、炭素数2~6のアルキルから2つの水素原子を除去することによって得られる二価基を指す。他の類似用語についても同様である。アルキレン基は、有機化合物中の他の基と2つの結合を形成する。
本開示の式(1A)で表される、ホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマーは以下の方法で合成される。
式(7)で表されるクロロシラン化合物を金属水酸化物により活性化させて式(7A)で表されるシラノール化合物に変換し、
有機塩基存在下、環状シロキサンおよびクロロシラン化合物の反応により、式(6A)で表される末端にヒドロシランを有するポリジメチルシロキサン含有モノマーを合成する工程と
式(6A)表される化合物から、ヒドロシリル化反応と、エポキシ基とカルボン酸との反応を組み合わせて、式(1A)を合成する工程から製造される。より詳しくは、式(6A)で表される化合物とエポキシ基を有するビニル化合物とのヒドロシリル化反応、さらに該反応後の化合物のエポキシ基とホスホリルコリン基を有するカルボン酸化合物のカルボン酸との反応、または、エポキシ基を有するビニル化合物のエポキシ基とホスホリルコリン基を有するカルボン酸化合物のカルボン酸との反応、さらに該反応後のホスホリルコリン基と水酸基を有するビニル化合物と式(6A)で表される化合物とのヒドロシリル化反応により式(1A)を合成する工程から製造される。
式(6A)で表される化合物は以下の方法で合成される。
式(7)で表されるクロロシラン化合物を溶媒に溶解させ、金属水酸化物を添加して、式(7A)で表されるシラノ―ル化合物に変換する。その後、貧溶媒を添加して、析出する金属塩をろ過により取り除く。
続いて、環状シロキサンを混合して、有機塩基触媒を添加して反応を開始し、クロロシラン化合物で反応を停止させることで合成される。このとき、混合するシラノール化合物と環状シロキサンのモル比を制御することによって、式(6A)中のaを所望の値で得ることができる。
金属水酸化物は、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化マグネシウム、水酸化カリウムなどが挙げられるが、副反応が生じにくく、金属塩の除去が容易という点から、水酸化リチウムが好ましい。
金属水酸化物は、クロロシラン化合物に対して、通常1.0mol等量~4.0mol等量、好ましくは、1.5mol等量~2.5mol等量添加する。
溶媒は、例えばジクロロメタン、テトラヒドロフラン、ジメチルスルホキシド、ジメチルホルムアミド、またはこれらの混合溶媒が挙げられるが、溶解性の面からテトラヒドロフランが好ましい。
溶媒は、金属水酸化物に対して、通常5等量~50等量、好ましくは、10質等量~30等量用いる。
貧溶媒は、例えばヘキサン、ヘプタン、シクロヘキサン、2-メチルペンタン、3-メチルペンタン、ベンゼン、トルエン、またはこれらの混合貧溶媒が挙げられ、特にヘキサン、ヘプタンが好ましい。
貧溶媒は、溶媒に対して、通常0.5等量~1.5等量、好ましくは0.8等量~1.2等量用いる。
また、環状シロキサンを混合する際に、溶媒を添加しても良い。この時添加する溶媒としては、前記の溶媒が挙げられるが、同一の溶媒を用いることが好ましい。添加する溶媒量は特に限定されないが、好ましくは、環状シロキサンに対して、1.0等量~10等量、好ましくは、1.5等量~5等量である。
有機塩基触媒は、触媒量の添加で効果を発揮するため、式(7A)で表されるシラノール基含有化合物に対して、通常0.01~0.5mol%、好ましくは0.05~0.2mol%添加する。
なお、有機塩基触媒は反応後に、分液精製を行うことで取り除くことができる。
ヒドロシリル化反応は、当業者に公知の反応であり、ケイ素―水素結合をもつヒドロシランが、金属触媒の存在下、不飽和結合に付加してケイ素―炭素結合を生成する反応を指す。
エポキシ基とカルボン酸との反応は、当業者に公知の反応であり、塩基触媒の存在下、エポキシ基の開環を伴いながら式(8)記載の結合を形成する反応を指す。塩基触媒としては、特に限定されないが、例えばトリエチルアミン、ジメチルアミン、ジイソプロピルエチルアミン、ジイソプロピルアミン、水酸化ナトリウム、水酸化カリウムなどが挙げられる。好ましくは、トリエチルアミン、水酸化ナトリウムである。
式(1A)で表される化合物は、式(6A)で表される化合物から、ヒドロシリル化反応と、エポキシ基とカルボン酸との反応を組み合わせて合成される。式(1A)で表される化合物の製造方法を以下に示す。
過剰量の式(9)で表されるエポキシ基を有するビニル化合物と式(10)で表されるホスホリルコリン基を有するカルボン酸化合物とのエポキシ基とカルボン酸との反応により、式(11)で表されるホスホリルコリン基と水酸基を有するビニル化合物を合成する。このとき未反応の式(9)化合物はエバポレーター等を用いた濃縮操作で取り除いてもよい。
式(1A)の合成に用いられる、エポキシ基を有するビニル化合物は、式(9)で表される。
式(1A)の合成に用いられる、ホスホリルコリン基を有するカルボン酸化合物は、式(10)で表される。
式(1A)の合成に用いられる、式(11)で表されるホスホリルコリン基と水酸基を有するビニル化合物は、式(9)で表されるエポキシ基を有するビニル化合物と、式(10)で表されるホスホリルコリン基を有するカルボン酸化合物との、エポキシ基とカルボン酸との反応により合成される。
本開示の組成物の例1は、式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマーのうち少なくとも1種類と、親水性モノマーを少なくとも1種類以上含む。
本開示の組成物は、当業者に既知の触媒または開始剤を用いて重合させることが可能である。
本開示の組成物の例1において、式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマーは全量基準で、10~60質量部であり、好ましくは15~55質量部であり、さらに好ましくは25~45質量部である。10質量部未満では、コンタクトレンズの透明性が低下する可能性がある。60質量部超では、本開示の組成物の粘性が高くなり、取り扱いが困難となる可能性がある。
本開示の組成物の例1において、親水性モノマーは全量基準で、20~80質量部であり、好ましくは25~70質量部、さらに好ましくは30~60質量部である。20質量部未満では、コンタクトレンズの親水性が低下する可能性がある。80質量部超では、十分な酸素透過性が得られない可能性がある。
親水性モノマーは、親水性の官能基と重合性のビニル基を有する化合物である。親水性モノマーは、例えば、2-(メタクリロイルオキシエチル)-2-(トリメチルアンモニオエチル)ホスフェート、2-ヒドロキシエチル(メタ)アクリレート、N-ビニルピロリドン、N,N-ジメチルアクリルアミド、2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、N-メチル-N-ビニルアセトアミド、2-ヒドロキシエチル(メタ)アクリルアミド、エチレングリコールモノビニルエーテル、ジエチレングリコールモノビニルエーテルおよびこれらの混合物からなる群より選択することができるが、特に限定されない。
本開示の組成物の例1において、式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー、親水性モノマー以外のその他の成分を含んでも良い。
本開示の組成物のその他の成分として例えば、シロキサンモノマーが挙げられる。シロキサンモノマーを該組成物に添加することにより、組成物重合物の酸素透過性や力学的特性を向上することが可能である。シロキサンモノマーは、シロキサンおよびビニル基を含む化合物であれば特に限定されないが、例えば、メタクリル酸2-ヒドロキシ-3-[3-[メチルビス(トリメチルシロキシ)シリル]プロポキシ]プロピルや4-(2-ヒドロキシエチル)=1-[3-トリス(トリメチルシロキシ)シリルプロピル]=2-メチリデンスクシネート、メタクリル酸3-[トリス(トリメチルシロキシ)シリル]プロピル、ポリジメチルシロキサンモノメタクリレートなどが挙げられる。
シロキサンモノマーは、モノマー全量基準で、通常5質量部~40質量部、好ましくは、8質量部~30質量部、より好ましくは10質量部~25質量部含まれる。
本開示の組成物のその他の成分として、例えば、架橋剤が挙げられる。架橋剤は、当業者に公知であり、例えば、テトラ(エチレングリコール)ジ(メタ)アクリレート、トリ(エチレングリコール)ジ(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、ジ(エチレングリコール)ジ(メタ)アクリレート、グリセロールジメタクリレート、アリル(メタ)アクリレート、N,N’-メチレンビス(メタ)アクリルアミド、N,N’-エチレンビス(メタ)アクリルアミド、N,N’-ジヒドロキシエチレンビス(メタ)アクリルアミド、イソシアヌル酸トリアリル、テトラエチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル、ジエチレングリコールジビニルエーテル、エチレングリコールジビニルエーテル、トリメチロールプロパントリ(メタ)アクリレート、およびそれらの組合せからなる群から選択される。架橋剤は組成物全量基準で通常0.1~5質量部、好ましくは0.3~3質量部、より好ましくは0.5~2質量部含まれる。
本開示の組成物の例1において、式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマーを100質量部とすると、1種類以上の親水性モノマーを33~800質量部、1種類以上のシロキサンモノマーを8~400質量部とすることもできる。
本開示の組成物の例2は、式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマーのうち少なくとも1種類、親水性モノマーを少なくとも1種類以上、親水性ポリマーを少なくとも1種類以上含む。
または、本開示の組成物の例2は、式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマーのうち少なくとも1種類と、親水性モノマーの少なくとも1種類以上、親水性ポリマーの少なくとも1種類以上、水酸基含有シロキサンモノマーの少なくとも1種類以上含む。
本開示の組成物の例2は、当業者に既知の触媒または開始剤を用いて重合させることが可能である。
本開示の組成物の例2において、水酸基含有シロキサンモノマーは、モノマー全量基準で、通常20質量部~90質量部、好ましくは、40質量部~80質量部含まれる。
親水性モノマーは、親水性の官能基と重合性のビニル基を有する化合物である。親水性モノマーは、例えば、2-ヒドロキシエチル(メタ)アクリレート、N-ビニルピロリドン、N,N-ジメチルアクリルアミド、2-(メタクリロイルオキシエチル)-2-(トリメチルアンモニオエチル)ホスフェート、2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、N-メチル-N-ビニルアセトアミド、およびこれらの混合物からなる群より選択することができるが、特に限定されない。
親水性ポリマーは、ポリアミド、ポリラクタム、ポリイミドおよびポリラクトンを例示することができる。好ましくは、これらは水性の環境内において水に対する水素結合により効果的にさらに親水性になる水素結合の受容体である。
本開示の組成物の例2において、式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー、親水性モノマーおよび親水性ポリマー以外のその他の成分を含んでもよい。
シロキサンモノマーもしくは水酸基含有シロキサンモノマーは、モノマー全量基準で、通常5質量部~50質量部、好ましくは、10質量部~40質量部、より好ましくは15質量部~30質量部含まれる。
本開示の組成物の例2において、式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマーを100質量部とすると、1種類以上の親水性モノマーを40~1800質量部、1種類以上の親水性ポリマーを0.2~300質量部、1種類以上のシロキサンモノマーを40~1800質量部とすることもできる。
式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー、N,N-ジメチルアクリルアミド(DMAA)、2-ヒドロキシブチルメタクリレート(HBMA)、N-ビニルピロリドン(NVP)およびポリビニルピロリドン(PVP)
式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー、DMAA、2-ヒドロキシエチルメタクリレート(HEMA)、NVPおよびPVP
式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー、DMAA、HBMA、NVP、2-(メタクリロイルオキシエチル)-2-(トリメチルアンモニオエチル)ホスフェート(MPC)およびPVP
式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー、DMAA、2-ヒドロキシプロピルメタクリレート(HPMA)、NVPおよびPVP
式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー、DMAA、HPMA、NVP、N-メチル-N-ビニルアセトアミド(MVA)およびPVP
式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー、DMAA、HBMA、NVPおよび4-(2-ヒドロキシエチル)=1-[3-トリス(トリメチルシロキシ)シリルプロピル]=2-メチリデンスクシネート(ETS)
式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー、DMAA、HEMA、NVPおよびETS
式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー、DMAA、HBMA、NVP、MPCおよびメタクリル酸2-ヒドロキシ-3-[3-[メチルビス(トリメチルシロキシ)シリル]プロポキシ]プロピル(SiGMA)
式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー、DMAA、HPMA、NVPおよびETS
式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー、DMAA、HPMA、NVP、MVAおよびETS
式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー、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(TRIS)、MPC、HBMA及びNVP
式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー、ETS、MPC、HEMA及びNVP
式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー、ETS、MPC、HBMA及びNVP
式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー、ETS、MPC、HBMA及びNVP
式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー、片末端メタクリロイルオキシプロピルポリジメチルシロキサン(MCR-M11)、SiGMA、MPC、HBMA及びNVP
式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー、TRIS、MPC、HEMA及びNVP
式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー、SiGMA、MPC、HBMA及びNVP
式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー、SiGMA、MPC、HEMA及びNVP
式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー、MCR-M11、SiGMA、MPC、HEMA及びNVP
式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー、MCR-M11、MPC、HBMA及びNVP
式(1A)で表されるホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマー、MCR-M11、MPC、HEMA及びNVP
本開示の式(1A)で表される化合物の構成例は、下記表1に例示するが、特に限定されない。
加えて、表1に記載のR1、W1、b、c、A0のX1、Y、Zは、それぞれ、他の組み合わせと変更して、本開示の式(1A)で表される化合物を構成しても良い。
本開示の重合物は、本開示の組成物の重合により得ることが可能であるが、重合においては、任意の溶剤、重合のラジカル開始剤としての任意の熱開始剤や光開始剤を使用することができる。
本開示の組成物の例1の場合、溶剤を配合しないのがより好ましい。
洗浄用に用いる溶媒は、医薬用、医薬部外品用、医療機器用の品質を備えたものであれば、いずれも用いることができる。
本開示の眼科デバイスは、本開示の重合物から実質的に構成させるまたは本開示の重合物を含む。なお、本開示での眼科デバイスとは、コンタクトレンズ、ソフトコンタクトレンズ、ハードコンタクトレンズ、眼内レンズおよび人工角膜を含むが、特に限定されない。
測定装置:日本電子社製JNM-AL400
溶媒:DMSO-d6
緩和時間:15秒
積算回数:32回
[合成例1-1]式(6A)で表される化合物の合成
メタクリル酸3-(クロロジメチルシリル)プロピル 10.8g(49.4mmol)を、テトラヒドロフラン 43.6gに溶解させて、水酸化リチウム 2.36g(98.5mmol)を添加した。30分経過後、ヘプタン 43.6gを添加して加圧ろ過を行い、不溶物を取り除いた。(この反応により、ビニル基を有するシラノール基含有化合物を得た。)
前記加圧ろ過のろ液に、テトラヒドロフラン 71.2gを添加して、ヘキサメチルシクロトリシロキサン 22.0g(98.8mmol){式(6A)中のa=6に相当量}を添加した。続いて、触媒溶液(別のフラスコで、ジアザビシクロウンデセン0.74gをテトラヒドロフラン7.52gに溶解させて調製した) 全量を添加した。4時間経過後、トリエチルアミン 6.60gを添加し、クロロジメチルシラン 5.14gを添加して反応を停止させた。
反応後の溶液をエバポレーターにて濃縮して、ヘプタンで希釈したのちにイオン交換水を用いて洗浄した。ヘプタン層を回収して、硫酸ナトリウムを用いて脱水を行い、最後にエバポレーターにて濃縮することで、式(6A){R1:-CH3、W1:-O-、a:6}で表される化合物を26.2g得た。
合成例1-1と同様の手法で、ヘキサメチルシクロトリシロキサンの仕込み量を変更させることで、下記の通り合成例1-2~合成例1-4の式(6A)化合物を得た。
合成例1-2 式(6A){R1:-CH3、W1:-O-、a:12}
合成例1-3 式(6A){R1:-CH3、W1:-O-、a:19}
合成例1-4 式(6A){R1:-CH3、W1:-O-、a:48}
合成例1-1にて得られた式(6A){R1:-CH3、W1:-O-、a:6}で表される化合物 3.00g、アリルグリシジルエーテル 0.81gをトルエン 7.07gに溶解させたのちに、10重量%のキシレン溶液に調整したKarstedt触媒(東京化成工業社製) 18μL加えて終夜でヒドロシリル化反応を行った。活性炭を0.01g加えて30分間攪拌を行い、加圧ろ過で活性炭を取り除き、エバポレーターで濃縮した。
続いて、特開2017-88530にも記載されている、本明細書の式(10){式(10)中、Y:式(3)、Z:式(5)}化合物 2.87gを添加して、メタノール5.31g、2-プロパノール 5.31g、トリエチルアミン0.29g添加後、昇温して還流状態で終夜反応(エポキシ基とカルボン酸との反応)を行った。
1H NMR分析により式(1A){R1:-CH3、W1:-O-、a:6、A0中、X1:-CH2CH2CH2-O-CH2-、Y:式(3)、Z:式(5)}であることが確認された。実施例1-1の合成結果を表1に示す。
1H NMR ( DMSO-d6) : δ = 0.0ppm(i)、0.5ppm(h,j)、1.6~1.7ppm(g,k)、1.9ppm(e)、3.2ppm(t)、3.3~3.8ppm(l,m,o,s)、4.0~4.5ppm(f,n,r)、5.6ppm,6.1ppm(d)、5.8ppm(u)、7.3ppm(q)、8.0ppm(p)
特開2013-234160にも記載されている、本明細書の式(10){式(10)中、Y:式(4)、R3:-CH3、X2:-CH3、Z:式(5)}化合物 3.67g、アリルグリシジルエーテル 1.21g、メタノール 3.76g、2-プロパノール 3.76g、トリエチルアミン 0.29g添加後、昇温して還流状態で終夜反応を行った。反応後、加圧ろ過にて不溶部を取り除き、エバポレーターを用いて濃縮を行った。
続いて、合成例1-1にて得られた式(6A)で表される化合物 3.00g、2-プロパノール 7.02g、4重量%の2-プロパノール溶液に調整した塩化白金触媒 72μLを加えて終夜で反応を行った。活性炭 0.05gを加えて30分間攪拌を行い、加圧ろ過で活性炭を取り除き、エバポレーターで濃縮した。
イオン交換水 21.4g、2-プロパノール 7.12g、ヘプタン 21.4gを混合し、攪拌した。静置後2層に分離し、下層を廃棄した。その後、イオン交換水、2-プロパノール、ヘプタン混合、攪拌と下層廃棄を2回繰り返し、エバポレーターにて濃縮を行い、透明の粘性物4.57gを得た。
1H NMR分析により式(1A){R1:-CH3、W1:-O-、a:6、A0中、X1:-CH2CH2CH2-O-CH2-、Y:式(4)、R3:-CH3、X2:-CH3、Z:式(5)}であることが確認された。実施例1-2の合成結果を表1に示す。
1H N M R ( DMSO-d6): δ = 0.0ppm(i)、0.5~0.6ppm(h,j)、1.2ppm(s)、1.6~1.7ppm(g,k)、1.9ppm(e)、2.6~2.9ppm(q,r)、3.2ppm(x)、3.3~3.8ppm(l,m,o,p,w)、3.9~4.7ppm(f,n,t,u,v)、5.6ppm,6.1ppm(d)、5.8ppm(y)
実施例1-1と同様の手法で、式(10)で表されるホスホリルコリン基を有するカルボン酸化合物を特開2005-187956に記載の式(10){Y:-CH2-、Z:式(5)}を使用して、合成反応を行うことで、式(1A){R1:-CH3、W1:-O-、a:6、A0中、X1:-CH2CH2CH2-O-CH2-、Y:-CH2-、Z:式(5)}が得られた。実施例1-3の合成結果を表1に示す。
実施例1-1と同様の手法で、合成例1-2で得られた式(6A)化合物と、アリルグリシジルエーテルではなく、1,2-エポキシ-5-ヘキセンを用いて同様に反応を行うことで、式(1A){R1:-CH3、W1:-O-、a:12、A0中、X1:-CH2CH2CH2CH2-、Y:式(3)、Z:式(5)}を得た。実施例1-4の合成結果を表1に示す。
実施例1-1と同様の手法で、合成例1-3で得られた式(6A)化合物を用いて同様に反応を行うことで、式(1A){R1:-CH3、W1:-O-、a:19、A0中、X1:-CH2CH2CH2-O-CH2-、Y:式(3)、Z:式(5)}を得た。実施例1-5の合成結果を表1に示す。
実施例1-1と同様の手法で、合成例1-4で得られた式(6A)化合物を用いて同様に反応を行うことで、式(1A){R1:-CH3、W1:-O-、a:48、A0中、X1:-CH2CH2CH2-O-CH2-、Y:式(3)、Z:式(5)}を得た。実施例1-6の合成結果を表1に示す。
式(1A)比較化合物として、MCR-M11{Gelest社製 片末端メタクリロイルオキシプロピルポリジメチルシロキサン(分子量≒900)}を用意した。用意した式(1A)比較化合物は、製品カタログから、式(1A)中のR1:-CH3、W1:-O-、a:約9に相当して、A0部分が-CH2CH2CH2CH3に置換された化合物であった。
合成例1-3にて得られた式(6A)で表される化合物 3.00g、1-ヘキセン 0.24gをトルエン 6.45gに溶解させたのちに、10重量%のキシレン溶液に調整したKarstedt触媒(東京化成工業社製) 10μLを加えて終夜で反応を行った。活性炭 0.01gを加えて30分間攪拌を行い、加圧ろ過で活性炭を取り除くことで、式(1A)中のR1:-CH3、W1:-O-、a:19に相当して、A0部分が-CH2CH2CH2CH2CH2CH3に置換された式(1A)比較化合物 3.01gが得られた。合成例1-6の合成結果を表1に示す。
合成例1-2にて得られた式(6A)で表される化合物 3.00g、3-ブテン-1-オール 0.47gをトルエン 6.45gに溶解させたのちに、10重量%のキシレン溶液に調整したKarstedt触媒(東京化成工業社製) 10μLを加えて終夜で反応を行った。活性炭 0.01gを加えて30分間攪拌を行い、加圧ろ過で活性炭を取り除くことで、式(1A)中のR1:-CH3、W1:-O-、a:12に相当して、A0部分が-CH2CH2CH2CH2OHに置換された式(1A)比較化合物 3.12gが得られた。合成例1-7の合成結果を表1に示す。
〇実施例2および比較例2で用いた成分
ホスホリルコリン基と水酸基を有するポリジメチルシロキサン含有モノマーとその比較化合物以外の実施例2および比較例で使用した組成物の成分を以下に示す。
DMAA:N,N-ジメチルアクリルアミド
HEMA:2-ヒドロキシエチルメタクリレート
HPMA:2-ヒドロキシプロピルメタクリレート(2-ヒドロキシプロピルエステル、2-ヒドロキシ-1-メチルエチルエステル混合物)
HBMA:2-ヒドロキシブチルメタクリレート
NVP:N-ビニルピロリドン
MVA:N-メチル-N-ビニルアセトアミド
MPC:2-(メタクリロイルオキシエチル)-2-(トリメチルアンモニオエチル)ホスフェート
ETS:4-(2-ヒドロキシエチル)=1-[3-トリス(トリメチルシロキシ)シリルプロピル]=2-メチリデンスクシネート
SiGMA:メタクリル酸2-ヒドロキシ-3-[3-[メチルビス(トリメチルシロキシ)シリル]プロポキシ]プロピル
PVP K90:ポリビニルピロリドン K90(富士フィルム和光純薬社製)
TEGDMA:テトラエチレングリコールジメタクリレート
HexOH:1-ヘキサノール
AIBN:2,2’-アゾビス(イソブチロニトリル)
実施例2および比較例2における評価方法は以下の通りである。
重合を行う前の組成物に均一性を以下の方法にて評価した。
調整した組成物を無色透明な容器に入れ、目視により以下の基準にてスコアを与えて評価した。
1:組成物が均一で透明である
2:組成物が不均一もしくは、白濁や沈殿物等がみられる。
「1」のスコアが与えられたものは重合工程を行い、重合物透明性、抗脂質付着性を評価した。「2」のスコアが与えられたものは以降の重合工程および、重合物透明性、抗脂質付着性の評価を実施しなかった。
組成物を重合して得られた重合物の透明性を以下の方法にて評価した。
重合物を生理食塩水中に一晩浸漬し、無風の室内にて、重合物をこの生理食塩液から取り出して照明にかざし、目視にて外観を観察し、以下の基準にてスコアを与えて評価した。
1 : 濁りがなく透明
2 : かすかに白濁
3 : 若干白濁があり半透明
4 : 白濁があり透明性が全くない
5 : 完全に白い
実施例で作製した重合物の抗脂質付着性を以下の手順で評価した。
まず、人工脂質を下記に記載の方法で調製した。続いて、生理食塩水中で一晩浸漬させた重合物を4mLの人工脂質に4時間浸漬させた後に、生理食塩水で軽くすすぎ、水気を取り除いて、目視にて外観を確認し、以下の基準にてスコアを与えて評価した。
1 : 白濁が無く透明である
2 : 白濁した部分がわずかにある
3 : 一部が白濁している
4 : 大部分が白濁している
5 : 全体が白濁している
1)以下に示す組成の混合脂質0.5gを、以下に示すリン酸・ホウ酸緩衝溶液100mLに混合した。
2)60℃でホモミキサーを用いて懸濁した。
3)1N塩酸でpH=7.0に調整した。
混合脂質の組成
オレイン酸 0.06g
リノレン酸 0.06g
パルミチン酸 0.06g
トリパルミチン酸 0.81g
セチルアルコール 0.20g
ミリスチン酸セチル 0.81g
コレステロール 0.08g
パルミチン酸コレステロール 0.08g
レシチン(卵由来) 2.83g
リン酸・ホウ酸緩衝液の組成
塩化ナトリウム 2.25g
リン酸二水素カリウム 1.25g
四ホウ酸ナトリウム・十水和物 5.65g
イオン交換水 全量を250mLとする
参考文献 岩井薫、森山摩里、今安正樹、田中英成:コンタクトレンズに関する脂質付着性に関する研究、日コレ誌、37、58-61、1995
コンタクトレンズの濡れ性はWBUT(Water-film Break Up Time)で評価した。ピンセット等を用いて、実施例のコンタクトレンズ状の重合物を生理食塩水中からゆっくり取り出し、水膜が切れるまでの時間を測定した。これをWBUTとし、以下の基準にてスコアを与えて評価した。
1:10秒以上
2:5秒以上、10秒未満
3:5秒未満
防汚性の評価として、以下に示す手順でコーティング性を評価した。
<コーティング性評価方法>
スーダンブラックB0.05gをトコフェロール10gに溶解させ、流動パラフィン40gを加えて均一に混合して、これを染色液とした。実施例のコンタクトレンズ状の重合物をガラスバイアルから取り出し、レンズ表面の水分を拭き取り、1mLの染色液に5分間浸漬させた。該重合物を取り出し、余分な染色液は生理食塩液と生理食塩液で湿らせた清浄な布で除去した。染色液で染色した実施例のコンタクトレンズ状の重合物を生理食塩液1.5mLに浸漬し、600nmの吸光度を測定した。染色前の実施例のコンタクトレンズ状の重合物の吸光度をA0、染色後の実施例のコンタクトレンズ状の重合物の吸光度をA1とした。
以下の式(1)に従い、染色により増加した吸光度を算出し、以下の基準にてスコアを与えて評価した。
吸光度=A1-A0 ・・・式(A)
1:0.05未満
2:0.05以上、0.10未満
3:0.10以上、0.15未満
4:0.15以上、0.2未満
5;0.2以上
実施例1-1で得られた式(1A)化合物 20.0質量部、DMAA 10.0質量部、HBMA 10.0質量部、NVP 30.0質量部、SiGMA 30.0質量部、PVP K90 5.00質量部、TEGDMA 1.00質量部、およびHexOH 30.0質量部を混合した。続いて、AIBN 0.50質量部を添加、混合して組成物を作製した。
得られた組成物について組成物均一性の評価を行ったところ、スコア「1」が与えられた。
続いて、前記組成物をコンタクトレンズ用モールドへと分注し、オーブン内へ置いた。オーブン内の窒素置換を行った後、100℃まで昇温し該温度で2時間維持し、組成物を重合させて重合物を得た。
上記重合物をモールドから取り出し、2-プロパノール40gに4時間浸漬した後、イオン交換水50gに4時間浸漬して未反応物等を除去して精製した。さらに重合物をISO-18369-3に記載の生理食塩水に浸漬し、コンタクトレンズ状の重合物を得た。
前記コンタクトレンズ状の重合物について、重合物透明性の評価を行ったところ「1」のスコアが与えられ、抗脂質付着性の評価を行ったところ「1」の評価が与えられた。実施例2-1の結果を表2に示す。
表2に示す組成に従ったこと以外は実施例2-1と同様にして実施例2-2~実施例2-6を行った。実施例2-1と同様に組成物均一性、重合物透明性、抗脂質付着性の評価を行った。
実施例2-2~実施例2-6の評価結果を表2に示す。
表2に示す組成に従い式(1A)で表される化合物 20.0質量部の代わりに合成例1-5で用意した式(1A)比較化合物 20.0質量部を用いたこと以外は、実施例2-1と同様にして比較例2-1を行った。実施例2-1と同様に組成物均一性、重合物透明性、抗脂質付着性の評価を行ったところ、組成物均一性は「1」、重合物透明性は「1」、抗脂質付着性は「5」のスコアが与えられた。比較例2-1の評価結果を表2に示す。
表2に示す組成に従い式(1A)で表される化合物 20.0質量部の代わりに合成例1-6で合成した式(1A)比較化合物 20.0質量部を用いたこと以外は、実施例2-1と同様に組成物を作製した。
得られた組成物について組成物均一性の評価を行ったところ、「2」のスコアが与えられた。そのため、以降の重合工程および、重合物透明性、抗脂質付着性の評価を実施しなかった。比較例2-2の評価結果を表2に示す。
表2に示す組成に従い式(1A)で表される化合物 20.0質量部の代わりに合成例1-7で合成した式(1A)比較化合物 20.0質量部を用いたこと以外は、実施例2-1と同様にして比較例2-3を行った。実施例2-1と同様に組成物均一性、重合物透明性、抗脂質付着性の評価を行ったところ、組成物均一性は「1」、重合物透明性は「4」、抗脂質付着性は「4」のスコアが与えられた。比較例2-3の評価結果を表2に示す。
実施例2-1~実施例2-3は、いずれも組成物均一性にて「1」、重合物透明性にて「1」のスコアが与えられたことから、親水性モノマーや親水性ポリマーとの非常に良好な相溶性を示した。
実施例2-4~実施例2-6は、いずれも組成物均一性にて「1」、重合物透明性にて「2」のスコアが与えられたことから、親水性モノマーや親水性ポリマーとの十分良好な相溶性を示した。
実施例2-1~実施例2-4は、いずれも抗脂質付着性にて「1」のスコアが与えられたことから、非常に高い抗脂質付着性を示した。
実施例2-5は、抗脂質付着性にて「2」のスコアが与えられたことから、高い抗脂質付着性を示した。
実施例2-6は、抗脂質付着性にて「3」のスコアが与えられたことから、抗脂質付着性を示した。
以上の結果より、実施例2-1~実施例2-6で用いられた式(1A)で表される化合物が、親水性モノマーや親水性ポリマーとの良好な相溶性と重合物への抗脂質付着性の付与を同時に示すことが確認された。
比較例2-2は、組成物均一性にて「2」のスコアが与えられ、親水性モノマーや親水性ポリマーとの良好な相溶性を示さなかった。
比較例2-3は、組成物均一性にて「1」のスコアが与えられたものの、重合物透明性にて「4」のスコアが与えられ、親水性モノマーや親水性ポリマーとの良好な相溶性を示さなかった。また、抗脂質付着性にて「4」のスコアが与えられたことから、抗脂質付着性を示さなかった。
以上の結果より、比較例2-1~比較例2-3で用いられた式(1A)比較化合物は、親水性モノマーや親水性ポリマーとの良好な相溶性と抗脂質付着性を同時に示さなかった。
実施例1-1で得られた式(1A)化合物 2.00g(40.0質量部)、TRIS 1.00g(20.0質量部)、MPC 0.50g(10.0質量部)、HBMA 1.10g(22.0質量部)を容器中で混合し、室温下で、MPCが溶解するまで撹拌した。さらに、NVP 0.4g(8.0質量部)、TEGDMA 0.05g(1.0質量部)、AIBN 0.025g(0.5質量部)を容器に添加し、室温下で、均一になるまで撹拌して組成物を得た。
得られた組成物について組成物均一性の評価を行ったところ、スコア「1」が与えられた。続いて、前記組成物をコンタクトレンズ用モールドへと分注し、オーブン内へ置いた。オーブン内の窒素置換を行った後、オーブン内を80℃まで昇温し、80℃で12時間維持することで組成物を重合させて重合体を得た。
各重合体をセルから取り出し、重合体を得た。重合体を50質量%2-プロパノール水溶液100mLに4時間浸漬後、イオン交換水100mLに4時間浸漬して未反応物等を除去して精製した。精製後の重合体を、ISO-18369-3に記載の生理食塩水中に浸漬し、膨潤(水和)させてコンタクトレンズ状の重合物を得た。前記コンタクトレンズ状の重合物について、各評価を行った。組成物中の各成分の配合割合、重合条件、および各評価結果を表3に示す。
組成物中の各成分の配合割合、および重合条件を表3に記載の通りとした以外は、実施例1と同様にして、コンタクトレンズ状の重合物を得た。実施例3-1と同様に各評価を行った。結果を表3に示す。
実施例3-2に関し、UV-LED照射器(照射光波長 405nm)で室温下、1.5mW/cm2の放射照度で、30分間UV照射することで組成物を重合させて重合体を得た。
組成物中の各成分の配合割合、および重合条件を表3に記載の通りとした以外は、実施例1と同様にして、コンタクトレンズ状の重合物を得た。実施例3-1と同様に各評価を行った。結果を表3に示す。
比較例3-1に関し、得られた組成物について組成物均一性の評価を行ったところ、「2」のスコアが与えられた。そのため、以降の重合工程および、各評価を実施しなかった。
比較例3-3に関し、得られた重合物について重合物透明性の評価を行ったところ、「2」のスコアが与えられた。そのため、以降の各評価を実施しなかった。
I-189:Bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide
EtOH:エタノール
NPA:1-プロパノール(ノルマルプロピルアルコール)
実施例3-1~実施例3-4は、いずれも組成物均一性にて「1」、重合物透明性にて「1」のスコアが与えられたことから、親水性モノマーとの非常に良好な相溶性を示した。
実施例3-1~実施例3-4は、いずれも濡れ性評価(親水性評価)にて「1」のスコアが与えられたことから、非常に高い親水性を示した。
実施例3-1~実施例3-3は、いずれも防汚性評価(コーティング性評価)にて「1」のスコアが与えられたことから、非常に高いコーティング性を示した。実施例3-4は、防汚性評価(コーティング性評価)にて「2」のスコアが与えられたことから、高いコーティング性を示した。
以上の結果より、実施例3-1~実施例3-4で用いられた式(1A)で表される化合物が、親水性モノマーとの良好な相溶性と重合物への親水性の付与及びコーティング性の付与を同時に示すことが確認された。
比較例3-2は、防汚性評価(コーティング性評価)にて「5」のスコアが与えられたことから、コーティング性を示さなかった。
(1)親水性モノマーや親水性ポリマーとの相溶性が良好である。
(2)本モノマー、親水性モノマーおよび親水性ポリマーを含む組成物を重合した重合物は透明性かつ抗脂質付着性を有する。
(3)本モノマー及び親水性モノマーを含む組成物を重合した重合物は透明性かつ表面処理なしで優れた表面親水性及びコーティング性を有する。
Claims (12)
- 式(1A)で表される化合物。
- 式(1A)で表される化合物の製造方法であって、
式(6A)で表される化合物とエポキシ基を有するビニル化合物とのヒドロシリル化反応、さらに該反応後の化合物のエポキシ基とホスホリルコリン基を有するカルボン酸化合物のカルボン酸との反応、または、
エポキシ基を有するビニル化合物のエポキシ基とホスホリルコリン基を有するカルボン酸化合物のカルボン酸との反応、さらに該反応後のホスホリルコリン基と水酸基を有するビニル化合物と式(6A)で表される化合物とのヒドロシリル化反応により、
式(1A)を合成する工程を含む製造方法。
- 式(6A)で表される、末端にヒドロシランを有するポリジメチルシロキサン含有モノマーの製造方法であって、
式(7)で表されるクロロシラン化合物を金属水酸化物により式(7A)で表されるシラノール化合物に変換し、次に、
有機塩基存在下、環状シロキサンおよびクロロシラン化合物の反応により、式(6A)で表される末端にヒドロシランを有するポリジメチルシロキサン含有モノマーを合成する工程を含む製造方法。
- 以下式(1A)で表される化合物と、親水性モノマーを1種類以上含む組成物。
- 以下式(1A)で表される化合物、親水性モノマーを1種類以上、親水性ポリマーを1種類以上含む組成物。
- 以下式(1A)で表される化合物、親水性モノマーを1種類以上、シロキサンモノマーを1種類以上含む組成物。
- 前記親水性モノマーが2-(メタクリロイルオキシエチル)-2-(トリメチルアンモニオエチル)ホスフェートであることを特徴とする、請求項4~6のいずれか1に記載の組成物。
- 以下式(1A)で表される化合物、親水性モノマーを1種類以上、水酸基含有シロキサンモノマーを1種類以上、親水性ポリマーを1種類以上含む組成物。
- 前記親水性ポリマーがポリアミド、ポリラクタム、ポリイミド、ポリラクトン、およびポリデキストランから成る群から1以上選択される、請求項5又は8のいずれか1に記載の組成物。
- 前記親水性ポリマーがポリビニルピロリドンである、請求項5又は8のいずれか1に記載の組成物。
- 請求項4~6及び8のいずれか1に記載の組成物を重合して得られた重合物。
- 請求項11に記載の重合物を含む眼科デバイス。
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