WO2013024801A1 - 医療デバイスおよびその製造方法 - Google Patents
医療デバイスおよびその製造方法 Download PDFInfo
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- WO2013024801A1 WO2013024801A1 PCT/JP2012/070437 JP2012070437W WO2013024801A1 WO 2013024801 A1 WO2013024801 A1 WO 2013024801A1 JP 2012070437 W JP2012070437 W JP 2012070437W WO 2013024801 A1 WO2013024801 A1 WO 2013024801A1
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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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/34—Macromolecular materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00009—Production of simple or compound lenses
- B29D11/00038—Production of contact lenses
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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
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
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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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/10—Materials for lubricating medical devices
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/02—Methods for coating medical devices
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/08—Coatings comprising two or more layers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/16—Materials or treatment for tissue regeneration for reconstruction of eye parts, e.g. intraocular lens, cornea
Definitions
- the present invention relates to a medical device and a manufacturing method thereof.
- a medical device is a soft contact lens (soft eye lens).
- Soft contact lens soft eye lens
- a commercially available soft contact lens generally uses a hydrogel material having a moisture content of about 25% to about 80%.
- a hydrous soft contact lens made of a hydrogel material contains water, a phenomenon occurs in which water evaporates from the contact lens. As a result, a certain percentage of contact lens wearers may feel more uncomfortable and feel uncomfortable than when they are naked. Some complained of symptoms called contact lens dry eye.
- hydrous soft contact lenses made of hydrogel materials are easily contaminated by components in tear fluid, and also contain a large amount of water, so there is also a risk of bacterial propagation.
- a platinum-based catalyst is added to a mixture of polydimethylsiloxane and methylhydrogenpolysiloxane having both molecular chain ends blocked with vinylmethylsilyl groups, A silicone rubber lens obtained by a method of heat-curing by a molding method is known (see Patent Document 1).
- Patent Documents 2 to 7 describe contact lens materials having high oxygen permeability mainly composed of polysiloxane having a plurality of polymerizable functional groups and TRIS type polysiloxane having a polymerizable functional group at one end.
- Patent Document 6 discloses a contact lens material made of a polymer obtained by copolymerizing a bifunctional organosiloxane macromer alone or with another monomer, and as a monomer used for copolymerization, Acrylic acid fluoroalkyl esters or methacrylic acid fluoroalkyl esters, and acrylic acid alkyl esters or methacrylic acid alkyl esters are disclosed.
- silicone rubber lenses are widely used because they have defects such as peeling of the hydrophilic treatment layer applied to improve the hydrophobicity of the lens surface, and sticking to the cornea due to excessive elasticity. It was not reached until it was made.
- a material mainly composed of polysiloxane having a plurality of polymerizable functional groups has high oxygen permeability and flexibility, and is considered to be one of materials suitable for contact lenses.
- the adhesiveness remains on the surface of the lens after polymerization, there is a concern that the lens surface adheres to the cornea, and the balance between mechanical properties such as flexibility and bending resistance of the lens is insufficient.
- Patent Document 7 discloses a polymer containing alkoxysilane and a silicone monomer as constituents as a material for a non-hydrous soft contact lens.
- alkoxysilane generally tends to undergo hydrolysis and condensation, and when condensation occurs, it functions as a cross-linking agent, so that the elastic modulus is increased.
- the contact lens becomes hard and the wearing feeling deteriorates.
- the silicone monomer when the silicone part has a branched structure, there is a problem that the shape recoverability of the contact lens is lowered when the content of the silicone monomer is increased.
- a method of coating and laminating two or more layers of polymer materials one by one is known (for example, Patent Documents). 8-10).
- a method of alternately coating two polymer materials having opposite charges one by one is called an LbL method or the like, and each layer of material is non-covalently bonded to another layer of a different material. It is considered.
- the high oxygen-permeable soft ophthalmic lens that clearly shows the usefulness of this method is only of a silicone hydrogel material, and its usefulness for a low hydrous soft ophthalmic lens has not been known.
- the conventional LbL coating is performed in multiple layers such as about 4 to 20 layers, which may increase the manufacturing process and increase the manufacturing cost.
- the present invention has been made in view of the above, and provides a medical device that is excellent in wettability and slipperiness, greatly reduces or avoids the phenomenon of sticking to the cornea and the like during wearing, and is soft and difficult to tear. With the goal.
- Another object of the present invention is to manufacture a medical device at a low cost by a simple process.
- the present invention has the following configuration.
- the present invention relates to a medical device in which a layer composed of an acidic polymer and a basic polymer is formed on at least a part of the surface of a low hydrous soft substrate, wherein the low hydrous soft substrate is 1 per molecule.
- a copolymer containing a monofunctional monomer component M having a polymerizable functional group and a silicone moiety is a main component.
- the number average molecular weight of the monofunctional monomer component M is preferably 300 to 120,000.
- the monofunctional monomer component M is preferably selected from the components represented by the following formula (M1).
- X 3 represents a polymerizable functional group.
- R 11 to R 19 each independently represents a substituent selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, a phenyl group, and a fluoroalkyl group having 1 to 20 carbon atoms.
- L 3 represents a divalent group.
- c and d each independently represents an integer of 0 to 700. However, c and d are not 0 at the same time.
- the substrate is (1) a copolymer comprising the component M and the following component A; or (2) a copolymer comprising the component M, the following component A and component B; Is preferably the main component;
- Component A a polysiloxane compound having a plurality of polymerizable functional groups per molecule and having a number average molecular weight of 6000 or more;
- Component B a polymerizable monomer having a fluoroalkyl group.
- the present invention is also a method for producing a medical device comprising the following steps 1a to 3a in this order; ⁇ Step 1a> Polymerizing a mixture containing component M, which is a monofunctional monomer having one polymerizable functional group per molecule and a silicone moiety, to obtain a molded body; ⁇ Step 2a> A step of washing and removing excess basic polymer solution after contacting the molded body with the basic polymer solution; ⁇ Step 3a> A step of washing and removing excess acidic polymer solution after bringing the molded body into contact with the acidic polymer solution.
- the present invention is a method for manufacturing a medical device including the following steps 1b to 4b in this order; ⁇ Step 1b> Polymerizing a mixture containing component M, which is a monofunctional monomer having one polymerizable functional group per molecule and a silicone moiety, to obtain a molded body; ⁇ Step 2b> A step of washing and removing excess acidic polymer solution after contacting the molded body with the acidic polymer solution; ⁇ Step 3b> A step of washing and removing excess basic polymer solution after contacting the molded body with the basic polymer solution; ⁇ Step 4b> A step of washing and removing excess acidic polymer solution after bringing the molded body into contact with the acidic polymer solution.
- the medical device of the present invention is excellent in slipperiness and wettability, the phenomenon of sticking to the cornea at the time of wearing, which has been a problem in conventional low hydrous soft ophthalmic lenses, can be greatly reduced or avoided. Moreover, since the medical device of the present invention has a low water content, it can reduce the risk of bacterial growth. Furthermore, the medical device of the present invention has an effect of exhibiting excellent mechanical properties that are not found in conventional medical devices, which are both soft and difficult to break by making the elastic modulus and elongation of the base material within desired ranges. . Moreover, the medical device of this invention has the effect that it is excellent in shape recovery property, when stress zero time falls.
- FIG. 1 is a schematic diagram illustrating an apparatus for measuring a surface friction coefficient of a sample of a medical device according to an embodiment of the present invention.
- FIG. 1 shows a state in which a standard measuring jig and a friction piece are set.
- FIG. 2 is a schematic diagram showing a configuration of a main part of the measuring jig and the friction element for measuring the surface friction coefficient of the sample of the medical device according to the embodiment of the present invention as seen from the A direction shown in FIG.
- FIG. 3 is a partial cross-sectional view illustrating a configuration of a main part of a measurement jig and a friction element for measuring a surface friction coefficient of a sample of a medical device according to an embodiment of the present invention.
- the medical device used in the present invention refers to a device that is used for medical purposes and is used in contact with a patient or in contact with a tissue collected from the patient, for example, blood or other body fluid.
- a tissue collected from the patient for example, blood or other body fluid.
- Preferable examples include ophthalmic lenses, endoscopes, catheters, infusion tubes, gas transport tubes, stents, sheaths, cuffs, tube connectors, access ports, drainage bags, blood circuits, skin materials or drug carriers.
- low water content means that the water content is 10% by mass or less.
- Soft means that the elastic modulus (tensile elastic modulus) is 10 MPa or less.
- the moisture content is determined by, for example, ⁇ (in the wet state) from the mass of the film-shaped dry test piece (the mass in the dry state) and the mass of the test piece in the wet state (the mass in the wet state). Mass) ⁇ (mass in the dry state) / mass in the wet state ⁇ ⁇ 100.
- the medical device of the present invention has a low water content, when used as an ophthalmic lens, the medical device has a feature that the eye feels dry and the wearer feels excellent. Moreover, since the medical device of the present invention has a low water content, it has an advantage that the risk of bacterial growth is low.
- the moisture content is more preferably 5% or less, further preferably 2% or less, and most preferably 1% or less. If the water content is too high, it is not preferable because the dryness of the eyes of the ophthalmic lens wearer increases and the risk of bacterial growth increases.
- the elastic modulus (tensile elastic modulus) of the medical device of the present invention is preferably 0.01 to 1.0 MPa, more preferably 0.1 to 0.8 MPa, still more preferably 0.1 to 0.7 MPa, 0.2 More preferably, ⁇ 0.6 MPa is more preferable, and 0.2 to 0.55 MPa is most preferable. If the elastic modulus is too small, it tends to be too soft and difficult to handle. If the elastic modulus is too large, it is too hard and the wearing feeling tends to be poor when it comes into contact with the patient's skin or when a lens is attached. An elastic modulus of 1 MPa or less is preferable because a good wearing feeling can be obtained. The elastic modulus is measured on a wet sample.
- the elongation (tensile elongation at break) of the medical device of the present invention is preferably 100% to 1000%, more preferably 200% to 700%. If the elongation is small, the medical device is easily broken, which is not preferable. If the elongation is too large, the medical device tends to be easily deformed, which is not preferable. The elongation is measured on a wet sample.
- the dynamic contact angle (advanced, immersion speed: 0.1 mm / sec) is preferably 100 ° or less, more preferably 90 ° or less. Preferably, it is 80 ° or less. From the viewpoint of preventing the wearer from sticking to the cornea, the dynamic contact angle is preferably lower, preferably 65 ° or less, more preferably 60 ° or less, further preferably 55 ° or less, and 50 ° or less. More preferred is 45 ° or less.
- the dynamic contact angle is measured against a borate buffer in a sample wet with borate buffer.
- the surface has excellent wettability from the viewpoint of familiarity with a living body. From this viewpoint, it is preferable that the liquid film holding time on the surface of the medical device is long.
- the liquid film retention time means that when a medical device immersed in a borate buffer is pulled up from the liquid and held in the air so that the surface (diameter direction in the case of an ophthalmic lens) is vertical, the medical device This is the time during which the liquid film on the surface is held without breaking.
- the liquid film holding time is preferably 5 seconds or longer, more preferably 10 seconds or longer, and most preferably 20 seconds or longer.
- the diameter is the diameter of a circle formed by the edge of the lens. Further, the liquid film retention time is measured on a sample in a wet state with a borate buffer.
- the surface of the medical device has excellent slipperiness from the viewpoint of preventing sticking to the cornea of the wearer. It is preferable to have.
- the surface friction coefficient ratio (Qa and Qb) measured by the method shown in the examples described later is small.
- the surface friction coefficient ratio (Qa) when wetted with a borate buffer is preferably 2 or less, more preferably 1.6 or less, and even more preferably 1 or less.
- Qa MIUa / MIUo
- MIUa represents the surface friction coefficient between the medical device and a smooth quartz glass plate when wetted with a borate buffer.
- MIUo represents the surface friction coefficient between “Accuview (registered trademark) oasis” and a smooth quartz glass plate when wetted with a borate buffer.
- the surface friction coefficient ratio Qa is preferably 1 or less, more preferably 0.8 or less, and most preferably 0.6 or less.
- the surface friction coefficient ratio (Qb) when wet with physiological saline is preferably 3 or less, more preferably 2 or less, and further preferably 1.5 or less.
- Qb MIUb / MIUo
- MIUb represents the surface friction coefficient between the medical device and a smooth quartz glass plate when wet with physiological saline.
- the medical device of the present invention tends to have a larger Qb than Qa, and in some cases, Qb can be very large.
- the physiological saline is a liquid similar to a body fluid (for example, tear fluid in the case of a contact lens), and from the viewpoint of preventing sticking to the biological surface of a medical device (cornea in the case of an ophthalmic lens)
- the surface friction coefficient ratio (Qb) when wet with physiological saline is also preferably small.
- the surface friction coefficient ratio Qb is preferably 1.5 or less, more preferably 1.0 or less, and most preferably 0.8 or less.
- the difference (Qb ⁇ Qa) between the surface friction coefficient ratio Qb when wetted with physiological saline and the surface friction coefficient ratio Qa when wetted with borate buffer is 1.6 or less. Is preferable, 1.3 or less is more preferable, and 1.0 or less is more preferable. If the difference between the surface friction coefficient ratio Qb and the surface friction coefficient ratio Qa is small, the difference between the slipperiness when the medical device is applied to a living body and the slipperiness before application (for example, when opened) tends to be small. Is preferable.
- the medical device of the present invention preferably has high oxygen permeability from the viewpoint of oxygen supply from the atmosphere to the patient's body tissue (eye in the case of an ophthalmic lens).
- the oxygen permeability coefficient [ ⁇ 10 ⁇ 11 (cm 2 / sec) mLO 2 / (mL ⁇ hPa)] is preferably 50 to 2000, more preferably 100 to 1500, still more preferably 200 to 1000, and most preferably 300 to 700. . If the oxygen permeability is excessively increased, other physical properties such as mechanical properties may be adversely affected, which is not preferable.
- the oxygen permeability coefficient is measured on a dry sample.
- the medical device of the present invention preferably has a shape recovery property, for example, a stress zero time of 1.00 seconds or less, more preferably 0.90 seconds or less, and 0.83 seconds or less. Is most preferred.
- the zero stress time is measured by the method described in the Examples on a sample wet with borate buffer.
- the antifouling property of the medical device can be evaluated by mucin adhesion, lipid (methyl palmitate) adhesion, and artificial tears immersion test.
- the mucin adhesion amount is preferably 5 ⁇ g / cm 2 or less, more preferably 4 ⁇ g / cm 2 or less, and most preferably 3 ⁇ g / cm 2 or less.
- the medical device of the present invention includes a lens-shaped or sheet-like molded body (hereinafter referred to as a base material) depending on the intended use, and an acidic polymer and a basic polymer are formed on at least a part of the surface of the base material. A layer is formed.
- a base material a lens-shaped or sheet-like molded body depending on the intended use
- an acidic polymer and a basic polymer are formed on at least a part of the surface of the base material.
- a layer is formed.
- the base material is mainly composed of a copolymer containing a monofunctional monomer component M having one polymerizable functional group and a silicone moiety per molecule.
- component M monofunctional monomer component M having one polymerizable functional group and silicone moiety per molecule
- the main component means a component that is contained in an amount of 50% by mass or more based on the mass of the base material in a dry state (100% by mass).
- the copolymer containing component M means a copolymer obtained by copolymerizing component M and other monomers.
- the silicone part represents an organic group having at least one Si—O—Si bond (siloxane bond).
- the silicone moiety of component M is preferably linear. If the silicone site is linear, the shape recoverability of the resulting medical device is improved.
- the term “linear” refers to a structure represented by a single linearly connected Si— (O—Si) n ⁇ 1 —O—Si bond starting from a silicon atom bonded to a group having a polymerizable group. (Where n represents an integer of 2 or more). In order for the obtained medical device to obtain sufficient shape recoverability, n is preferably an integer of 3 or more, more preferably 4 or more, still more preferably 5 or more, and most preferably 6 or more. Further, “the silicone moiety is linear” means that the silicone moiety has the linear structure described above and does not have Si—O—Si bonds that do not satisfy the conditions of the linear structure. To do.
- the number average molecular weight of component M is preferably 300 to 120,000. When the number average molecular weight of the component M is within this range, a base material that is flexible and excellent in wearing feeling and excellent in mechanical properties such as bending resistance can be obtained.
- the number average molecular weight of component M is more preferably 500 or more because a base material excellent in mechanical properties such as bending resistance and excellent in shape recoverability can be obtained.
- the number average molecular weight of the component M is more preferably in the range of 1000 to 25000, and still more preferably in the range of 5000 to 15000. When the number average molecular weight of the component M is too small, mechanical properties such as bending resistance and shape recovery tend to be low, and particularly when the number is less than 500, bending resistance and shape recovery may be low. When the number average molecular weight of the component M is too large, flexibility and transparency tend to decrease, which is not preferable.
- the number average molecular weight of the component M is a polystyrene-equivalent number average molecular weight measured by a gel permeation chromatography method (GPC method) using chloroform as a solvent.
- GPC method gel permeation chromatography method
- the mass average molecular weight and the dispersity are also measured by the same method.
- the number average molecular weight and mass average molecular weight of other components used as the base material of the present invention are measured by the same method.
- a mass average molecular weight may be represented by Mw and a number average molecular weight may be represented by Mn.
- molecular weight 1000 may be described as 1 kD.
- the notation “Mw33 kD” represents “mass average molecular weight 33000”.
- a radical polymerizable functional group is preferable, and one having a carbon-carbon double bond is more preferable.
- preferred polymerizable functional groups include vinyl group, allyl group, (meth) acryloyl group, ⁇ -alkoxymethylacryloyl group, maleic acid residue, fumaric acid residue, itaconic acid residue, crotonic acid residue, isocrotonic acid Examples include acid residues and citraconic acid residues. Of these, a (meth) acryloyl group is most preferred because of its high polymerizability.
- (meth) acryloyl represents both methacryloyl and acryloyl, and the same applies to terms such as (meth) acryl and (meth) acrylate.
- Component M preferably has a structure represented by the following formula (M1).
- X 3 represents a polymerizable functional group.
- R 11 to R 19 each independently represents a substituent selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, a phenyl group, and a fluoroalkyl group having 1 to 20 carbon atoms.
- L 3 represents a divalent group.
- c and d each independently represents an integer of 0 to 700. However, c and d are not 0 at the same time.
- X 3 is preferably the radical polymerizable functional group.
- R 11 to R 19 are hydrogen; those having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, decyl group, dodecyl group, octadecyl group and the like.
- Alkyl group phenyl group, trifluoromethyl group, trifluoroethyl group, trifluoropropyl group, tetrafluoropropyl group, hexafluoroisopropyl group, pentafluorobutyl group, heptafluoropentyl group, nonafluorohexyl group, hexafluorobutyl group , Heptafluorobutyl group, octafluoropentyl group, nonafluoropentyl group, dodecafluoroheptyl group, tridecafluoroheptyl group, dodecafluorooctyl group, tridecafluorooctyl group, hexadecafluorodecyl group, heptadecafluorodecyl group, Tetrafluo Propyl group, a pentafluoropropyl group, tetradecanoyl perflu
- L 3 is preferably a divalent group having 1 to 20 carbon atoms.
- a group selected from the groups represented by the following formulas (LE1) to (LE12) is preferable because the compound of the formula (M1) has an advantage that it can be easily obtained with high purity, and among them, the following formulas (LE1), ( The group selected from the groups represented by LE3), (LE9) and (LE11) is more preferred, the group selected from the groups represented by the following formulas (LE1) and (LE3) is more preferred, and the following formula ( Most preferred is the group represented by LE1).
- the following formula (LE1) ⁇ (LE12) the terminal of the left is attached to the polymerizable functional group X 3, is depicted as an end of the right side is attached to a silicon atom.
- c and d each independently represents an integer of 0 to 700. However, c and d are not 0 at the same time.
- the total value of c and d (c + d) is preferably 3 or more, more preferably 10 or more, more preferably 10 to 500, more preferably 30 to 300, and even more preferably 50 to 200.
- c is preferably 3 to 700, more preferably 10 to 500, more preferably 30 to 300, and further preferably 50 to 200. In this case, the value of c is determined by the molecular weight of component M.
- component M In the base material, only one type of component M may be used, or two or more types may be used in combination.
- the base material contains the component M and the component A which is a polysiloxane compound having a plurality of polymerizable functional groups per molecule and having a number average molecular weight of 6000 or more. It is preferable that the coalescence is a main component.
- R a and R b are monovalent organic groups, and the repeating structure (r) may be a combination of the same or different R a and R b ) .
- Component A is a polysiloxane compound having a plurality of polymerizable functional groups, and the number of polymerizable functional groups in Component A may be two or more per molecule, but more flexible (low elastic modulus) medical care From the viewpoint that a device is easily obtained, two per molecule are preferable.
- Component A may have a polymerizable functional group at any position of the molecular chain, but a structure having a polymerizable functional group at both ends of the molecular chain is particularly preferable.
- the number average molecular weight of component A is preferably 6000 or more. When the number average molecular weight of component A is within this range, a medical device having flexibility and excellent wearing feeling and excellent mechanical properties such as bending resistance can be obtained.
- the number average molecular weight of the polysiloxane compound of component A is preferably 8000 or more because a medical device having excellent mechanical properties such as bending resistance can be obtained.
- the number average molecular weight of component A is preferably in the range of 8000 to 100,000, more preferably in the range of 9000 to 70000, and still more preferably in the range of 10,000 to 50000.
- the medical device of the present invention When the medical device of the present invention is used for a low hydrous soft ophthalmic lens or the like, it is preferable that the medical device has high transparency. As a criterion for transparency, it is preferable that the material is transparent and free from turbidity when visually observed. Furthermore, the ophthalmic lens preferably has little or no turbidity when observed with a lens projector, and most preferably no turbidity is observed.
- the dispersity (the value obtained by dividing the mass average molecular weight by the number average molecular weight) is preferably 6 or less, more preferably 3 or less, still more preferably 2 or less, and most preferably 1.5 or less.
- the degree of dispersion of component A is small, compatibility with other components is improved, transparency of the resulting medical device is improved, extractable components contained in the obtained medical device are reduced, and accompanying medical device molding Advantages such as a small shrinkage rate occur.
- the medical device is an ophthalmic lens
- the molding ratio is preferably in the range of 0.85 to 2.0, more preferably in the range of 0.9 to 1.5, and most preferably in the range of 0.91 to 1.3.
- polymerizable functional group of Component A a functional group capable of radical polymerization is preferable, and one having a carbon-carbon double bond is more preferable.
- preferred polymerizable functional groups include vinyl group, allyl group, (meth) acryloyl group, ⁇ -alkoxymethylacryloyl group, maleic acid residue, fumaric acid residue, itaconic acid residue, crotonic acid residue, isocrotonic acid Examples include acid residues and citraconic acid residues. Of these, a (meth) acryloyl group is most preferred because of its high polymerizability.
- the polymerizable functional groups in the molecule may be the same or different polymerizable functional groups.
- the polymerizable functional group of Component A is more preferably copolymerizable with the polymerizable functional group of Component M because a medical device having good mechanical properties can be easily obtained.
- the component M and the component A are more preferably the same as the polymerizable functional group of the component M because the medical device having good surface characteristics can be easily obtained by uniformly copolymerizing the component M and the component A.
- the polymerizable functional group of component A and the polymerizable functional group of component M are both (meth) acryloyl groups.
- Component A preferably has the structure of the following formula (A1).
- X 1 and X 2 each independently represent a polymerizable functional group.
- R 1 to R 8 each independently represents a substituent selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, a phenyl group, and a fluoroalkyl group having 1 to 20 carbon atoms.
- L 1 and L 2 each independently represents a divalent group.
- a and b each independently represents an integer of 0 to 1500. However, a and b are not 0 at the same time.
- X 1 and X 2 are preferably radical polymerizable functional groups, preferably those having a carbon-carbon double bond.
- preferred polymerizable functional groups include vinyl group, allyl group, (meth) acryloyl group, ⁇ -alkoxymethylacryloyl group, maleic acid residue, fumaric acid residue, itaconic acid residue, crotonic acid residue, isocrotonic acid Examples include acid residues and citraconic acid residues. Of these, a (meth) acryloyl group is most preferred because of its high polymerizability.
- R 1 to R 8 include hydrogen; a C 1-20 carbon atom such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, decyl group, dodecyl group, octadecyl group, etc.
- Alkyl group phenyl group, trifluoromethyl group, trifluoroethyl group, trifluoropropyl group, tetrafluoropropyl group, hexafluoroisopropyl group, pentafluorobutyl group, heptafluoropentyl group, nonafluorohexyl group, hexafluorobutyl group , Heptafluorobutyl group, octafluoropentyl group, nonafluoropentyl group, dodecafluoroheptyl group, tridecafluoroheptyl group, dodecafluorooctyl group, tridecafluorooctyl group, hexadecafluorodecyl group, heptadecafluorodecyl group, Tetrafluorop Propyl group, a pentafluoropropyl group, tetradecanoyl per
- L 1 and L 2 are preferably divalent groups having 1 to 20 carbon atoms.
- a group selected from the groups represented by the following formulas (LE1) to (LE12) is preferable because the compound of the formula (A1) has an advantage that it can be easily obtained with high purity, and among them, the following formulas (LE1), ( The group selected from the groups represented by LE3), (LE9) and (LE11) is more preferred, the group selected from the groups represented by the following formulas (LE1) and (LE3) is more preferred, and the following formula ( Most preferred is the group represented by LE1).
- the following formula (LE1) ⁇ (LE12) the terminal of the left is attached to the polymerizable functional group X 1 or X 2, is depicted as an end of the right side is attached to a silicon atom.
- a and b each independently represent an integer of 0 to 1500. However, a and b are not 0 at the same time.
- the total value of a and b (a + b) is preferably 80 or more, more preferably 100 or more, more preferably 100 to 1400, more preferably 120 to 950, and still more preferably 130 to 700.
- R 1 to R 8 are all methyl groups
- b 0, and a is preferably 80 to 1500, more preferably 100 to 1400, more preferably 120 to 950, and still more preferably 130 to 700.
- the value of a is determined by the molecular weight of the polysiloxane compound of component A.
- Component A may be used alone or in combination of two or more.
- the mass ratio of the component M and the component A contained in the copolymer is such that the component A is 5 to 200 parts by mass, more preferably 7 to It is preferably 150 parts by mass, most preferably 10 to 100 parts by mass.
- the base material of the medical device contains an appropriate amount of the component M, the crosslinking density is reduced, the degree of freedom of the polymer is increased, and an appropriately soft base material having a low elastic modulus can be realized.
- the content of the component M is less than 5 parts by mass with respect to 100 parts by mass of the component A, the crosslinking density increases and the substrate becomes hard.
- the content of Component M exceeds 200 parts by mass with respect to 100 parts by mass of Component A, it is not preferable because it becomes too soft and easily broken.
- the base material is preferably composed mainly of a copolymer containing Component M, Component A, and Component B which is a polymerizable monomer having a fluoroalkyl group. .
- Component B has water and oil repellency due to a decrease in the critical surface tension due to the fluoroalkyl group, thereby suppressing the medical device surface from being contaminated with components such as proteins and lipids in tear fluid. There is. In addition, Component B has an effect of providing a medical device that is flexible and excellent in wearing feeling and excellent in mechanical properties such as bending resistance.
- Preferred specific examples of the fluoroalkyl group of Component B are trifluoromethyl group, trifluoroethyl group, trifluoropropyl group, tetrafluoropropyl group, hexafluoroisopropyl group, pentafluorobutyl group, heptafluoropentyl group, nonafluoro group.
- it is a C2-C8 fluoroalkyl group such as a trifluoroethyl group, a tetrafluoropropyl group, a hexafluoroisopropyl group, an octafluoropentyl group, and a dodecafluorooctyl group, most preferably trifluoroethyl group It is a group.
- the polymerizable functional group of Component B is preferably a radical polymerizable functional group, more preferably a carbon-carbon double bond.
- preferred polymerizable functional groups include vinyl group, allyl group, (meth) acryloyl group, ⁇ -alkoxymethylacryloyl group, maleic acid residue, fumaric acid residue, itaconic acid residue, crotonic acid residue, isocrotonic acid
- acid residue and citraconic acid residue include a (meth) acryloyl group because of high polymerizability among them.
- (Meth) acrylic acid fluoroalkyl ester is most preferred as component B because it is highly effective in obtaining a medical device that is flexible and excellent in wearing feeling and excellent in mechanical properties such as bending resistance.
- Specific examples of such (meth) acrylic acid fluoroalkyl esters include trifluoroethyl (meth) acrylate, tetrafluoroethyl (meth) acrylate, trifluoropropyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, and pentafluoropropyl.
- Trifluoroethyl (meth) acrylate, tetrafluoroethyl (meth) acrylate, hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, and dodecafluorooctyl (meth) acrylate are preferably used. Most preferred is trifluoroethyl (meth) acrylate. Only one type of component B may be used, or two or more types may be used in combination.
- the content of Component B in the copolymer is preferably 10 to 500 parts by weight, more preferably 20 to 400 parts by weight, and still more preferably 20 to 200 parts by weight with respect to 100 parts by weight of Component A.
- the amount of component B used is too small, the substrate tends to become cloudy or mechanical properties such as bending resistance tend to be insufficient.
- copolymer used for a base material in addition to Component M, Component A and Component B, those obtained by further copolymerizing a component different from Component M, Component A and Component B (hereinafter Component C) It may be used.
- Component C is preferably one that lowers the glass transition point of the copolymer to room temperature or below 0 ° C. Since these reduce the cohesive energy, they have the effect of imparting rubber elasticity and softness to the copolymer.
- the polymerizable functional group of Component C is preferably a radical polymerizable functional group, and more preferably has a carbon-carbon double bond.
- preferred polymerizable functional groups include vinyl group, allyl group, (meth) acryloyl group, ⁇ -alkoxymethylacryloyl group, maleic acid residue, fumaric acid residue, itaconic acid residue, crotonic acid residue, isocrotonic acid
- acid residue and citraconic acid residue include a (meth) acryloyl group because of high polymerizability among them.
- component C suitable for improving mechanical properties such as flexibility and bending resistance are (meth) acrylic acid alkyl esters, preferably (meth) acrylic acid having an alkyl group having 1 to 20 carbon atoms. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) ) Acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-heptyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate , Isodecyl (meth) acrylate, n-lauryl (meth)
- (Meth) acrylate, n-octyl (meth) acrylate, n-lauryl (meth) acrylate, and n-stearyl (meth) acrylate are more preferred. If the carbon number of the alkyl group is too large, the transparency of the resulting medical device may decrease, which is not preferable.
- the monomers described below can be copolymerized as component C as desired.
- Examples of the monomer for improving mechanical properties include aromatic vinyl compounds such as styrene, tert-butylstyrene, and ⁇ -methylstyrene.
- Examples of the monomer for improving the surface wettability include methacrylic acid, acrylic acid, itaconic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, glycerol methacrylate, polyethylene Glycol methacrylate, N, N-dimethylacrylamide, N-methylacrylamide, N, N-dimethylaminoethyl methacrylate, methylenebisacrylamide, diacetone acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylacetamide, and N- Examples include vinyl-N-methylacetamide.
- N, N-dimethylacrylamide, N-methylacrylamide, N, N-dimethylaminoethyl methacrylate, methylenebisacrylamide, diacetone acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylacetamide, and N-vinyl- Monomers containing amino or amide groups such as N-methylacetamide are preferred.
- a monomer having an amino group such as N, N-dimethylaminoethyl methacrylate is preferable in that it has good compatibility with a dye.
- Examples of monomers for improving the dimensional stability of medical devices include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, and bisphenol A diester.
- Methacrylate, vinyl methacrylate, acrylic methacrylate and acrylates corresponding to these methacrylates, divinylbenzene, triallyl isocyanurate and the like can be mentioned.
- only one type of component C may be used, or two or more types may be used in combination.
- Component C is preferably used in an amount of 0.001 to 400 parts by weight, more preferably 0.01 to 300 parts by weight, still more preferably 0.01 to 200 parts by weight, and most preferably 0 to 100 parts by weight of Component A. 0.01 to 30 parts by mass.
- amount of component C used is too small, it is difficult to obtain the effect expected of component C.
- amount of component C used is too large, the resulting medical device tends to become cloudy or mechanical properties such as bending resistance tend to be insufficient, such being undesirable.
- the medical device of the present invention further includes components (component Ck) such as an ultraviolet absorber, a dye, a colorant, a wetting agent, a slip agent, a medicine and a nutritional supplement component, a compatibilizing component, an antibacterial component, and a release agent. Also good. Any of the above-described components can be contained in a non-reactive form or a copolymerized form.
- component Ck When component Ck is used, the preferred amount of component Ck used is 0.00001 to 100 parts by weight, more preferably 0.0001 to 30 parts by weight, and still more preferably 0.0001 to 10 parts by weight per 100 parts by weight of component A. Part by mass. When the amount of component Ck used is too small, the effects expected for components such as ultraviolet absorbers and colorants tend to be insufficient. When there is too much usage-amount of component Ck, there exists a tendency for white turbidity to arise in the obtained medical device, and it is not preferable.
- the wearer's body tissue in the case of an ophthalmic lens
- the wearer's body tissue in the case of an ophthalmic lens
- a coloring agent when included, a medical device is colored, identification becomes easy, and the convenience at the time of handling improves.
- any of the above-described components can be contained in a non-reactive form or a copolymerized form.
- the above components are copolymerized, that is, when an ultraviolet absorber having a polymerizable functional group or a colorant having a polymerizable functional group is used, the component is copolymerized and immobilized on the substrate. This is preferable because the possibility of
- One form of the base material of the medical device according to the present invention includes a component (component Ck) selected from an ultraviolet absorber and a colorant as a copolymerization component, two or more types of component C, component M, component A and component B. It is preferable to include.
- component C it is preferable to select at least one type from (meth) acrylic acid alkyl esters having 1 to 10 carbon atoms and at least one type from monomers for improving the surface wettability.
- the affinity with ultraviolet absorbers and colorants increases, and it becomes easy to obtain a transparent substrate.
- the preferred amount to be used is 0.01 to 20 parts by weight, more preferably 0.05 to 10 parts by weight, and even more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of Component A. It is.
- the preferred amount of use is 0.00001 to 5 parts by weight, more preferably 0.0001 to 1 part by weight, and still more preferably 0.0001 to 0.5 parts by weight with respect to 100 parts by weight of Component A Part.
- the base material of the medical device of the present invention obtained by copolymerizing a component selected from the above components preferably has a crosslinking degree in the range of 2.0 to 18.3.
- the degree of crosslinking is represented by the following formula (Q1).
- Qn represents the total millimolar amount of monomers having n polymerizable groups per molecule
- Wn represents the total mass (kg) of monomers having n polymerizable groups per molecule.
- the degree of cross-linking of the substrate is less than 2.0, it is too soft and difficult to handle, and when it is greater than 18.3, it is too hard and the wearing feeling tends to deteriorate.
- a more preferable range of the degree of crosslinking is 3.5 to 16.0, a further preferable range is 8.0 to 15.0, and a most preferable range is 9.0 to 14.0.
- the base material preferably contains 5% by mass or more of silicon atoms in order to have high oxygen permeability and to obtain strong adhesion without using a covalent bond with the polymer coated on the surface.
- the silicon atom content (% by mass) is calculated based on the dry substrate mass (100% by mass).
- the silicon atom content of the substrate is preferably 5% by mass to 36% by mass, more preferably 7% by mass to 30% by mass, further preferably 10% by mass to 30% by mass, and most preferably 12% by mass to 26% by mass. . If the silicon atom content is too high, the elastic modulus may increase, which is not preferable.
- the content of silicon atoms in the substrate can be measured by the following method.
- the sufficiently dried substrate is weighed in a platinum crucible, sulfuric acid is added, and heat ashing is performed with a hot plate and a burner.
- the ashed product is melted with sodium carbonate, and water is added to dissolve it by heating.
- nitric acid is added and the volume is adjusted with water.
- a silicon atom is measured by ICP emission spectrometry, and content in a base material is calculated
- a method for producing a medical device substrate that is, a lens-shaped or sheet-shaped molded body
- a known method can be used. For example, a method of once obtaining a round bar or a plate-like polymer and processing it into a desired shape by cutting or the like, a mold polymerization method, a spin cast polymerization method, or the like can be used.
- a medical device is obtained by cutting, freezing cutting at a low temperature is suitable.
- a method for producing an ophthalmic lens by polymerizing a raw material composition containing the component M by a mold polymerization method will be described below.
- a raw material composition is filled in a gap between two mold members having a certain shape.
- the material for the mold member include resin, glass, ceramics, and metal.
- an optically transparent material is preferable, and therefore resin or glass is preferably used.
- a gasket may be used to give a constant thickness to the ophthalmic lens and prevent liquid leakage of the raw material composition filled in the gap.
- the mold filled with the raw material composition in the gap is subsequently irradiated with active light such as ultraviolet rays, visible light, or a combination thereof, or heated in an oven or a liquid tank, etc. Is polymerized.
- active light such as ultraviolet rays, visible light, or a combination thereof
- Is polymerized There may be a method in which two polymerization methods are used in combination. That is, heat polymerization can be performed after photopolymerization, or photopolymerization can be performed after heat polymerization.
- light containing ultraviolet light such as light from a mercury lamp or ultraviolet lamp (for example, FL15BL, Toshiba) is irradiated for a short time (usually 1 hour or less).
- the temperature of the composition is gradually raised from around room temperature, and the temperature is raised to 60 ° C. to 200 ° C. over several hours to several tens of hours. It is preferred for maintaining the quality and quality and enhancing the reproducibility.
- a thermal polymerization initiator or a photopolymerization initiator typified by a peroxide or an azo compound in order to facilitate the polymerization.
- thermal polymerization those having optimum decomposition characteristics at a desired reaction temperature are selected.
- azo initiators and peroxide initiators having a 10-hour half-life temperature of 40 to 120 ° C. are suitable.
- Photoinitiators for photopolymerization include carbonyl compounds, peroxides, azo compounds, sulfur compounds, halogen compounds, and metal salts. These polymerization initiators are used alone or in combination.
- the amount of the polymerization initiator is preferably up to 5% by mass with respect to the polymerization mixture.
- a polymerization solvent can be used.
- Various organic and inorganic solvents can be used as the solvent.
- solvents include water; methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, t-butyl alcohol, t-amyl alcohol, tetrahydrolinalol, ethylene glycol, diethylene glycol, triethylene glycol, Alcohol solvents such as tetraethylene glycol and polyethylene glycol; methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol di Glycol ether solvents such as tilether, triethylene glycol dimethyl ether and polyethylene glycol dimethyl ether; ester solvents
- the medical device of the present invention requires that a layer made of an acidic polymer and a basic polymer (hereinafter referred to as a coating layer) is formed on at least a part of the substrate surface.
- a coating layer By having a coating layer, good wettability and slipperiness are imparted to the surface of the medical device, and an excellent wearing feeling can be given.
- the inventors form a coating layer composed of an acidic polymer and a basic polymer on the surface even if the medical device of the present invention is low in water content and softness and the substrate is neutral.
- a coating layer composed of an acidic polymer and a basic polymer on the surface even if the medical device of the present invention is low in water content and softness and the substrate is neutral.
- the medical device of the present invention greatly reduces or avoids the phenomenon of sticking to the cornea during wearing, which has been a problem in low hydrous soft ophthalmic lenses, which is an example of the usage of a conventional medical device. Can do.
- the coating layer does not need to have a covalent bond with the base material. It is preferable that the coating layer does not have a covalent bond with the base material because it can be manufactured in a simple process. Even if the coating layer does not have a covalent bond with the substrate, it has practical durability.
- the coating layer is obtained by treating the substrate surface with an acidic polymer solution (“solution” means an aqueous solution), which will be described in detail below, and a basic polymer solution (“solution” means an aqueous solution). It is formed.
- the aqueous solution is a solution containing water as a main component.
- the coating layer is preferably composed of one or more kinds of acidic polymers and one or more kinds of basic polymers.
- Use of two or more kinds of acidic polymers or two or more kinds of basic polymers is more preferable because properties such as slipperiness and antifouling properties are easily expressed on the surface of the medical device.
- the tendency becomes stronger, which is more preferable.
- the coating layer is preferably formed by performing treatment with one or more acidic polymer solutions one or more times and treatment with one or more basic polymer solutions one or more times.
- the coating layer is preferably treated with one or more acidic polymer solutions and with one or more basic polymer solutions, preferably 1 to 5 times, more preferably 1 to 3 times, more preferably 1 to 2 each. It is formed in the surface of a base material by performing once.
- the number of treatments with the acidic polymer solution and the number of treatments with the basic polymer solution may be different.
- the coating layer is formed by performing treatment twice or three times in total, once or twice with the treatment with the acidic polymer solution and once or twice with the treatment with the basic polymer solution. It is preferable.
- the coating layer is preferably treated twice with one or more acidic polymer solutions and once with a basic polymer solution, preferably once with two acidic polymer solutions and once with a basic polymer solution. It is particularly preferable that the film is formed by performing the treatment three times in total.
- one of the preferred embodiments of the medical device of the present invention is one in which the coating layer is formed from one kind of acidic polymer and one kind of basic polymer.
- the coating layer is formed from two kinds of acidic polymers and one kind of basic polymer.
- the inventors have also confirmed that, when the coating layer only includes treatment with either one of the acidic polymer solution and the basic polymer solution, almost no expression of wettability or slipperiness is observed.
- the basic polymer a homopolymer or copolymer having a plurality of basic groups along the polymer chain can be suitably used.
- the basic group an amino group and a salt thereof are preferable.
- suitable examples of such basic polymers include poly (allylamine), poly (vinylamine), poly (ethyleneimine), poly (vinylbenzyltrimethylamine), polyaniline, poly (aminostyrene), poly (N, N Amino group-containing (meth) acrylate polymers such as -dialkylaminoethyl methacrylate), amino group-containing (meth) acrylamide polymers such as poly (N, N-dimethylaminopropylacrylamide), and salts thereof.
- the above are examples of homopolymers, but these copolymers (that is, copolymers of basic monomers constituting the basic polymer, or copolymers of basic monomers and other monomers) are also preferably used. be able to.
- the basic monomer constituting the copolymer is preferably a monomer having an allyl group, a vinyl group, and a (meth) acryloyl group in terms of high polymerizability. Most preferred are monomers having a (meth) acryloyl group.
- suitable basic monomers constituting the copolymer include allylamine, vinylamine (N-vinylcarboxylic acid amide as a precursor), vinylbenzyltrimethylamine, amino group-containing styrene, amino group-containing (meth) acrylate. Amino group-containing (meth) acrylamide, and salts thereof.
- amino group-containing (meth) acrylates amino group-containing (meth) acrylamides, and salts thereof are more preferable because of their high polymerizability.
- N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminopropylacrylamide And their salts are most preferred.
- the basic polymer may be a polymer having a quaternary ammonium structure.
- a polymer compound having a quaternary ammonium structure can impart antimicrobial properties to a medical device when used for coating a medical device.
- the acidic polymer a homopolymer or copolymer having a plurality of acidic groups along the polymer chain can be suitably used.
- the group having acidity a carboxyl group, a sulfonic acid group, and a salt thereof are preferable, and a carboxyl group and a salt thereof are most preferable.
- suitable examples of such acidic polymers include polymethacrylic acid, polyacrylic acid, poly (vinyl benzoic acid), poly (thiophene-3-acetic acid), poly (4-styrene sulfonic acid), polyvinyl sulfonic acid, Poly (2-acrylamido-2-methylpropanesulfonic acid) and salts thereof.
- the acidic monomer constituting the copolymer is preferably a monomer having an allyl group, a vinyl group, and a (meth) acryloyl group in terms of high polymerizability.
- Monomers having an acryloyl group are most preferred.
- suitable acidic monomers constituting the copolymer include (meth) acrylic acid, vinyl benzoic acid, styrene sulfonic acid, vinyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and these It is salt. Of these, (meth) acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, and salts thereof are more preferable, and (meth) acrylic acid and salts thereof are most preferable.
- At least one of the basic polymer and the acidic polymer is a polymer having a group selected from an amide group and a hydroxyl group in addition to a basic group or an acidic group.
- the basic polymer and / or the acidic polymer has an amide group, it is preferable because a surface having not only wettability but also slipperiness can be formed.
- the basic polymer and / or the acidic polymer has a hydroxyl group, it is preferable because a surface excellent not only in wettability but also in antifouling property against tears can be formed.
- Two or more of the two or three treatments (coating) performed on the molded body with the acidic polymer solution and the basic polymer solution are polymers having a group selected from a hydroxyl group and an amide group. More preferred. That is, it is preferable that the coating layer of the medical device includes two or more selected from an acidic polymer having a hydroxyl group, a basic polymer having a hydroxyl group, an acidic polymer having an amide group, and a basic polymer having an amide group. In this case, it is preferable because the effect of forming a slippery surface or the effect of forming a surface excellent in antifouling property against tears can be more remarkably exhibited.
- the coating layer contains at least one selected from an acidic polymer having a hydroxyl group and a basic polymer having a hydroxyl group, and at least one selected from an acidic polymer having an amide group and a basic polymer having an amide group. More preferably. In this case, it is preferable because both the effect of forming a slippery surface and the effect of forming a surface excellent in antifouling property against tears can be exhibited.
- Examples of the basic polymer having an amide group include polyamides having an amino group, partially hydrolyzed chitosan, and a copolymer of a basic monomer and a monomer having an amide group.
- Examples of the acidic polymer having an amide group include a polyamide having a carboxyl group and a copolymer of an acidic monomer and a monomer having an amide group.
- Examples of the basic polymer having a hydroxyl group include an aminopolysaccharide such as chitin, a copolymer of a basic monomer and a monomer having a hydroxyl group, and the like.
- Examples of the acidic polymer having a hydroxyl group include polysaccharides having acidic groups such as hyaluronic acid, chondroitin sulfate, carboxymethyl cellulose, and carboxypropyl cellulose, and copolymers of acidic monomers and monomers having amide groups.
- a monomer having an amide group a monomer having a (meth) acrylamide group and N-vinylcarboxylic acid amide (including cyclic ones) are preferable from the viewpoint of ease of polymerization.
- Preferable examples of such monomers include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylacetamide, N-methyl-N-vinylacetamide, N-vinylformamide, N, N-dimethylacrylamide, N, N-diethyl Mention may be made of acrylamide, N-isopropylacrylamide, N- (2-hydroxyethyl) acrylamide, acryloylmorpholine, and acrylamide. Among these, N-vinylpyrrolidone and N, N-dimethylacrylamide are preferable from the viewpoint of slipperiness, and N, N-dimethylacrylamide is most preferable.
- the monomer having a hydroxyl group examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyethyl (meth) acrylamide, glycerol (meth) acrylate, caprolactone-modified 2-hydroxy
- examples thereof include ethyl (meth) acrylate, N- (4-hydroxyphenyl) maleimide, hydroxystyrene, and vinyl alcohol (a carboxylic acid vinyl ester as a precursor).
- a monomer having a (meth) acryloyl group is preferable from the viewpoint of ease of polymerization, and a (meth) acrylic acid ester monomer is more preferable.
- hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and glycerol (meth) acrylate are preferred in terms of antifouling properties against tears, and hydroxyethyl (meth) acrylate is the most preferred. preferable.
- Preferred examples of the copolymer of the basic monomer and the monomer having an amide group include N, N-dimethylaminoethyl methacrylate / N-vinylpyrrolidone copolymer, N, N-dimethylaminoethyl methacrylate / N, N-dimethyl.
- Most preferred is N, N-dimethylaminopropylacrylamide / N, N-dimethylacrylamide copolymer.
- the copolymer of the acidic monomer and the monomer having an amide group include (meth) acrylic acid / N-vinylpyrrolidone copolymer, (meth) acrylic acid / N, N-dimethylacrylamide copolymer, 2- Acrylamide-2-methylpropanesulfonic acid / N-vinylpyrrolidone copolymer and 2-acrylamido-2-methylpropanesulfonic acid / N, N-dimethylacrylamide copolymer. Most preferred is a (meth) acrylic acid / N, N-dimethylacrylamide copolymer.
- the copolymer of the basic monomer and the monomer having a hydroxyl group include N, N-dimethylaminoethyl methacrylate / hydroxyethyl (meth) acrylate copolymer, N, N-dimethylaminoethyl methacrylate / glycerol (meth).
- Acrylate copolymers N, N-dimethylaminopropylacrylamide / hydroxyethyl (meth) acrylate, and N, N-dimethylaminopropylacrylamide / glycerol (meth) acrylate copolymers.
- Most preferred is N, N-dimethylaminoethyl methacrylate / hydroxyethyl (meth) acrylate copolymer.
- the copolymer of an acidic monomer and a monomer having a hydroxyl amide group include (meth) acrylic acid / hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / glycerol (meth) acrylate copolymer, 2-acrylamido-2-methylpropanesulfonic acid / hydroxyethyl (meth) acrylate copolymer and 2-acrylamido-2-methylpropanesulfonic acid / glycerol (meth) acrylate copolymer. Most preferred is a (meth) acrylic acid / hydroxyethyl (meth) acrylate copolymer.
- the copolymerization ratio is [number of moles of basic monomer or acidic monomer] / [number of moles of other monomer] of 1/99 to 99/1 is preferable, 2/98 to 90/10 is more preferable, and 10/90 to 80/20 is still more preferable.
- the copolymerization ratio is within this range, functions such as easy slipperiness and antifouling property against tears are easily developed.
- the acidic polymer and the basic polymer As a method for producing the acidic polymer and the basic polymer, known methods can be used. For example, the monomer is blended in the solvent at the predetermined ratio described above, and after the polymerization initiator is added, the polymerization reaction is performed at the predetermined temperature while refluxing in the presence of an inert medium. The reactant obtained by the reaction is immersed in a solvent to remove unreacted monomer components, and then washed and dried to obtain a polymer. In this way, homopolymers or copolymers of two or more can be produced.
- the molecular weight of the acidic polymer and the basic polymer can be changed to change various properties of the coating layer, such as thickness. Specifically, increasing the molecular weight generally increases the thickness of the coating layer. However, if the molecular weight is too large, handling may increase due to increased viscosity. Therefore, the acidic polymer and basic polymer used in the present invention preferably have a molecular weight of 2000 to 150,000. More preferably, the molecular weight is 5000 to 100,000, and even more preferably 75,000 to 100,000.
- the molecular weight of the acidic polymer and the basic polymer is a mass average molecular weight in terms of polyethylene glycol measured by a gel permeation chromatography method (aqueous solvent).
- coating layer can be accomplished in a number of ways, as described, for example, in WO 99/35520, WO 01/57118 or US Patent Publication No. 2001-0045676.
- a layer made of an acidic polymer and a basic polymer (hereinafter referred to as a coating layer) is formed on at least a part of the surface of the base material. At least a part of the layer is crosslinked. May be. Moreover, in the medical device of this invention, at least one part may be bridge
- crosslinking means that the polymers are bonded by creating a bridge structure using their own functional groups or crosslinking agents.
- the cross-linking can be caused by irradiating radiation with at least an acidic polymer and a basic polymer attached to the substrate.
- the radiation is preferably various ion beams, electron beams, positron beams, X-rays, ⁇ rays and neutron beams, and more preferably electron beams and ⁇ rays. Most preferred is gamma rays.
- the medical device may become too hard due to cross-linking inside the substrate due to irradiation. In that case, excessive crosslinking inside the substrate can be suppressed by appropriately replacing component A in the substrate with component M and copolymerizing.
- the medical device of the present invention contains 1 to 5 acidic polymer solutions and 1 or more basic polymer solutions to 1 to 5 on the surface of a lens-shaped or sheet-shaped molded body (base material) depending on the intended use. It is obtained by applying the coating layer once, more preferably 1 to 3 times, more preferably 1 to 2 times.
- the number of application steps of the acidic polymer solution and the application step of the basic polymer solution may be different. From the viewpoint of shortening the production process, the total of the application process of the acidic polymer solution and the application process of the basic polymer solution is preferably 2 times or 3 times.
- the acidic polymer solution and the basic polymer solution are usually solutions containing one kind of polymer.
- one type means a polymer group having the same monomer type.
- the number of polymers synthesized by changing the compounding ratio is not one.
- solutions of one (same) polymer are not regarded as one solution having different concentrations.
- the coating layer is preferably applied in a configuration selected from the following configurations 1 to 4.
- the following notation indicates that each coating process is performed on the surface of the molded body in order from the left.
- Configuration 1 Application of basic polymer solution / Application of acidic polymer solution
- Configuration 2 Application of acidic polymer solution / Application of basic polymer solution
- Configuration 3 Application of basic polymer solution / Application of acidic polymer solution /
- Configuration 4 Application of acidic polymer solution / Application of basic polymer solution / Application of acidic polymer solution
- configurations 1 and 4 are preferable, and the obtained medical device has particularly excellent wettability and shape recovery. In order to show the property, the configuration 4 is more preferable.
- one or more basic polymer solutions and / or one or more acidic polymer solutions can be used.
- the acidic polymer solutions used for the innermost layer and the outermost layer in the configuration 4 may be the same or different types of acidic polymer solutions may be used.
- the surface of the substrate may be untreated or treated.
- that the surface of the substrate has been treated means that the surface of the substrate is subjected to surface treatment or surface modification by a known method.
- Suitable examples of the surface treatment or surface modification include plasma treatment, chemical modification, chemical functionalization, and plasma coating.
- One of the preferred embodiments (embodiment P1) of the method for producing a medical device of the present invention includes the following steps 1a to 3a in this order.
- ⁇ Step 1a> Polymerizing a mixture containing component M, which is a monofunctional monomer having one polymerizable functional group per molecule and a silicone moiety, to obtain a molded body;
- ⁇ Step 2a> A step of washing and removing excess basic polymer solution after contacting the molded body with the basic polymer solution;
- one of the more preferable embodiments (embodiment P2) of the method for producing a medical device of the present invention includes the following steps 1b to 4b in this order.
- Step 1b> Polymerizing a mixture containing component M, which is a monofunctional monomer having one polymerizable functional group per molecule and a silicone moiety, to obtain a molded body;
- Step 2b> A step of washing and removing excess acidic polymer solution after contacting the molded body with the acidic polymer solution;
- Step 4b> A step of washing and removing excess acidic polymer solution after bringing the molded body into contact with the acidic polymer solution.
- the mixture to be polymerized contains one polymerizable functional group per molecule, a component M that is a monofunctional monomer having a silicone moiety, and a plurality of polymerizable functional groups per molecule. More preferably, it is a mixture comprising Component A which is a polysiloxane compound having a number average molecular weight of 6000 or more and Component B which is a polymerizable monomer having a fluoroalkyl group.
- a layer composed of the acidic polymer and the basic polymer can be formed on the molded body. Thereafter, it is preferable to sufficiently wash away excess polymer.
- various coating methods such as a dipping method (dip method), a brush coating method, a spray coating method, a spin coating method, a die coating method, and a squeegee method can be used. Applicable.
- the immersion time can be changed according to many factors.
- the immersion of the shaped body in the acidic polymer solution or the basic polymer solution is preferably performed for 1 to 30 minutes, more preferably 2 to 20 minutes, and most preferably 1 to 5 minutes.
- the concentration of the acidic polymer solution and the basic polymer solution can be varied depending on the nature of the acidic polymer or basic polymer, the desired coating layer thickness, and many other factors.
- the concentration of the preferred acidic polymer or basic polymer is 0.001 to 10% by mass, more preferably 0.005 to 5% by mass, and most preferably 0.01 to 3% by mass.
- the pH of the acidic polymer solution and the basic polymer solution is preferably maintained at 2 to 5, more preferably 2.5 to 4.5.
- the washing and removal of excess acidic polymer and basic polymer is generally performed by rinsing the molded body after coating with clean water or an organic solvent.
- the rinsing is preferably performed by immersing the molded body in water or an organic solvent, or by exposing it to a water flow or an organic solvent flow. Although rinsing may be completed in one step, it has been found that it is more efficient to perform the rinsing step multiple times.
- Rinsing is preferably performed in steps 2-5. It is preferred to spend 1-3 minutes for each immersion in the rinse solution.
- Pure water is also preferred as the rinsing solution, but is preferably buffered to a pH of 2-7, more preferably 2-5, and even more preferably 2.5-4.5 to increase the adhesion of the coating layer.
- An aqueous solution is also preferably used.
- the method for manufacturing a medical device according to the present invention may include a step of drying or removing an excessive rinse solution.
- the molded body can be dried to some extent by simply leaving the molded body in an air atmosphere, but it is preferable to enhance drying by sending a gentle air flow to the surface.
- the flow rate of the air flow can be adjusted as a function of the strength of the material to be dried and the mechanical fixing of the material. It is not necessary to dry the molded body completely. Here, rather than drying the molded body, it is important to remove droplets of the solution adhered to the surface of the molded body. Therefore, it is only necessary to dry to the extent that the film of water or solution on the surface of the molded body is removed, which is preferable because it leads to shortening of the process time.
- the acidic polymer and the basic polymer are preferable to apply alternately. By applying alternately, it is possible to obtain a medical device having excellent wettability and slipperiness that cannot be obtained by only one of them, and also excellent wearing feeling.
- the coating layer of the medical device of the present invention can be asymmetric.
- asymmetric means having a coating layer different between the first surface of the medical device and the second surface opposite to the first surface.
- the “different coating layer” means that the coating layer formed on the first surface and the coating layer formed on the second surface have different surface characteristics or functionality.
- the thickness of the coating layer can be adjusted by adding one or more salts such as sodium chloride to the acidic polymer solution or the basic polymer solution.
- a preferable salt concentration is 0.1 to 2.0% by mass. As the salt concentration increases, the polyelectrolyte takes a more spherical conformation. However, if the concentration is too high, the polymer electrolyte does not deposit well even if it is deposited on the surface of the molded body. A more preferable salt concentration is 0.7 to 1.3% by mass.
- Another preferred embodiment of the method for producing a medical device of the present invention further includes the following step 5.
- Step 5> A step of irradiating the molded body with radiation after forming a layer composed of an acidic polymer and a basic polymer on the molded body by the above-mentioned step.
- the irradiation of radiation may be performed in a state where the molded body is immersed in the coating liquid, or may be performed after the molded body is drawn out of the coating liquid and washed. Moreover, it is also preferable to perform radiation irradiation in a state where the molded body is immersed in a liquid other than the coating liquid. In this case, it is preferable because the irradiation rays act more efficiently.
- the solvent for the liquid used for immersing the coated molded body various organic and inorganic solvents are applicable and there is no particular limitation.
- water For example, water; various alcohol solvents such as methanol, ethanol, propanol, 2-propanol, butanol, tert-butanol, tert-amyl alcohol, 3,7-dimethyl-3-octanol; benzene, toluene, xylene, etc.
- alcohol solvents such as methanol, ethanol, propanol, 2-propanol, butanol, tert-butanol, tert-amyl alcohol, 3,7-dimethyl-3-octanol
- benzene toluene, xylene, etc.
- the molded body If the molded body is irradiated with radiation in a sealed state, the molded body can be sterilized at the same time.
- ⁇ rays are preferably used as radiation.
- the dose of ⁇ -rays to be irradiated is too small, sufficient bonding between the molded body and the coating layer cannot be obtained, and if it is too large, the physical properties of the molded body are lowered, so 0.1 to 100 kGy is preferable, and 15 to 50 kGy is more preferable, and 20 to 40 kGy is most preferable.
- the durability for example, scuffing durability
- the medical device may become too hard due to cross-linking in the molded body due to irradiation.
- component A in the molded body by appropriately replacing component A in the molded body with component M and copolymerizing, excessive crosslinking inside the molded body can be suppressed.
- the medical device of the present invention is useful as a low hydrous soft ophthalmic lens, for example, an ophthalmic lens such as a low hydrous soft contact lens, an intraocular lens, an artificial cornea, a corneal inlay, a corneal onlay, and an eyeglass lens. Among them, it is particularly suitable for a low water content soft contact lens.
- the wet state means a state where the sample is immersed in pure water or borate buffer at room temperature (25 ° C.) for 24 hours or more.
- the measurement of physical properties in a wet state is performed as soon as possible after removing the sample from pure water or borate buffer and wiping off surface moisture.
- the dry state means a state in which a wet sample is vacuum-dried at 40 ° C. for 16 hours.
- the degree of vacuum in the vacuum drying is 2 hPa or less.
- the measurement of physical property values in a dry state is performed as soon as possible after the vacuum drying.
- the borate buffer is a “salt solution” described in Example 1 of JP-T-2004-517163. Specifically, 8.48 g of sodium chloride, 9.26 g of boric acid, 1.0 g of sodium borate (sodium tetraborate decahydrate), and 0.10 g of ethylenediaminetetraacetic acid are dissolved in pure water and 1000 mL. An aqueous solution.
- Moisture content A contact lens-shaped test piece was used. After being immersed in a borate buffer solution and placed in a constant temperature bath at 40 ° C. for 24 hours or more, the surface moisture was wiped off with a wiping cloth (“Kimwipe” (registered trademark) manufactured by Nippon Paper Crecia), and the mass (Ww) was measured. Then, this test piece was dried at 40 degreeC for 16 hours with the vacuum dryer, and mass (Wd) was measured. Then, the moisture content was calculated
- Moisture content (%) 100 ⁇ (Ww ⁇ Wd) / Ww (4) Wettability
- a contact lens-shaped test piece was immersed in a borate buffer solution in a beaker for 24 hours or more at room temperature.
- the beaker containing the test piece and borate buffer was put on an ultrasonic cleaner (1 minute).
- the test piece was pulled up from the borate buffer solution, and the state of the surface when the diametrical direction was held vertically in the air was visually observed and judged according to the following criteria.
- the diameter is a diameter of a circle formed by the edge of the contact lens.
- E The liquid film on the surface cuts instantaneously (less than 1 second).
- the dynamic contact angle was measured on a wet sample with a borate buffer solution using a dynamic wettability tester WET-6000 manufactured by Reska Co., Ltd.
- a dynamic contact angle sample a film-shaped test piece having a size of about 5 mm ⁇ 10 mm ⁇ 0.1 mm cut from a sample molded into a film shape, or a strip-shaped test piece having a width of 5 mm cut from a contact lens-like sample is used.
- the immersion speed was 0.1 mm / sec and the immersion depth was 7 mm.
- FIG. 1 is a schematic diagram showing an apparatus for measuring a surface friction coefficient.
- FIG. 2 is a schematic diagram showing the configuration of the main parts of the measuring jig 11 and the friction piece 20 as viewed from the direction A shown in FIG.
- FIG. 3 is a partial cross-sectional view showing configurations of main parts of the measuring jig 11 and the friction piece 20.
- a Teflon (registered trademark) plate (65 mm ⁇ 100 mm ⁇ 1.0 mm, omitted in FIG. 3) is placed horizontally on the sample stage 10 of the apparatus 1, and a quartz glass plate 10 a (55 mm ⁇ 55 mm) having a smooth surface thereon. 90 mm ⁇ 1.0 mm) was placed horizontally and fixed. Teflon (registered trademark) plates and quartz glass plates having sufficiently high flatness were used.
- the surface of the quartz glass plate 10a is wiped with “Kimwipe” for each measurement to be in a clean and dry state.
- the sample S is placed on the tip of the mounting holder 21 of the friction element 20, and then pressed by the packing 22 and fixed by the nut 23.
- a borate buffer solution in the following condition A, a physiological saline in the following condition B, Each 0.1 mL was hung.
- the measuring jig 11 is quickly attached to the apparatus 1, and the sample stage 10 is moved in the horizontal direction (arrow Y) at a speed of 1.0 mm / sec in a state where all three samples S are in contact with the quartz glass plate 10a.
- the stress (F) in the horizontal direction when moved is detected by the friction detector 12 and measured by the force meter 13.
- the surface friction coefficient (MIU) was determined by the following equation.
- MIU F / W The moving distance was 30 mm, and MIU measurement was performed every 0.1 second.
- the surface friction coefficient was defined as the average value of MIU in a section (minimum 5 mm) in which the MIU was stable at a moving distance of 5 to 25 mm (the value obtained by dividing the total MIU at each time in the section by the number of MIU data).
- condition A The surface friction coefficient in condition A at this time was MIUa, and the surface friction coefficient in condition B was MIUb.
- Condition A Measurement was performed using a sample in a wet state with a borate buffer.
- Condition B Measurement was performed using a sample in a wet state with physiological saline.
- a monomer mixture was obtained by filtering through a membrane filter (0.45 ⁇ m) to remove insoluble matters.
- This monomer mixture was put into a test tube, deaerated while being stirred with a touch mixer at a reduced pressure of 20 Torr (27 hPa), and then returned to atmospheric pressure with argon gas. This operation was repeated three times. Inject a monomer mixture into a contact lens mold made of transparent resin (poly-4-methylpentene-1) in a glove box in a nitrogen atmosphere and use a fluorescent lamp (Toshiba, FL-6D, daylight color, 6W, 4) And polymerized by light irradiation (8000 lux, 20 minutes).
- the entire mold was immersed in a 60% by mass isopropyl alcohol aqueous solution, and the contact lens-shaped molded body was peeled from the mold.
- the obtained molding was immersed in a large excess of 80% by mass isopropyl alcohol aqueous solution at 60 ° C. for 2 hours. Further, the molded body was immersed in a large excess amount of 50 mass% isopropyl alcohol aqueous solution at room temperature for 30 minutes, then immersed in a large excess amount of 25 mass% isopropyl alcohol aqueous solution at room temperature for 30 minutes, and then a large excess amount of pure water. It was immersed in water at room temperature for 30 minutes.
- the molded body was placed in a sealed vial bottle soaked in clean pure water, and autoclaved at 121 ° C. for 30 minutes.
- the obtained molded body had an edge diameter of about 14 mm and a center thickness of about 0.07 mm.
- the water content of the obtained molded body was less than 1%.
- the same operation was performed using two glass plates and a gasket as a mold to obtain a film-like sample of 60 mm ⁇ 60 mm ⁇ 0.25 mm.
- Reference Examples 2-12 A molded body was obtained in exactly the same manner as in Reference Example 1 except that the amounts used of Component M, Component A, and Component B were changed to the amounts described in Table 1. The water content of the obtained molded body was less than 1%.
- FM0705 Compound of Formula (M2) Mw 930, Mn 769, Chisso FM0711: Compound of Formula (M2) Mw 1500, Mn 1300, Chisso FM0721: Compound of Formula (M2) Mw 6800, Mn 6500, Chisso FM0725: Formula (M2) ) Mw 13300, Mn 12800, Chisso.
- Reference Examples 13-14 As Reference Example 13, a molded body was obtained in exactly the same manner as in Example 1 except that Component M was not included and Component A was changed to 50 parts by mass. The water content of the obtained molded body was less than 1%. Further, as Reference Example 14, a molded article was obtained in the same manner as in Example 1 except that instead of Component M, branched silicone (TRIS) was blended with a monofunctional monomer in the composition shown in Table 1.
- TMS branched silicone
- the component M is a polydimethylsiloxane having a methacryloyl group at one end represented by the formula (M2) (FM0721, nitrogen, mass average molecular weight 68 kD, number average molecular weight 65 kD) (10 parts by mass), and the component A is the formula (A2 ) Polydimethylsiloxane (FM7726, nitrogen, weight average molecular weight 29 kD, number average molecular weight 26 kD) (40 parts by mass) having methacryloyl groups at both ends represented by Industrial) (45 parts by mass), Component C as 2-ethylhexyl acrylate (2-EHA, 3 parts by mass), Component C as N, N-dimethylaminoethyl acrylate (DMAEA, 1 part by mass), Component Ck as a polymerizable group UV absorber (RUVA-93, Otsuka Chemical) (1) The amount unit), and the following estimation formula (C3H)
- a colorant having a polymerizable group represented by the formula [Uniblue A (Sigma Aldrich) treated with hydrochloric acid] (0.5 parts by mass), polymerization initiator “Irgacure (registered trademark)” 819 (Ciba Specialty Chemicals) 1 part by mass) and t-amyl alcohol (10 parts by mass) as a solvent were mixed and stirred.
- the monomer mixture was obtained by filtering with a membrane filter (0.45 ⁇ m) to remove insoluble matters.
- This monomer mixture was put into a test tube, deaerated while being stirred with a touch mixer at a reduced pressure of 20 Torr (27 hPa), and then returned to atmospheric pressure with argon gas. This operation was repeated three times.
- a monomer mixture is injected into a contact lens mold made of transparent resin (poly-4-methylpentene-1) in a glove box in a nitrogen atmosphere, and a fluorescent lamp (Toshiba, FL-6D, daylight color, 6W, 4 pieces) is used. Polymerization was performed by light irradiation (8000 lux, 20 minutes). After the polymerization, the entire mold was immersed in a 60% by mass isopropyl alcohol aqueous solution, and the contact lens-shaped molded body was peeled from the mold. The obtained molding was immersed in a large excess of 80% by mass isopropyl alcohol aqueous solution at 60 ° C. for 2 hours.
- the molded body was immersed in a large excess amount of 50 mass% isopropyl alcohol aqueous solution at room temperature for 30 minutes, then immersed in a large excess amount of 25 mass% isopropyl alcohol aqueous solution at room temperature for 30 minutes, and then a large excess amount of pure water. It was immersed in water at room temperature for 30 minutes. Finally, the molded body was placed in a sealed vial bottle soaked in clean pure water, and autoclaved at 121 ° C. for 30 minutes.
- the obtained molded body had an edge diameter of about 14 mm and a center thickness of about 0.10 mm.
- the obtained molded body had a moisture content of less than 1%, a tensile modulus of elasticity of 0.579 MPa, and a breaking elongation of 511%, which was transparent and free from turbidity, and was suitable as a contact lens.
- the same operation was performed using two glass plates and a gasket as a mold to obtain a film-like sample of 60 mm ⁇ 60 mm ⁇ 0.25 mm.
- Table 1 shows the evaluation results of elongation, elastic modulus, and zero stress time for the molded bodies obtained in Reference Examples 1 to 15.
- the solid content was dried in a vacuum dryer at 60 ° C. overnight. After putting liquid nitrogen and crushing with a spatula, it was dried with a vacuum dryer at 60 ° C. for 3 hours.
- pure water refers to water purified by filtration through a reverse osmosis membrane.
- Examples 1-12, 14 and Comparative Examples 1-2 A layer (coating layer) composed of an acidic polymer and a basic polymer was formed on the molded bodies obtained in Reference Examples 1 to 15.
- the molded body obtained in Reference Example 1 was immersed in a PAA solution for 30 minutes and then immersed in three pure water baths for 5 minutes.
- the molded body was immersed in the PEI solution A for 30 minutes, and then immersed in three pure water baths for 5 minutes.
- the molded body was immersed in a CPDA solution for 30 minutes and then immersed in three pure water baths for 5 minutes, respectively, and then the slipperiness, wettability, and dynamic contact angle were evaluated (Example 1).
- the molded bodies obtained in Examples 1 to 12 and 14 had improved wettability. Further, when the dynamic contact angles of the molded bodies obtained in Examples 11 to 12 and Comparative Example 1 were compared, the dynamic contact angles of the molded bodies of Examples 11 to 12 were reduced. Although the reasons for these are not clear, the molded bodies of Examples 1 to 12 and 14 have a stickiness on the surface compared to the molded body before the coating of Comparative Example 1 at the stage before coating. It is possible that the polymer has become easier to adhere.
- Comparative Example 3 The molded body obtained in Reference Example 12 was immersed in a 1% by weight PVP K90 aqueous solution (polyvinylpyrrolidone, Sigma-Aldrich Japan, molecular weight 360,000) for 30 minutes at room temperature, and then taken out with a finger. There was sex. The slipperiness evaluation criteria was A. After that, it was rinsed lightly with pure water in a beaker and touched with a human finger. E in terms of evaluation of slidability.
- PVP K90 aqueous solution polyvinylpyrrolidone, Sigma-Aldrich Japan, molecular weight 360,000
- Example 13 The molded body obtained in Example 12 was immersed in a borate buffer solution in a sealed vial and irradiated with ⁇ rays.
- the gamma ray dose was 35 kGy.
- Table 2 shows the evaluation results of slipperiness, wettability, dynamic contact angle, and scrubbing durability.
- Example 15 The surface friction coefficient (MIUa) between the molded body obtained in Example 14 and the quartz glass plate when wetted with a borate buffer solution and the surface friction coefficient between the quartz glass plate when wetted with physiological saline (MIUb) was measured. The measurement results are shown in Table 3.
- Comparative Example 4 The molded body (before coating) obtained in Reference Example 15 was subjected to the same measurement as in Example 15 with a borate buffer solution.
- the present invention relates to a medical device, and is preferably used for a device used in contact with a patient or in contact with a tissue collected from the patient, for example, blood or other body fluid, such as an ophthalmic lens or a skin material.
- a device used in contact with a patient or in contact with a tissue collected from the patient for example, blood or other body fluid, such as an ophthalmic lens or a skin material.
- it is useful as an ophthalmic lens such as a low hydrous soft ophthalmic lens, for example, a low hydrous soft contact lens, an intraocular lens, an artificial cornea, a corneal inlay, a corneal onlay, and an eyeglass lens.
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Abstract
Description
(1)前記成分Mおよび下記成分Aを含む共重合体;または
(2)前記成分M、下記成分Aおよび成分Bを含む共重合体;
を主成分とすることが好ましい;
成分A:1分子あたり複数の重合性官能基を有し、数平均分子量が6000以上のポリシロキサン化合物;
成分B:フルオロアルキル基を有する重合性モノマー。
<工程1a>
1分子あたり1個の重合性官能基、およびシリコーン部位を有する単官能モノマーである成分Mを含む混合物を重合し、成型体を得る工程;
<工程2a>
成型体を塩基性ポリマー溶液に接触させた後、余剰の該塩基性ポリマー溶液を洗浄除去する工程;
<工程3a>
成型体を酸性ポリマー溶液に接触させた後、余剰の該酸性ポリマー溶液を洗浄除去する工程。
<工程1b>
1分子あたり1個の重合性官能基、およびシリコーン部位を有する単官能モノマーである成分Mを含む混合物を重合し、成型体を得る工程;
<工程2b>
成型体を酸性ポリマー溶液に接触させた後、余剰の該酸性ポリマー溶液を洗浄除去する工程;
<工程3b>
成型体を塩基性ポリマー溶液に接触させた後、余剰の該塩基性ポリマー溶液を洗浄除去する工程;
<工程4b>
成型体を酸性ポリマー溶液に接触させた後、余剰の該酸性ポリマー溶液を洗浄除去する工程。
Qa=MIUa/MIUo
ここで、MIUaは、該医療デバイスの、ホウ酸緩衝液による湿潤時における平滑な石英ガラス板との間の表面摩擦係数を表す。MIUoは“アキュビュー(登録商標)オアシス”の、ホウ酸緩衝液による湿潤時における平滑な石英ガラス板との間の表面摩擦係数を表す。
Qb=MIUb/MIUo
ここで、MIUbは、該医療デバイスの、生理食塩水による湿潤時における平滑な石英ガラス板との間の表面摩擦係数を表す。
構成2:酸性ポリマー溶液の塗布/塩基性ポリマー溶液の塗布
構成3:塩基性ポリマー溶液の塗布/酸性ポリマー溶液の塗布/塩基性ポリマー溶液の塗布
構成4:酸性ポリマー溶液の塗布/塩基性ポリマー溶液の塗布/酸性ポリマー溶液の塗布
これらの構成の中でも、構成1および構成4が好ましく、得られる医療デバイスが特に優れた濡れ性および形状回復性を示すために構成4がより好ましい。
<工程1a>
1分子あたり1個の重合性官能基、およびシリコーン部位を有する単官能モノマーである成分Mを含む混合物を重合し、成型体を得る工程;
<工程2a>
成型体を塩基性ポリマー溶液に接触させた後、余剰の該塩基性ポリマー溶液を洗浄除去する工程;
<工程3a>
成型体を酸性ポリマー溶液に接触させた後、余剰の該酸性ポリマー溶液を洗浄除去する工程。
<工程1b>
1分子あたり1個の重合性官能基、およびシリコーン部位を有する単官能モノマーである成分Mを含む混合物を重合し、成型体を得る工程;
<工程2b>
成型体を酸性ポリマー溶液に接触させた後、余剰の該酸性ポリマー溶液を洗浄除去する工程;
<工程3b>
成型体を塩基性ポリマー溶液に接触させた後、余剰の該塩基性ポリマー溶液を洗浄除去する工程。
<工程4b>
成型体を酸性ポリマー溶液に接触させた後、余剰の該酸性ポリマー溶液を洗浄除去する工程。
<工程5>
成型体上に前記工程により酸性ポリマーおよび塩基性ポリマーからなる層を形成した後、前記成型体に放射線を照射する工程。
(分析方法および評価方法)
本明細書において、湿潤状態とは、試料を室温(25℃)の純水またはホウ酸緩衝液中に24時間以上浸漬した状態を意味する。湿潤状態での物性値の測定は、試料を純水またはホウ酸緩衝液中から取り出し、表面水分を拭き取った後、可及的速やかに実施される。
特に断らない場合は、GPC法により、以下の条件でポリスチレン換算の質量平均分子量ならびに数平均分子量を測定した。
ポンプ 東ソー DP-8020
検出器 東ソー RI-8010
カラムオーブン 島津 CTO-6A
オートサンプラ 東ソー AS-8010
カラム:東ソー TSKgel GMHHR-M(内径7.8mm×30cm、粒子径5μm)×2本
カラム温度:35℃
移動相:クロロホルム
流速:1.0mL/分
サンプル濃度:0.4質量%
注入量:100μL
標準サンプル:ポリスチレン(分子量1010~109万)
(2)応力ゼロ時間
応力ゼロ時間は、ホウ酸緩衝液による湿潤状態のサンプルを用いて測定した。レンズ形状に成型した成型体のレンズ中央付近から幅5mm、長さ約1.5cmの短冊状サンプルを切り出し、(株)サン科学製レオメータCR-500DXを用いて測定した。チャック幅を5mmに設定してサンプルを取り付け、速度100mm/分で5mm引っ張った後、同速度で初期長(5mm)まで戻す操作を3回繰り返した。2回目の初期長まで戻す途中の応力がゼロになった時点から、3回目の引っ張りを開始した後の応力がかかり始める(ゼロではなくなる)時点までの時間の長さを求め、応力ゼロ時間とした。
コンタクトレンズ形状の試験片を使用した。ホウ酸緩衝液に浸漬して40℃恒温槽に24時間以上おいた後、表面水分をワイピングクロス(日本製紙クレシア製”キムワイプ”(登録商標))で拭き取って質量(Ww)を測定した。その後、該試験片を真空乾燥器で40℃、16時間乾燥し、質量(Wd)を測定した。その後、次式にて含水率を求めた。得られた値が1%未満の場合は測定限界以下と判断し、「1%未満」と表記した。
含水率(%)=100×(Ww-Wd)/Ww
(4)濡れ性
コンタクトレンズ形状の試験片を、室温でビーカー中のホウ酸緩衝液中に24時間以上浸漬した。試験片とホウ酸緩衝液の入ったビーカーを超音波洗浄器にかけた(1分間)。試験片をホウ酸緩衝液から引き上げ、空中に直径方向が垂直になるように保持した際の表面の様子を目視観察し、下記の基準で判定した。ここで直径とはコンタクトレンズの縁部が形成する円の直径である。
A:表面の液膜が20秒以上保持する
B:表面の液膜が10秒以上20秒未満で切れる
C:表面の液膜が5秒以上10秒未満で切れる
D:表面の液膜が1秒以上5秒未満で切れる
E:表面の液膜が瞬時に切れる(1秒未満)。
動的接触角は、(株)レスカ製動的濡れ性試験器WET-6000を用い、ホウ酸緩衝液による湿潤状態のサンプルにて測定した。動的接触角サンプルとして、フィルム状に成型したサンプルから切り出した5mm×10mm×0.1mm程度のサイズのフィルム状の試験片、またはコンタクトレンズ状サンプルから切り出した幅5mmの短冊状試験片を使用し、ホウ酸緩衝液に対する前進時の動的接触角を測定した。浸漬速度は0.1mm/sec、浸漬深さは7mmとした。
ホウ酸緩衝液による湿潤状態のサンプルを用いて測定した。コンタクトレンズ形状のサンプルから規定の打抜型を用いて幅(最小部分)5mm、長さ14mm、厚さ0.2mmの試験片を切り出した。該試験片を用い、オリエンテック社製のテンシロン RTM-100型を用いて引張試験を実施し、弾性率(引張弾性率)と伸度(引張破断伸度)を求めた。引張速度は100mm/分で、グリップ間の距離(初期)は5mmであった。
易滑性は湿潤状態のサンプル(コンタクトレンズ形状)を人指で5回擦った時の感応評価で行った。
A:非常に優れた易滑性がある
B:AとCの中間程度の易滑性がある
C:中程度の易滑性がある
D:易滑性がほとんど無い(CとEの中間程度)
E:易滑性が無い。
(8)擦り洗い耐久性
手のひらの中央に窪みを作ってそこにホウ酸緩衝液による湿潤状態のサンプル(コンタクトレンズ形状)を置き、そこに洗浄液(ボシュロム、“レニュー(登録商標)”)を加えて、もう一方の手の人差し指の腹で表裏10回ずつ擦った。その後、さらに親指と人差し指でサンプルを挟み洗浄液をサンプルにかけながら両面を20回擦った。擦り洗い後のサンプルをホウ酸緩衝液中に浸漬した。その後、(7)易滑性評価を行った。
コンタクトレンズ形状のサンプルまたは直径14mmの円状に切り取ったフィルム形状のサンプルを用いて測定を実施した。測定装置としては、摩擦感テスターKES-SE(カトーテック株式会社)を使用した。図1は、表面摩擦係数を測定する装置を示す模式図である。図2は、図1に示すA方向からみた測定治具11および摩擦子20の要部の構成を示す模式図である。図3は、測定治具11および摩擦子20の要部の構成を示す部分断面図である。まず、装置1の試料台10にテフロン(登録商標)製の板(65mm×100mm×1.0mm、図3では省略)を水平に置き、その上に表面が平滑な石英ガラス板10a(55mm×90mm×1.0mm)を水平に置き固定した。テフロン(登録商標)製の板と石英ガラス板は十分に平面性の高いものを用いた。ここで、石英ガラス板10aは、測定毎に表面を“キムワイプ”で拭き取って清浄で乾いた状態とする。測定では、図2,図3に示す測定治具11(重さ62g=W)の摩擦子20にサンプルSを3枚取り付けて測定を行った。このとき、サンプルSは、摩擦子20の取付ホルダ21の先端に載置された後、パッキン22によって押えられ、ナット23で固定される。サンプルSが摩擦子20の端部から突出して固定された状態で、3枚のサンプルの各々の中央部に、下記条件Aにおいてはホウ酸緩衝液を、下記条件Bにおいては生理食塩水を、各0.1mL垂らした。その後、速やかに測定治具11を装置1に取り付け、3枚のサンプルSがすべて石英ガラス板10aと接触した状態で、試料台10を水平方向(矢印Y)に1.0mm/秒の速度で移動させたときの水平方向の応力(F)が、摩擦検出部12が検出し、力計13によって測定される。表面摩擦係数(MIU)は次式で求めた。
移動距離は30mmとし、MIUの測定は0.1秒毎に実施した。
条件A:ホウ酸緩衝液による湿潤状態のサンプルを用いて測定を実施した。
条件B:生理食塩水による湿潤状態のサンプルを用いて測定を実施した。
前記(10)に記載の方法で“アキュビュー(登録商標)オアシス”(ジョンソン・エンド・ジョンソン株式会社)の条件Aでの表面摩擦係数(MIUo)を測定した。表面摩擦係数比QaとQbは以下の式で求めた。
Qa=MIUa/MIUo
Qb=MIUb/MIUo。
参考例1
成分Mとして下記式(M2)
成分Aとして下記式(A2)
成分Mと成分A、成分Bの使用量を表1中に記載した量に変更した以外は参考例1と全く同様にして成型体を得た。得られた成型体の含水率はいずれも1%未満であった。
FM0711:式(M2)の化合物 Mw 1500、Mn 1300、チッソ
FM0721:式(M2)の化合物 Mw 6800、Mn 6500、チッソ
FM0725:式(M2)の化合物 Mw 13300、Mn 12800、チッソ。
参考例13として、成分Mを含まず、成分Aを50質量部に変更した以外は実施例1と全く同様にして成型体を得た。得られた成型体の含水率は1%未満であった。また、参考例14として、成分Mに換えて、単官能モノマーで分岐型シリコーン(TRIS)を、表1中の組成で配合した以外は実施例1と全く同様にして成型体を得た。
成分Mとして前記式(M2)で表される片末端にメタクリロイル基を有するポリジメチルシロキサン(FM0721、チッソ、質量平均分子量68kD、数平均分子量65kD)(10質量部)、成分Aとして前記式(A2)で表される両末端にメタクリロイル基を有するポリジメチルシロキサン(FM7726、チッソ、質量平均分子量29kD、数平均分子量26kD)(40質量部)、成分Bとしてトリフルオロエチルアクリレート(ビスコート3F、大阪有機化学工業)(45質量部)、成分Cとして2-エチルヘキシルアクリレート(2-EHA、3質量部)、成分CとしてN,N-ジメチルアミノエチルアクリレート(DMAEA、1質量部)、成分Ckとして重合性基を有する紫外線吸収剤(RUVA-93、大塚化学)(1質量部)、および下記の推定構造式(C3H)
実施例においてコーティングに供した共重合体の合成例を示すが、本合成例において各共重合体の分子量は以下に示す条件で測定した。
装置:島津製作所製 Prominence GPCシステム
ポンプ:LC-20AD
オートサンプラ:SIL-20AHT
カラムオーブン:CTO-20A
検出器:RID-10A
カラム:東ソー社製GMPWXL(内径7.8mm×30cm、粒子径13μm)
溶媒:水/メタノール=1/1(0.1N硝酸リチウム添加)
流速:0.5mL/分
測定時間:30分
サンプル濃度:0.1質量%
注入量:100μL
標準サンプル:Agilent社製ポリエチレンオキシド標準サンプル(0.1kD~1258kD)。
<CPDA:N,N-ジメチルアクリルアミド/アクリル酸(モル比2/1)>
500mL三口フラスコにN,N-ジメチルアクリルアミド(59.50g、0.600mol)、アクリル酸(21.62g、0.300mol)、純水(325.20g)、重合開始剤VA-061(和光純薬、0.1408g、0.562mmol)、2-メルカプトエタノール(43.8μL、0.63mmol)を加え、三方コック、還流冷却管、温度計およびメカニカルスターラを装着した。モノマー濃度は20質量%であった。三口フラスコ内部を真空ポンプで脱気して、アルゴン置換を3回繰り返した後、混合物を50℃で0.5時間撹拌し、その後70℃に昇温して、6.5時間撹拌した。重合終了後、重合反応液をエバポレータで400gまで濃縮し、2-プロパノール/n-ヘキサン=500mL/500mL中に注ぎ入れて静置後、上澄み液をデカンテーションで除いた。得られた固形分を2-プロパノール/n-ヘキサン=250mL/250mLで3回洗浄した。固形分を真空乾燥機で60℃、一晩乾燥させた。液体窒素を入れ、スパチュラで破砕した後、真空乾燥機で60℃、3時間乾燥させた。このようにして得られた共重合体の分子量はMn:55kD、Mw:192kD(Mw/Mn=3.5)であった。
以下、純水とは逆浸透膜で濾過して精製した水を表す。
<PEI溶液>
ポリエチレンイミン(P3143、シグマアルドリッチ、分子量75万)を純水に溶解して1質量%水溶液とした。
<PAA溶液>
ポリアクリル酸(169-18591、和光純薬工業、分子量25万)を純水に溶解して1.2質量%水溶液とした。
<CPDA溶液>
合成例1で得られたCPDA共重合体を、純水に溶解して1質量%水溶液とした。
参考例1~15で得られた成型体に、酸性ポリマーおよび塩基性ポリマーからなる層(コーティング層)を形成した。参考例1で得られた成型体をPAA溶液に30分間浸漬した後、3つの純水浴にそれぞれ5分間浸漬した。次に該成型体をPEI溶液Aに30分間浸漬した後、3つの純水浴にそれぞれ5分間浸漬した。次に該成型体をCPDA溶液に30分間浸漬した後、3つの純水浴にそれぞれ5分間浸漬した後、易滑性、濡れ性および動的接触角を評価した(実施例1)。同様にして、参考例2~14で得られた成型体に酸性ポリマーおよび塩基性ポリマーからなる層を形成して、易滑性、濡れ性および動的接触角を評価した(実施例2~12および比較例1~2)。評価結果を表2に示した。
参考例12で得られた成型体を1質量%PVP K90水溶液(ポリビニルピロリドン、シグマアルドリッチジャパン、分子量36万)に室温で30分間浸漬した後、取り出し人指で触ったところ非常に優れた易滑性があった。易滑性評価基準でAであった。その後、ビーカー中の純水で軽く濯ぎ洗いし、人指で触ったところ易滑性がなかった。易滑性評価基準でEであった。
実施例12で得られた成型体を、密閉バイアル瓶中のホウ酸緩衝液中に浸漬した状態で入れ、γ線照射した。γ線線量は、35kGyであった。易滑性、濡れ性、動的接触角、擦り洗い耐久性の評価結果を表2に示した。
実施例14で得られた成型体の、ホウ酸緩衝溶液による湿潤時における石英ガラス板との間の表面摩擦係数(MIUa)および生理食塩水による湿潤時における石英ガラス板との間の表面摩擦係数(MIUb)を測定した。測定結果を表3に示した。
参考例15で得られた成型体(コーティング前)について、ホウ酸緩衝液で実施例15と同様の測定を行ったところ、表面摩擦係数はMIUa=2.638、表面摩擦係数比はQa=2.745/0.305=9.000であり、実施例15よりも劣った。
市販シリコーンハイドロゲルソフトコンタクトレンズ製品“O2 オプティクス(登録商標)”(チバビジョン株式会社)について、ホウ酸緩衝液で実施例15と同様の測定を行ったところ、表面摩擦係数はMIUa=2.638、表面摩擦係数比はQa=2.638/0.305=8.647であり、実施例15よりも劣った。
10 試料台
10a 石英ガラス板
11 測定治具(アルミニウム製)
12 摩擦検出部
13 力計
20 摩擦子
21 取付ホルダ(アルミニウム製)
22 パッキン(“テフロン(登録商標)”製)
23 ナット(アルミニウム製)
S サンプル
Claims (14)
- 低含水性軟質基材の表面の少なくとも一部に、酸性ポリマーおよび塩基性ポリマーからなる層が形成された医療デバイスであって、前記低含水性軟質基材が、1分子あたり1個の重合性官能基およびシリコーン部位を有する単官能モノマー成分Mを含む共重合体を主成分とする医療デバイス。
- 前記シリコーン部位が、直鎖状である請求項1または2に記載の医療デバイス。
- 前記基材が、
(1)前記成分Mおよび下記成分Aを含む共重合体;または
(2)前記成分M、下記成分Aおよび成分Bを含む共重合体;
を主成分とする請求項1~4のいずれかに記載の医療デバイス;
成分A:1分子あたり複数の重合性官能基を有し、数平均分子量が6000以上のポリシロキサン化合物;
成分B:フルオロアルキル基を有する重合性モノマー。 - 前記成分Aの重合性官能基が、成分Mの重合性官能基と共重合可能な重合性官能基である請求項5記載の医療デバイス。
- 前記成分Mと前記成分Aとの質量比は、成分Aが100質量部に対して成分Mが5~200質量部である請求項5に記載の医療デバイス。
- 前記酸性ポリマーおよび塩基性ポリマーからなる層が、酸性ポリマー1種、および塩基性ポリマー1種のみから形成された請求項1~7のいずれかに記載の医療デバイス。
- 前記酸性ポリマーおよび塩基性ポリマーからなる層が、2種の酸性ポリマーおよび1種の塩基性ポリマーから形成された請求項1~7いずれかに記載の医療デバイス。
- 前記酸性ポリマーおよび塩基性ポリマーからなる層を形成する前記酸性ポリマーおよび前記塩基性ポリマーのうちの少なくとも1種が、水酸基およびアミド基から選ばれた基を有するポリマーである請求項1~9のいずれか1つに記載の医療デバイス。
- 低含水性軟質眼用レンズである請求項1~10のいずれか1つに記載の医療デバイス。
- 下記工程1a~工程3aをこの順に含む医療デバイスの製造方法;
<工程1a>
1分子あたり1個の重合性官能基およびシリコーン部位を有する単官能モノマーである成分Mを含む混合物を重合し、成型体を得る工程;
<工程2a>
成型体を塩基性ポリマー溶液に接触させた後、余剰の該塩基性ポリマー溶液を洗浄除去する工程;
<工程3a>
成型体を酸性ポリマー溶液に接触させた後、余剰の該酸性ポリマー溶液を洗浄除去する工程。 - 下記工程1b~工程4bをこの順に含む医療デバイスの製造方法;
<工程1b>
1分子あたり1個の重合性官能基、およびシリコーン部位を有する単官能モノマーである成分Mを含む混合物を重合し、成型体を得る工程;
<工程2b>
成型体を酸性ポリマー溶液に接触させた後、余剰の該酸性ポリマー溶液を洗浄除去する工程;
<工程3b>
成型体を塩基性ポリマー溶液に接触させた後、余剰の該塩基性ポリマー溶液を洗浄除去する工程;
<工程4b>
成型体を酸性ポリマー溶液に接触させた後、余剰の該酸性ポリマー溶液を洗浄除去する工程。 - 前記混合物がさらに、1分子あたり複数の重合性官能基を有し、数平均分子量が6000以上のポリシロキサン化合物である成分A、および、フルオロアルキル基を有する重合性モノマーである成分Bを含む請求項12または13に記載の医療デバイスの製造方法。
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KR101900993B1 (ko) | 2011-08-17 | 2018-09-20 | 도레이 카부시키가이샤 | 의료 디바이스, 코팅 용액의 조합 및 의료 디바이스의 제조 방법 |
KR101602402B1 (ko) * | 2014-04-29 | 2016-03-10 | 주식회사 엠아이텍 | 스텐트 |
KR20180012777A (ko) * | 2015-05-27 | 2018-02-06 | 도레이 카부시키가이샤 | 피부 점착 시트 및 시트상 피부 외용제 |
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CN110603061A (zh) * | 2017-05-10 | 2019-12-20 | 东丽株式会社 | 医疗器械 |
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CN109701086A (zh) * | 2019-03-11 | 2019-05-03 | 脉通医疗科技(嘉兴)有限公司 | 一种医用管材及其制备方法 |
JP6954490B1 (ja) * | 2020-01-16 | 2021-10-27 | 東レ株式会社 | 医療デバイスの製造方法 |
CN114539484B (zh) * | 2022-02-11 | 2024-03-19 | 浙江脉通智造科技(集团)有限公司 | 交联型尼龙医用器材及其制备方法、尼龙组合物及应用 |
US20230350100A1 (en) * | 2022-04-29 | 2023-11-02 | Alcon Inc. | Method for making silicone hydrogel contact lenses |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015153403A1 (en) * | 2014-03-31 | 2015-10-08 | Johnson & Johnson Vision Care, Inc. | Silicone acrylamide copolymer |
WO2015153404A1 (en) * | 2014-03-31 | 2015-10-08 | Johnson & Johnson Vision Care, Inc. | Silicone acrylamide copolymer |
JP2017517585A (ja) * | 2014-03-31 | 2017-06-29 | 東レ株式会社 | シリコーンアクリルアミド共重合体 |
US9745460B2 (en) | 2014-03-31 | 2017-08-29 | Johnson & Johnson Vision Care, Inc. | Silicone acrylamide copolymer |
AU2015241171B2 (en) * | 2014-03-31 | 2018-02-22 | Johnson & Johnson Vision Care, Inc. | Silicone acrylamide copolymer |
RU2682256C2 (ru) * | 2014-03-31 | 2019-03-18 | Джонсон Энд Джонсон Вижн Кэа, Инк. | Силиконовый акриламидный сополимер |
US10240034B2 (en) | 2014-03-31 | 2019-03-26 | Johnson & Johnson Vision Care, Inc. | Silicone acrylamide copolymer |
Also Published As
Publication number | Publication date |
---|---|
US9632212B2 (en) | 2017-04-25 |
KR20140049045A (ko) | 2014-04-24 |
JP6036299B2 (ja) | 2016-11-30 |
EP2745854A4 (en) | 2015-04-15 |
TW201313264A (zh) | 2013-04-01 |
US20140198295A1 (en) | 2014-07-17 |
EP2745854B1 (en) | 2018-02-07 |
EP2745854A1 (en) | 2014-06-25 |
JPWO2013024801A1 (ja) | 2015-03-05 |
TWI551307B (zh) | 2016-10-01 |
CN103747812A (zh) | 2014-04-23 |
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