JP2013057932A - Soft resin device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a soft resin device which is used in a wet state and the wet state of which preferable for usage can be easily grasped by a user, and to provide a manufacturing method of the soft resin device.SOLUTION: A soft resin device 10 includes: a substrate 11; and a coating layer 12 which is composed of a hydrophilic polymer formed on at least one part of a surface of the substrate 11, a thickness of which changes in the air, and which is in, according to the thickness, in order from a large thickness range, a perfectly wet state, a semi-wet state, and a dry state. When the coating layer 12 is in the semi-wet state, a recess 13 is formed in the coating layer 12.

Description

  The present invention relates to a soft resin device.

  In recent years, soft materials such as hydrogels, silicone rubbers, and silicone hydrogels have become medical devices such as soft contact lenses (soft ophthalmic lenses) and skin coating materials, biotechnology devices such as cell culture sheets, and facial packs. It is used as a beauty device or the like (see, for example, Patent Documents 1 to 5).

  Such a soft material is used after being subjected to surface modification (coating or the like) according to the application (device). For example, in the case of a soft ophthalmic lens that is one of medical devices, a treatment for imparting hydrophilicity to a surface of a base material (hereinafter referred to as a soft base material) formed of a soft material is performed. There are various methods for modifying the surface of a soft substrate, and among them, a method of coating and laminating two or more layers of polymer materials one by one (for example, patents) is known. References 6-8). Among them, the 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 the material is non-covalently bonded to another layer of a different material. It is believed that. The high oxygen permeability soft ophthalmic lens for which the usefulness of this method is clearly stated is only for silicone hydrogel materials, and the usefulness for other materials (for example, low hydrous soft base materials) is known. It was not done. Moreover, the conventional LbL coating was performed by the multilayer of about 4-20 layers.

JP 54-81363 A Japanese Patent Laid-Open No. 54-24047 JP-T-2001-527141 Japanese translation of PCT publication No. 2003-500686 Special table 2010-513608 gazette Japanese translation of PCT publication No. 2002-501211 JP 2005-538418 A Special table 2009-540369

  By the way, among soft resin devices formed of a soft resin material, soft resin devices used in a wet state, such as soft ophthalmic lenses, are usually stored in a storage solution. In such a soft resin device, the wet state starts to be lost immediately after the soft resin device is taken out of the storage solution. Therefore, the user must use the soft resin device (attached to a predetermined part) immediately after taking out the soft resin device from the storage solution. In addition, when the soft resin device has been dried and the wet state has been lost beyond a predetermined state (a state suitable for use), the user can immerse the soft resin device in a storage solution again. It is necessary to take measures to regain the wet state or to stop using the soft resin device. However, it is very difficult for the user to grasp whether or not the soft resin device is in a state suitable for use.

  The present invention has been made in view of the above, and in a soft resin device used in a wet state, the user can easily grasp whether or not the soft resin device is in a state suitable for use. An object of the present invention is to provide a soft resin device that can be manufactured and a method for manufacturing the same.

  In order to achieve the above object, the present invention has the following configuration.

  The soft resin device of the present invention comprises a base material and a hydrophilic polymer formed on at least a part of the surface of the base material. The thickness changes in the atmosphere, and the thickness varies depending on the thickness. A layer having a completely wet state, a semi-wet state, and a dry state in order from the larger range, and a recess is formed in the layer in the semi-wet state. Hereinafter, such a concave portion may be simply expressed as a “concave portion”.

  Preferably, in the soft resin device, the concave portion appears when the layer shifts from the completely wet state to the semi-wet state.

  Preferably, in the soft resin device, the concave portion disappears when the layer moves from the semi-wet state to the dry state.

  Preferably, in the soft resin device, the diameter of the recess is 0.1 μm or more and 200 μm or less, and the depth of the recess is 1 μm or more and 1000 μm or less.

  Preferably, the hydrophilic polymer is composed of an acidic polymer and a basic polymer.

  The soft resin device of the present invention is preferably used in a wet state and a semi-wet state.

In the above, it is preferable that the base material is composed mainly of a polymer of the following component A or a copolymer of the following component A and component B;
Component 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.

  In this specification, a polysiloxane compound is a compound having a Si—O—Si—O—Si bond.

  The soft resin device of the present invention is preferably a soft ophthalmic lens.

  The soft resin device of the present invention is a soft resin device comprising a base material and a layer made of a hydrophilic polymer formed on at least a part of the surface of the base material. When taken out from the state immersed in water or borate buffer solution to the atmosphere, a concave portion that can be visually observed is formed on at least a part of the time range from 5 seconds to 30 minutes after removal. In addition, it may be characterized in that the concave portion disappears to such an extent that it is not visually observed until 5 seconds after the removal and after 30 minutes after the removal.

  In the soft resin device of the present invention, when the layer on the surface of the soft resin device is in a semi-moist state, a recess is formed in the layer. For this reason, the user can easily grasp whether or not the soft resin device is in a state suitable for use by observing the surface of the soft resin device.

FIG. 1 is a cross-sectional view schematically showing the structure of the soft resin device of the present invention.

  The soft resin device of the present invention comprises a base material and a hydrophilic polymer formed on at least a part of the surface of the base material. The thickness changes in the atmosphere, and the thickness varies depending on the thickness. A layer having a completely wet state, a semi-wet state, and a dry state in order from the larger range is provided, and when the layer is in a semi-wet state, a recess is formed in the layer. This recess appears when the layer moves from a completely wet state to a semi-wet state, and disappears when the layer moves from a semi-wet state to a dry state. The diameter of the recess is preferably larger from the viewpoint of visibility. Specifically, the diameter is preferably 0.1 μm or more, more preferably 0.5 μm or more, and further preferably 1 μm or more. On the other hand, the diameter of the concave portion is preferably smaller from the viewpoint of appearance quality, and specifically, 200 μm or less is preferable, 100 μm or less is more preferable, 50 μm or less is further preferable, and 20 μm or less is most preferable. Similarly, the depth of the recess is preferably deeper from the viewpoint of visibility. Specifically, the depth is preferably 1 μm or more, more preferably 5 μm or more, and most preferably 7 μm or more. On the other hand, the depth of the concave portion is preferably shallow from the viewpoint of appearance quality, specifically, preferably 1000 μm or less, more preferably 500 μm or less, and most preferably 200 μm or less. When a plurality of recesses appear, at least one recess has a diameter and a depth in the above range. Moreover, although the size of the concave portion changes with time, it is sufficient that there is a time zone in which the concave portion having the above diameter and depth appears. Preferably, when the depth of the recess is maximum, the recess has the above diameter and depth.

  Here, in the present specification, the completely wet state is a state in which the layer is substantially swollen by the liquid, and the thickness of the layer is substantially the maximum among the values that the soft resin device can take. I mean. The semi-wet state refers to a state where the moisture in the layer is reduced and the thickness of the layer is reduced compared to the completely wet state, and is determined by the appearance of a recess on the surface of the layer. . Note that the completely wet state and the semi-wet state are included in a so-called moist state (wet state). The dry state refers to a state in which the moisture in the layer is further reduced compared to the semi-wet state and the thickness of the layer is reduced, and is determined by the fact that the concave portion is not observed.

  The soft resin device of the present invention is a soft resin device comprising a base material and a layer made of a hydrophilic polymer formed on at least a part of the surface of the base material. When taken out from the state immersed in water or borate buffer solution to the atmosphere, a concave portion that can be visually observed is formed on at least a part of the time range from 5 seconds to 30 minutes after removal. In addition, it may be characterized in that the concave portion disappears to such an extent that it is not visually observed until 5 seconds after the removal and after 30 minutes after the removal.

  Here, the air is air at normal temperature (20 ± 15 ° C.), normal humidity (relative humidity 45 to 85%), and substantially no wind. Strictly speaking, the temperature is 25 ± 3 ° C., the relative humidity is 55 ± 5%, and the atmosphere is substantially windless. After being taken out into the atmosphere, the surface of the soft resin device is held in a state where it is not touched except in the atmosphere.

  After taking out the soft resin device from pure water or borate buffer, a time range in which a concave portion is formed on the surface and visually observed is at least partly between 5 seconds and 5 minutes after removal. More preferably, the time range is at least part of the time range from 10 seconds to 1 minute later.

  As the soft resin device of the present invention, specifically, a soft ophthalmic lens, an intraocular lens, an ophthalmic lens such as an artificial cornea, a corneal inlay, a corneal onlay, or the like is used by being attached to a biological surface to protect or protect the biological surface. Medical devices such as dressings to be treated (skin dressings, wound dressings, skin protection materials, skin drug carriers, etc.), separation membrane devices such as gas-liquid separation membranes, liquid-liquid separation membranes, plate materials, stamps , Image forming devices such as stamp stands (red meat), biotechnology devices such as cell culture sheets or scaffolds for tissue regeneration, beauty devices such as facial packs, seafood freshness keeping sheets, heat-cooled sheets, daily necessities, etc. Is mentioned. The said base material is shape | molded by various forms, such as a spherical crown shape (contact lens shape), a sheet form, and a film form, according to the use of a soft resin device.

  The substrate is preferably made of a low hydrous soft material. Low water content means that the water content is 10% by mass or less. Moreover, the soft means that the tensile elastic modulus is 10 MPa or less.

  Here, the moisture content is, for example, the mass of the test piece in the dry state T in a film shape (mass in the dry state T) and the mass when the surface moisture of the test piece in the wet state T is wiped off (in the wet state T). Mass), {(mass in wet state T) − (mass in dry state T) / mass in wet state T} × 100.

  In this specification, the wet state T means a state in which a sample is immersed in pure water or borate buffer at room temperature (25 ° C.) for 24 hours or more. The measurement of physical property values in a wet state is performed as soon as possible after the sample is taken out from pure water or borate buffer.

  Moreover, in this specification, the dry state T means the state which vacuum-dried the sample of the wet state T at 40 degreeC for 16 hours. The degree of vacuum in the vacuum drying is 2 hPa or less. The measurement of the physical property value in the dry state T is performed as soon as possible after the vacuum drying.

  In this specification, 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 were dissolved in pure water to make 1000 mL. It is.

  When the soft resin device of the present invention is an ophthalmic lens having a low hydrous soft material as a base material, the soft resin device has a feature that a wearer's eyes have a small dry feeling and an excellent wearing feeling. In addition, when the soft resin device of the present invention is a medical device such as a skin covering material or a wound covering material, or a beauty device such as a facial pack, the dry feeling felt by the user while being applied to the surface of a living body. It has the characteristics of being small and excellent in wearing feeling.

  Furthermore, when the soft resin device of the present invention is a medical device or biotechnology device based on a low hydrous soft material, there is an advantage that the risk of bacterial growth is small. 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, for example, the dryness of the eyes of the ophthalmic lens wearer is increased and the risk of bacterial growth is increased, which is not preferable.

  The tensile elastic modulus of the soft resin device of the present invention is preferably 0.01 to 5 MPa, more preferably 0.1 to 3 MPa, further preferably 0.1 to 2 MPa, still more preferably 0.1 to 1 MPa, and 1 to 0.6 MPa is most preferable. If the tensile modulus is too small, it tends to be too soft and difficult to handle. When the tensile elastic modulus is too large, it tends to be too hard and the wearing feeling tends to be poor. When the tensile modulus of elasticity is 2 MPa or less, a good wearing feeling is obtained, and when it is 1 MPa or less, a better wearing feeling is obtained, which is preferable. The tensile elastic modulus is measured on a sample in a wet state T with a borate buffer.

  The tensile elongation of the soft resin device of the present invention is preferably 100% to 1000%, more preferably 200% to 700%. If the tensile elongation is small, the soft resin device is easily broken, which is not preferable. If the tensile elongation is too large, the soft resin device tends to be deformed, which is not preferable. The tensile elongation is measured on a sample in a wet state T with a borate buffer.

  The soft resin device of the present invention is important from the viewpoint of familiarity with the living body that is excellent in surface wettability, and the dynamic contact angle (advancing, immersion speed: 0.1 mm / sec) is preferably 100 ° or less, 90 ° or less is more preferable, and 80 ° or less is more preferable. 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 solution in a sample in a wet state T with a borate buffer solution.

  In the soft resin device of the present invention, excellent surface wettability is important from the viewpoint of familiarity with a living body. In particular, when the soft resin device is an ophthalmic lens, excellent wettability of the surface is important from the viewpoint of preventing the ophthalmic lens from sticking to the wearer's cornea. From this viewpoint, it is preferable that the liquid film holding time on the surface of the soft resin device is long. Here, the liquid film retention time means that when a soft resin device immersed in a borate buffer solution is pulled up from the solution and held in the air so that the surface (diameter direction in the case of a spherical crown shape) is vertical, the soft film device is soft. This is the time during which the liquid film on the surface of the resin device is held without being cut. The liquid film holding time is preferably 5 seconds or longer, more preferably 10 seconds or longer, and most preferably 20 seconds or longer. Here, the diameter is the diameter of a circle formed by the edge of the spherical crown. Further, the liquid film retention time is measured on a sample in a wet state with a borate buffer.

  From the viewpoint of smooth movement when contacted with body tissue, especially in the case of an ophthalmic lens, the surface of the soft resin device has excellent slipperiness from the viewpoint of preventing sticking to the wearer's cornea Is preferred. As an index representing slipperiness, it is preferable that the friction measured by the method shown in the examples of the present specification is small. The friction is preferably 60 gf (0.59 N) or less, more preferably 50 gf (0.49 N) or less, further preferably 40 gf (0.39 N) or less, and most preferably 30 gf (0.29 N) or less. Further, if the friction is extremely small, handling at the time of detachment tends to be difficult, so the friction is preferably 5 gf (0.049 N) or more, preferably 10 gf (0.098 N) or more. Friction is measured on samples in a wet state T with borate buffer.

In a soft resin device such as an ophthalmic lens, the antifouling property can be evaluated by mucin adhesion, lipid (methyl palmitate) adhesion, and artificial tear immersion test. The smaller the amount of adhesion by these evaluations, the better the feeling of wearing and the lower the risk of bacterial propagation. The mucin adhesion amount is preferably 5 μg / cm ² or less, more preferably 4 μg / cm ² or less, and most preferably 3 μg / cm ² or less.

The soft resin 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 transmission coefficient is measured on a sample in a dry state T.

  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 content of silicon atoms is too large, the tensile 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. Then, nitric acid is added and the volume is adjusted with water. About this solution, a silicon atom is measured by ICP emission spectrometry, and content in a base material is calculated | required.

  The base material is a polymer of component A which is a polysiloxane compound having a plurality of polymerizable functional groups per molecule and a number average molecular weight of 6000 or more, or a compound having the component A and a polymerizable functional group. Thus, it is preferable that the main component is a copolymer with a compound different from Component A. Here, 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 number average molecular weight of component A is preferably 6000 or more. The inventors have found that when the number average molecular weight of Component A is within this range, a soft resin device having flexibility, excellent wearing feeling, and excellent mechanical properties such as bending resistance can be obtained. The number average molecular weight of the component A polysiloxane compound is preferably 8000 or more because a soft resin 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 10000 to 50000. When the number average molecular weight of component A is too small, mechanical properties such as bending resistance tend to be low, and particularly when it is less than 6000, bending resistance is low. When the number average molecular weight of component A is too large, flexibility and transparency tend to decrease, which is not preferable.

  When the soft resin device of the present invention is an ophthalmic lens, since the ophthalmic lens is an optical product, it is preferable that the transparency is high. 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) of component A is preferably 6 or less, more preferably 3 or less, still more preferably 2 or less, and most preferably 1.5 or less. When the dispersion degree of the component A is small, the compatibility with other components is improved, the transparency of the obtained lens is improved, the extractable components contained in the obtained lens are reduced, and the shrinkage rate accompanying the lens molding is reduced. Advantages such as smaller size occur. The shrinkage rate associated with lens molding can be evaluated by lens molding ratio = [lens diameter] / [diameter of void portion of mold]. The closer the lens molding ratio is to 1, the easier it is to manufacture a high-quality lens stably. 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.

  In the present invention, the number average molecular weight of component A is a number average molecular weight in terms of polystyrene measured by a gel permeation chromatography method (GPC method) using chloroform as a solvent. The mass average molecular weight and the dispersity (value obtained by dividing the mass average molecular weight by the number average molecular weight) are also measured by the same method.

  In the present specification, the mass average molecular weight may be represented by Mw and the number average molecular weight may be represented by Mn. Moreover, molecular weight 1000 may be described as 1 kD. For example, the notation “Mw33 kD” represents “mass average molecular weight 33000”.

  Component A is a polysiloxane compound having a plurality of polymerizable functional groups. The number of polymerizable functional groups of component A may be two or more per molecule, but two per molecule are preferable from the viewpoint of easily obtaining a soft resin device having a more flexible (low elastic modulus). . In particular, a structure having a polymerizable functional group at both ends of the molecular chain is preferable.

  As the 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. Examples of preferred polymerizable functional groups include vinyl group, allyl group, (meth) acryloyl group, α-alkoxymethylacryloyl group, maleic acid residue, fumaric acid residue, itaconic acid residue, crotonic acid residue, isocrotone Examples include acid residues and citraconic acid residues. Of these, a (meth) acryloyl group is most preferred because of its high polymerizability.

  In the present specification, the term (meth) acryloyl represents both methacryloyl and acryloyl, and the same applies to terms such as (meth) acryl and (meth) acrylate.

  Component A preferably has a structure represented by the following formula (A1).

In 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. Examples of preferred polymerizable functional groups include vinyl group, allyl group, (meth) acryloyl group, α-alkoxymethylacryloyl group, maleic acid residue, fumaric acid residue, itaconic acid residue, crotonic acid residue, isocrotone Examples include acid residues and citraconic acid residues. Of these, a (meth) acryloyl group is most preferred because of its high polymerizability.

Preferred specific examples of R ^{1 to} R ⁸ are hydrogen; C 1-20 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, Tetrafluorop Propyl group, a pentafluoropropyl group, tetradecanoyl perfluorooctyl group, pentadecafluorooctyl group, octadecanol fluoro decyl, and fluoroalkyl group having 1 to 20 carbon atoms such as nonafluorobutyl heptadecafluorodecyl group. Among these, hydrogen and a methyl group are more preferable from the viewpoint of imparting good mechanical properties and high oxygen permeability to the soft resin device, and a methyl group is most preferable.

L ¹ and L ² are preferably divalent groups having 1 to 20 carbon atoms. Among them, the group 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. Among them, the following formulas (LE1), (LE3), (LE9) ) And (LE11) are more preferred, groups represented by the following formulas (LE1) and (LE3) are more preferred, and groups represented by the following formula (LE1) are most preferred. Incidentally, 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.

  In formula (A1), a and b each independently represent the number of repeating units. a and b each independently preferably ranges from 0 to 1500. The total value (a + b) of a and 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.

When all of R ^{1 to} R ⁸ are 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. In this case, the value of a is determined by the molecular weight of the polysiloxane compound of component A.

  Only one type of component A of the present invention may be used, or two or more types may be used in combination.

  As another compound copolymerized with Component A, Component B which is a polymerizable monomer having a fluoroalkyl group is preferable. Component B has water and oil repellency due to a decrease in the critical surface tension due to the fluoroalkyl group, which causes the surface of the soft resin device to be contaminated with components such as proteins and lipids in tears and body fluids. There is an effect to suppress. In addition, Component B has an effect of giving a soft resin 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. Hexyl group, hexafluorobutyl group, heptafluorobutyl group, octafluoropentyl group, nonafluoropentyl group, dodecafluoroheptyl group, tridecafluoroheptyl group, dodecafluorooctyl group, tridecafluorooctyl group, hexadecafluorodecyl group , Heptadecafluorodecyl group, tetrafluoropropyl group, pentafluoropropyl group, tetradecafluorooctyl group, pentadecafluorooctyl group, octadecafluorodecyl group, and nonadecafluoro Is a fluoroalkyl group having 1 to 20 carbon atoms such as sill groups. More preferably, 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, and most preferably trifluoroethyl group. It is a group.

  As the polymerizable functional group of Component B, a functional group capable of radical polymerization is preferable, and one having a carbon-carbon double bond is more preferable. Examples of preferred polymerizable functional groups include vinyl group, allyl group, (meth) acryloyl group, α-alkoxymethylacryloyl group, maleic acid residue, fumaric acid residue, itaconic acid residue, crotonic acid residue, isocrotone Examples of the 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 has a great effect of obtaining a soft resin device that is flexible and excellent in wearing feeling and has excellent 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. (Meth) acrylate, hexafluorobutyl (meth) acrylate, hexafluoroisopropyl (meth) acrylate, heptafluorobutyl (meth) acrylate, octafluoropentyl (meth) acrylate, nonafluoropentyl (meth) acrylate, dodecafluoropentyl (meta ) Acrylate, dodecafluoroheptyl (meth) acrylate, dodecafluorooctyl (meth) acrylate, and tridecafluoroheptyl (meth) Acrylate, and the like. 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.

  The B component of the present invention may be used alone or in combination of two or more.

  The content of Component B in the copolymer is preferably 10 to 500 parts by mass, more preferably 20 to 400 parts by mass, and still more preferably 20 to 200 parts by mass with respect to 100 parts by mass of Component A. When the amount of component B used is too small, the resulting soft resin device tends to become cloudy or mechanical properties such as bending resistance tend to be insufficient.

  In addition to Component A and Component B, a copolymer obtained by further copolymerizing a component different from Component A and Component B (hereinafter referred to as Component C) may be used as the copolymer used for the substrate.

  Component C is preferably one that lowers the glass transition point of the copolymer to room temperature or 0 ° C. or lower. 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. Examples of preferred polymerizable functional groups include vinyl group, allyl group, (meth) acryloyl group, α-alkoxymethylacryloyl group, maleic acid residue, fumaric acid residue, itaconic acid residue, crotonic acid residue, isocrotone Examples of the acid residue and citraconic acid residue include a (meth) acryloyl group because of high polymerizability among them.

  Examples of 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) a Examples include relate, tridecyl (meth) acrylate, n-dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and n-stearyl (meth) acrylate, and more preferably n-butyl. (Meth) acrylate, n-octyl (meth) acrylate, n-lauryl (meth) acrylate, and n-stearyl (meth) acrylate. Among these, (meth) acrylic acid alkyl esters having 1 to 10 carbon atoms in the alkyl group are more preferred. If the carbon number of the alkyl group is too large, the transparency of the resulting lens may be lowered, which is not preferable.

  Furthermore, in order to improve mechanical properties, surface wettability, dimensional stability of a soft resin device, and the like, the monomers described below can be copolymerized as desired.

  Examples of the monomer for improving mechanical properties include aromatic vinyl compounds such as styrene, tert-butylstyrene, and α-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, and polyethylene. Glycol methacrylate, N, N-dimethylacrylamide, N-methylacrylamide, dimethylaminoethyl methacrylate, methylenebisacrylamide, diacetone acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylacetamide, and N-vinyl-N- And methyl acetamide. Among them, N, N-dimethylacrylamide, N-methylacrylamide, dimethylaminoethyl methacrylate, methylenebisacrylamide, diacetone acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylacetamide, and N-vinyl-N-methylacetamide Monomers containing amide groups such as are preferred.

  Examples of monomers for improving the dimensional stability of flexible resin devices include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, and bisphenol A. Examples include dimethacrylate, vinyl methacrylate, acrylic methacrylate and acrylates corresponding to these methacrylates, divinylbenzene, triallyl isocyanurate, and the like.

  Only one type of component C may be used, or two or more types may be used in combination.

  The preferred amount of component C used is 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. When the amount of component C used is too small, it is difficult to obtain the effect expected of component C. When the amount of component C used is too large, the resulting soft resin device tends to become cloudy or mechanical properties such as bending resistance tend to be insufficient.

  Furthermore, as a copolymer used for the base material, a copolymer obtained by further copolymerizing component M in addition to component A may be used. Component M is “a monofunctional monomer having one polymerizable functional group and a siloxanyl group per molecule”.

  In this specification, the siloxanyl group means a group having a Si—O—Si bond.

The siloxanyl group of component M is preferably linear. If the siloxanyl group is linear, the shape recoverability of the obtained soft resin device is improved. Here, the straight chain is 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 soft resin 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. Here, “the siloxanyl group is linear” means that the siloxanyl group has the above linear structure and does not have a Si—O—Si bond that does not satisfy the conditions of the linear structure. means.

  It is preferable that a base material has a copolymer containing the component M whose number average molecular weight is 300-120,000 as a main component. Here, 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 number average molecular weight of the component M is preferably 300 to 120,000. When the number average molecular weight of the component M is in this range, a base material that is flexible (low elastic modulus), 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 polymerizable functional group of Component M is preferably a radical polymerizable functional group, and more preferably has a carbon-carbon double bond. Examples of preferred polymerizable functional groups include vinyl group, allyl group, (meth) acryloyl group, α-alkoxymethylacryloyl group, maleic acid residue, fumaric acid residue, itaconic acid residue, crotonic acid residue, isocrotone Examples include acid residues and citraconic acid residues. Of these, a (meth) acryloyl group is most preferred because of its high polymerizability.

  Component M preferably has a structure represented by the following formula (ML1).

In the formula, 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 a radical polymerizable functional group, and preferably has a carbon-carbon double bond. Examples of preferred polymerizable functional groups include vinyl group, allyl group, (meth) acryloyl group, α-alkoxymethylacryloyl group, maleic acid residue, fumaric acid residue, itaconic acid residue, crotonic acid residue, isocrotone 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 group of component M is more preferably copolymerizable with the polymerizable functional group of component A, since a soft resin device having good mechanical properties can be easily obtained. Since it is easy to obtain a soft resin device having good surface characteristics by being uniformly copolymerized, it is more preferably the same as the polymerizable functional group of Component A.

Preferred specific examples of R ^{11 to} R ¹⁹ are hydrogen; C 1-20 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, Tetrafluo Propyl group, a pentafluoropropyl group, tetradecanoyl perfluorooctyl group, pentadecafluorooctyl group, octadecanol fluoro decyl, and fluoroalkyl group having 1 to 20 carbon atoms such as nonafluorobutyl heptadecafluorodecyl group. Among these, hydrogen and a methyl group are more preferable from the viewpoint of imparting good mechanical properties and high oxygen permeability to the soft resin device, and a methyl group is most preferable.

L ³ is preferably a divalent group having 1 to 20 carbon atoms. Among them, the group represented by the following formulas (LE1) to (LE12) is preferable because the compound of the formula (ML1) has an advantage that it can be easily obtained with high purity, and among them, the following formulas (LE1), (LE3), (LE9) ) And (LE11) are more preferred, groups represented by the following formulas (LE1) and (LE3) are more preferred, and groups represented by the following formula (LE1) are most preferred. Incidentally, 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.

  In formula (ML1), the total value (c + d) of c and d is preferably 3 or more, more preferably 10 or more, more preferably 10 to 500, more preferably 30 to 300, and still more preferably 50 to 200.

When all of R ^{11 to} R ¹⁸ are methyl groups, d = 0, and c is preferably 3 to 700, more preferably 10 to 500, more preferably 30 to 300, and still more preferably 50 to 200. In this case, the value of c is determined by the molecular weight of component M.

  In the base material of the soft resin device of the present invention, only one type of component M may be used, or two or more types may be used in combination.

  When the base material of the soft resin device of the present invention contains an appropriate amount of component M, the crosslink density is reduced, the degree of freedom of the polymer is increased, and a moderately soft base material having a low elastic modulus can be realized. it can. On the other hand, when there is too little content of the component M, a crosslinking density will become high and a base material will become hard. Moreover, when there is too much content of the component M, since it will become too soft and it will become easy to tear, it is unpreferable.

  Moreover, in the base material of the soft resin device of the present invention, the mass ratio of the component M and the component A is 5 to 200 parts by mass, more preferably 7 to 150 parts by mass, with respect to 100 parts by mass of the component A. It is preferably 10 to 100 parts by mass. When content of the component M is less than 5 mass parts with respect to 100 mass parts of component A, a crosslinking density will become high and a base material will become hard. On the other hand, when 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 soft resin device of the present invention may further contain components 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. Any of the above-described components can be contained in a non-reactive form or a copolymerized form.

  When the soft resin device of the present invention is an ophthalmic lens and the substrate contains an ultraviolet absorber, the eye of the ophthalmic lens wearer can be protected from harmful ultraviolet rays. In addition, when a colorant is included, the ophthalmic lens is colored to facilitate identification and improve convenience during handling.

  Any of the above-described components can be contained in a non-reactive form or a copolymerized form. When the above components are copolymerized, that is, when a UV absorber having a polymerizable group or a colorant having a polymerizable group is used, the component is copolymerized and immobilized on the base material, so that elution is possible This is preferable because the property is reduced.

  The substrate is preferably composed of a component selected from an ultraviolet absorber and a colorant, and two or more components C (hereinafter referred to as component Ck) other than these components. In that case, as the component Ck, it is preferable that at least one kind is selected from (meth) acrylic acid alkyl esters having 1 to 10 carbon atoms, and at least one kind is selected from the monomers for improving the surface wettability. By using two or more types of component Ck, the affinity with the ultraviolet absorber and the colorant increases, and it becomes easy to obtain a transparent substrate.

  When using a ultraviolet absorber, the preferable usage-amount is 0.01-20 mass parts with respect to 100 mass parts of component A, More preferably, it is 0.05-10 mass parts, More preferably, it is 0.1-2 mass parts. It is. When using a coloring agent, the preferable usage-amount is 0.00001-5 mass parts with respect to 100 mass parts of component A, More preferably, it is 0.0001-1 mass part, More preferably, it is 0.0001-0.5 mass. Part. When there is too little content of a ultraviolet absorber or a coloring agent, it will become difficult to obtain an ultraviolet absorption effect and a coloring effect. On the contrary, when it is too much, it becomes difficult to dissolve these components in the base material. The preferable usage-amount of component Ck is 0.1-100 mass parts with respect to 100 mass parts of component A, respectively, More preferably, it is 1-80 mass parts, More preferably, it is 2-50 mass parts. When the amount of the component Ck used is too small, there is a tendency that it becomes difficult to obtain a transparent substrate due to insufficient affinity with the ultraviolet absorber or the colorant. Even when the amount of the component Ck used is too large, the resulting soft resin device tends to be clouded or has insufficient mechanical properties such as bending resistance, which is not preferable.

  Moreover, it is preferable that the base material of the soft resin device of this invention is a range whose crosslinking degree is 2.0-18.3. The degree of crosslinking is represented by the following formula (Q1).

  In the formula (Q1), Qn represents a total millimolar amount of monomers having n polymerizable groups per molecule, and Wn represents a total mass (kg) of monomers having n polymerizable groups per molecule. When the molecular weight of the monomer has a distribution, the millimolar amount is calculated using the number average molecular weight.

  If the degree of cross-linking of the substrate of the present invention is less than 2.0, it is too soft and difficult to handle, and if it exceeds 18.3, it is too hard and the feeling of wearing or use tends to be unfavorable. 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.

  As a method for producing a base material of the soft resin device of the present invention, for example, a molded body such as a lens shape or a sheet shape, 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. When the lens is obtained by cutting, freezing cutting at a low temperature is suitable.

  As an example, a method for producing an ophthalmic lens as a soft resin device by polymerizing a raw material composition containing component A by a mold polymerization method will be described below. First, a raw material composition is filled in a gap between two mold members having a certain shape. Examples of the material for the mold member include resin, glass, ceramics, and metal. In the case of performing photopolymerization, an optically transparent material is preferable, and therefore resin or glass is preferably used. Depending on the shape of the mold member and the properties of the raw material composition, 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. 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. As a specific mode of photopolymerization, 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). When thermal polymerization is performed, the temperature of the composition is gradually increased from around room temperature, and the temperature is increased 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.

  In the polymerization, it is preferable to add a thermal polymerization initiator or a photopolymerization initiator typified by a peroxide or an azo compound in order to facilitate the polymerization. In the case of performing thermal polymerization, those having optimum decomposition characteristics at a desired reaction temperature are selected. In general, 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.

  In the polymerization, a polymerization solvent can be used. Various organic and inorganic solvents can be used as the solvent. Examples of 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 such as ethyl acetate, butyl acetate, amyl acetate, ethyl lactate and methyl benzoate; aliphatics such as normal hexane, normal heptane and normal octane Hydrocarbon solvents; cycloaliphatic hydrocarbon solvents such as cyclohexane and ethylcyclohexane; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbon solvents such as benzene, toluene and xylene; and Examples include petroleum solvents. These solvents may be used alone or in combination of two or more.

  In the soft resin device of the present invention, a layer made of a hydrophilic polymer (hereinafter referred to as a coating layer) needs to be formed on at least a part of the substrate surface. By having a coating layer, good wettability and slipperiness are imparted to the surface of the lens, and an excellent wearing feeling can be given.

In the present invention, the hydrophilic polymer is a polymer that satisfies any of the following conditions.
(1) A polymer that dissolves in water at 25 ° C. at a concentration of 0.01% by mass or more. However, heating may be performed during the dissolution process.
(2) A polymer having a moisture content of 10% by mass or more at 25 ° C. when the coating layer is formed. However, it is based on the dry mass of the coating layer. Here, the moisture content is a value not including the mass of water adhering to the surface.

  The inventors have found that the soft resin device of the present invention has a hydrophilic polymer, preferably an acidic polymer and a basic polymer on the surface, regardless of whether the substrate is low in water content and soft, or the substrate is neutral. It has been found that by forming a coating layer made of a polymer, it is possible to impart sufficient wettability, slipperiness and antifouling property to the surface of the soft resin device. As a result, when the soft resin device of the present invention is used as, for example, a low hydrous soft ophthalmic lens, the phenomenon of sticking to the cornea during wearing, which has been a problem in conventional low hydrous soft ophthalmic lenses, is greatly reduced. It can be avoided.

  The coating layer of the soft resin device of the present invention does not need to have a covalent bond with the substrate. 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 of the soft resin device of the present invention is based on an acidic polymer solution (“solution” means an aqueous solution) and a basic polymer solution (“solution” means an aqueous solution) described in detail below. It is preferable to form by processing the surface of the material. Here, the aqueous solution is a solution containing water as a main component.

  The acidic polymer solution and the basic polymer solution of the present invention are usually one kind (one kind means a group of polymers produced by one synthesis reaction. Even if one kind (same) polymer is used, the concentration is low). However, it is not regarded as one type of solution, and even if the constituent monomer types are the same, the polymer synthesized by changing the blending ratio is not one type).

  The coating layer is preferably composed of one or more acidic polymers and one or more basic polymers. It is more preferable to use two or more kinds of acidic polymers or two or more kinds of basic polymers because properties such as easy slipping and antifouling properties are easily expressed on the surface of the soft resin device. In particular, when two or more kinds of acidic polymers and one or more kinds of basic polymers are used, 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.

  In addition, the coating layer is preferably treated 1 to 5 times, more preferably 1 to 3 times, and still more preferably 1 to 5 times each of the treatment with one or more acidic polymer solutions and the treatment with one or more basic polymer solutions. It is formed on the surface of the substrate by performing twice. The number of treatments with the acidic polymer solution and the number of treatments with the basic polymer solution may be different.

  In the soft resin device of the present invention, the treatment with one or more acidic polymer solutions and the treatment with one or more basic polymer solutions give excellent wettability and slipperiness in a very small number of times of 2 or 3 times in total. I found that I could do it. This is very important industrially from the viewpoint of shortening the manufacturing process. In that sense, in the soft resin device of the present invention, the total of the treatment with the acidic polymer solution and the treatment with the basic polymer solution is preferably 2 times or 3 times.

  The coating layer according to the soft resin device of the present invention is preferably subjected to treatment with two kinds of acidic polymer solutions once and treatment with a basic polymer solution once.

  In addition, the inventors have also confirmed that expression of wettability and slipperiness is hardly observed when the coating layer contains only one of an acidic polymer and a basic polymer.

  As the basic polymer, a homopolymer or copolymer having a plurality of basic groups along the polymer chain can be suitably used. As the basic group, an amino group and a salt thereof are preferable. For example, suitable examples of such basic polymers include poly (allylamine), poly (vinylamine), poly (ethyleneimine), poly (vinylbenzyltrimethylamine), polyaniline, poly (aminostyrene), poly (N, N An amino group-containing (meth) acrylate polymer such as -dialkylaminoethyl methacrylate), an amino group-containing (meth) acrylamide polymer such as poly (N, N-dimethylaminopropylacrylamide), and salts thereof. The above is an example of a homopolymer, but these copolymers (that is, a copolymer of basic monomers constituting the above basic polymer, or a copolymer of a basic monomer and another monomer) are also preferably used. be able to.

  When the basic polymer is a copolymer, 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. Examples of 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. Of these, 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. When the polymer compound having a quaternary ammonium structure is used, for example, as a coating for a soft ophthalmic lens, it can impart antimicrobial properties to the soft ophthalmic lens.

  As the acidic polymer, a homopolymer or copolymer having a plurality of acidic groups along the polymer chain can be suitably used. As 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. For example, 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 above are examples of homopolymers, but these copolymers (that is, copolymers of acidic monomers constituting the acidic polymer, or copolymers of acidic monomers and other monomers) can also be suitably used. .

  When the acidic polymer is a copolymer, 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. Examples of 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 Salt. Among 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.

  It is preferable that 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. When 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 is easily formed. When 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 and the like can be formed.

  More preferably, two or more of the acidic polymer and the basic polymer are polymers having a group selected from a hydroxyl group and an amide group. That is, the soft resin device preferably contains 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, a copolymer of an acidic monomer and a monomer having an amide group, and the like.

  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.

  As the monomer having an amide group, a monomer having a (meth) acrylamide group and an N-vinylcarboxylic acid amide (including a cyclic one) are preferable from the viewpoint of ease of polymerization. Suitable 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 easy slipping, and N, N-dimethylacrylamide is most preferable.

  Preferable examples of the monomer having a hydroxyl group 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). As the monomer having a hydroxyl group, 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. Of these, 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.

  Specific 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. Acrylamide copolymer, N, N-dimethylaminopropylacrylamide / N-vinylpyrrolidone copolymer, and N, N-dimethylaminopropylacrylamide / N, N-dimethylacrylamide copolymer. Most preferred is N, N-dimethylaminopropylacrylamide / N, N-dimethylacrylamide copolymer.

  Specific preferred examples of 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- An acrylamide-2-methylpropanesulfonic acid / N-vinylpyrrolidone copolymer and a 2-acrylamido-2-methylpropanesulfonic acid / N, N-dimethylacrylamide copolymer. Most preferred is a (meth) acrylic acid / N, N-dimethylacrylamide copolymer.

  Preferred examples of 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 an N, N-dimethylaminoethyl methacrylate / hydroxyethyl (meth) acrylate copolymer.

  Specific preferred examples of the copolymer of the acidic monomer and the monomer having an amide group include (meth) acrylic acid / hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / glycerol (meth) acrylate copolymer, 2 -Acrylamide-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.

  In the case of using a copolymer of the above basic monomer or acidic monomer and another monomer, the copolymerization ratio of [mass of basic monomer or acidic monomer] / [mass of other monomer] is 1/99 to 99 / 1 is preferable, 2/98 to 90/10 is more preferable, and 10/90 to 80/20 is further preferable. When the copolymerization ratio is within this range, functions such as easy slipperiness and antifouling property against tears are easily developed.

  To change various properties of the coating layer, such as thickness, the molecular weight of the acidic and basic polymers can be varied. 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 2000000. More preferably, the molecular weight is 5000 to 1000000, and even more preferably 7500 to 700000. 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).

  Application of the coating layer can be accomplished in a number of ways, for example as described in WO 99/35520, WO 01/57118 or US 2001-0045676.

  In the soft resin device of the present invention, a layer made of a hydrophilic polymer (hereinafter referred to as a coating layer) is formed on at least a part of the surface of the substrate, but at least a part of the layer is crosslinked. Also good. Moreover, in the soft resin device of this invention, at least one part may be bridge | crosslinked between the said base material and the said layer. Here, the term “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 a hydrophilic polymer attached to the substrate. The radiation is preferably various ion beams, electron beams, positron beams, X-rays, γ rays and neutron beams, and more preferably electron beams and γ rays. Most preferred is gamma rays.

  By causing cross-linking in the coating layer or between the coating layer and the substrate as described above, the surface of the soft resin device is given good wettability and easy slipperiness, and gives an excellent wearing feeling. it can. On the other hand, there are cases where cross-linking occurs inside the base material due to irradiation and the soft resin device becomes too hard. In that case, excessive crosslinking inside the substrate can be suppressed by appropriately replacing component A in the substrate with component M and copolymerizing.

  Next, the manufacturing method of the soft resin device of this invention is demonstrated. In the soft resin device of the present invention, one or more acidic polymer solutions and one or more basic polymer solutions are each applied to the surface of the substrate 1 to 5 times, more preferably 1 to 3 times, more preferably each. It is obtained by coating once or twice to form a coating layer. The number of application steps of the acidic polymer solution and the application step of the basic polymer solution may be different.

  In the method for producing a soft resin device of the present invention, the inventors have performed the application process of one or more acidic polymer solutions and the application process of one or more basic polymer solutions in a very small number of times such as 2 or 3 times in total. It was found that excellent wettability and slipperiness can be imparted. This is very important industrially from the viewpoint of shortening the manufacturing process. In that sense, the total of the application step of the acidic polymer solution and the application step of the basic polymer solution is preferably twice or three times.

  In addition, in the soft resin device of the present invention, the inventors have almost exhibited the wettability and the slipperiness only by applying either one of the application step of the acidic polymer solution or the application step of the basic solution once. At the same time, I confirmed that I could not see it.

  From the viewpoint of wettability, slipperiness, and shortening of the manufacturing process, 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 / Basic polymer solution Configuration 4: Application of acidic polymer solution / Application of basic polymer solution / Application of acidic polymer solution Among these configurations, Configurations 1 and 4 show that the obtained soft resin device exhibits particularly excellent wettability. Is more preferable.

  In applying the acidic polymer solution and the basic polymer solution, the surface of the substrate may be untreated or treated. Here, 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 preferable aspects of the manufacturing method of the soft resin device of this invention includes the following process 1-process 3 in this order.
<Step 1>
A step of polymerizing a mixture of monomers to obtain a molded body having a desired shape such as a lens shape or a sheet shape.
<Process 2>
A step of washing and removing excess basic polymer solution after bringing the molded body into contact with the basic polymer solution.
<Step 3>
A step of washing and removing excess acidic polymer solution after bringing the molded body into contact with the acidic polymer solution.

  As described above, by sequentially bringing a molded body having a desired shape into contact with an acidic polymer solution and a basic polymer solution, a layer composed of an acidic polymer and a basic polymer can be formed on the molded body. Thereafter, it is preferable to sufficiently wash away excess polymer.

  As a method for bringing the molded body into contact with an acidic polymer solution or a basic polymer solution, various coating methods such as dipping method (dip method), brush coating method, spray coating method, spin coating method, die coating method, squeegee method, etc. Applicable.

  When contacting the solution by a dipping method, the dipping time can be varied depending on 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 vary depending on the nature of the acidic or basic polymer, the desired coating layer thickness, and a number of 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.

  Further, from the viewpoint of easy slipping, the concentration of the acidic polymer solution and the basic polymer solution is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass, and 1% by mass. -5 mass% is further more preferable.

  The acidic polymer solution and the basic polymer solution pH are preferably maintained at 2 to 5, more preferably 2.5 to 4.5.

  Washing off 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 a 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.

  A step of drying or removing the excess rinsing solution may be included. 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 fixturing 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 the 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 the process time can be shortened.

  The acidic polymer and the basic polymer are preferably applied alternately. By alternately applying, it is possible to obtain a soft resin device having excellent wettability and slipperiness that cannot be obtained with only one polymer, and also excellent wearing feeling.

  The coating layer can be asymmetric. Here, “asymmetric” means having a different coating layer on the first surface of the soft resin device and the second surface on the opposite side. Here, 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% by mass 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% by mass to 1.3% by mass.

Another preferred embodiment of the method for producing a soft resin device of the present invention further includes the following step 4.
<Step 4>
A step of irradiating the molded product obtained by the method including the steps 1 to 3 in this order.

  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. In this case, the solvent for the liquid used for immersing the coated molded body is applicable to various organic and inorganic solvents and is not particularly limited. Examples include water, methanol, ethanol, propanol, 2-propanol, butanol, tert-butanol, tert-amyl alcohol, various alcohol solvents such as 3,7-dimethyl-3-octanol, benzene, toluene, xylene, etc. Various aromatic hydrocarbon solvents, hexane, heptane, octane, decane, petroleum ether, kerosene, ligroin, parafine and other aliphatic hydrocarbon solvents, acetone, methyl ethyl ketone, methyl isobutyl ketone and other ketone solvents, Various ester solvents such as ethyl acetate, butyl acetate, methyl benzoate, dioctyl phthalate, ethylene glycol diacetate, diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dialkyl ether, diethylene glycol dial These are various glycol ether solvents such as ether, triethylene glycol dialkyl ether, tetraethylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polyethylene glycol-polypropylene glycol block copolymer, polyethylene glycol-polypropylene glycol random copolymer, They can be used alone or in combination. Of these, water is most preferred. When irradiation with radiation is performed in a state in which the molded body is immersed in an aqueous liquid, examples of the aqueous liquid include pure water, physiological saline, and a phosphate buffer (preferably pH 7.1 to 7.3). ) And boric acid buffer solutions (preferably pH 7.1 to 7.3) are suitable.

  If radiation is irradiated in a state where the molded body is sealed in a container, there is an advantage that the molded body can be sterilized at the same time.

  As radiation, γ rays are preferably used. In this case, if the dose of γ-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 reduced, so 0.1-100 kGy is preferable. 50 kGy is more preferable, and 20 to 40 kGy is most preferable. Thereby, at least a part in the coating layer and at least a part between the coating layer and the molded body are cross-linked, and the durability (for example, scuffing durability) of the coating layer can be improved.

Next, further features of the soft resin device of the present invention thus produced will be described.
FIG. 1 is a cross-sectional view schematically showing a part of the structure of the soft resin device of the present invention. As shown in FIGS. 1A to 1C, the soft resin device 10 includes a base material 11 and a coating layer 12 made of an acidic polymer and a basic polymer formed on the surface of the base material 11.

FIG. 1A shows a completely wet state in which the entire surface of the soft resin device 10 is covered with a predetermined liquid such as a storage liquid, and the coating layer 12 is almost completely swollen. At this time, the thickness t ₁ of the coating layer 12 is the maximum within the range that the soft resin device 10 can take. At this time, the surface of the coating layer 12 is almost flat, and unevenness or the like is hardly observed.

FIG. 1B shows a quasi-wet state in which the soft resin device 10 is taken out of the liquid and exposed to the atmosphere, and the drying is slightly advanced. For example, after the soft resin device 10 is taken out of the liquid, when a certain time (for example, about 30 seconds) elapses, the coating layer 12 is in a semi-wet state. The thickness t ₂ (t ₂ <t ₁ ) of the coating layer 12 gradually decreases as the drying of the soft resin device 10 proceeds.

Further, when the coating layer 12 shifts from the completely wet state to the semi-moist state, the concave portion 13 appears on the surface of the coating layer 12. The size of the recess 13, depending on the components of the thickness _{t 2} and a coating layer 12 of the coating layer 12, for example, the diameter D is about 0.1μm about ～200Myuemu, the depth d of about 1μm about ~1000μm It is.

  In addition, when the recessed part 13 appears in the coating layer 12, the soft resin device 10 can be immersed in the said predetermined liquid, for example, and the coating layer 12 can be returned to a complete wet state again. In this case, the recess 13 disappears as the coating layer 12 swells.

FIG. 1C shows a dried state in which the coating layer 12 is dried beyond the semi-wet state. For example, when about 1 minute elapses after the soft resin device 10 is taken out from the liquid, the coating layer 12 is in a dry state. The thickness of the coating layer 12 t ₃ has become thinner than the thickness t _2, also be 1/100 or less in thickness t ₁ in a completely wet state. For example, when the thickness t ₁ is 90 μm or more, the thickness t ₃ may be 0.1 μm or less.

  Moreover, when the coating layer 12 shifts from the semi-wet state to the dry state, the concave portion 13 generated in the coating layer 12 disappears.

Here, when the soft resin device 10 is an ophthalmic lens, when the coating layer 12 is in a completely wet state and a semi-wet state (so-called moist state), the soft resin device 10 is in a state suitable for use or used. It can be said that it is possible. On the other hand, when the soft resin device is in a dry state, with the thickness t ₃ of the coating layer 12 becomes insufficient, and the loss of desirable properties of the coating layer 12 described above, can not state or use unsuitable in use It becomes.

  Therefore, the user can easily determine whether or not the soft resin device 10 is suitable for use by observing the surface of the soft resin device 10 when using the soft resin device 10. Can do. For example, after the soft resin device 10 is taken out of the liquid, if the recess 13 has not yet appeared, the user can determine that the soft resin device 10 is in a state suitable for use. In this case, the user may use the soft resin device 10 as it is (attached to a predetermined part). Further, when the recess 13 starts to appear on the surface of the soft resin device 10 after the soft resin device 10 is taken out of the liquid, the user has slightly dried the soft resin device 10 as compared with the completely wet state. Therefore, it can be determined that it is in a usable state. In this case, the user preferably uses the soft resin device 10 as soon as possible or recovers the wet state by immersing the soft resin device 10 again in a liquid such as a storage solution. Further, when time passes and the concave portion 13 once appeared on the surface of the soft resin device 10 disappears, the user can determine that the soft resin device 10 is not in a state suitable for use. If it is dried to this extent, it is not preferable to use the soft resin device 10 as it is, so the user uses the soft resin device 10 after recovering the wet state by immersing the soft resin device 10 again in a liquid such as a storage solution. Alternatively, it is preferable to take measures such as canceling the use of the soft resin device 10.

Here, if the number of the concave portions appearing in the soft resin device of the present invention is too large, the appearance quality deteriorates, which is not preferable. On the other hand, if the number of concave portions is too small, the visibility is lowered, and it becomes difficult to distinguish between a completely wet state, a semi-wet state, and a dry state, which is not preferable. The number of recesses is preferably larger from the viewpoint of visibility, preferably 1 or more, more preferably 5 or more, and most preferably 10 or more per 10 cm ² of the surface area of the soft resin device. On the other hand, the number of recesses is preferably smaller from the viewpoint of appearance quality, preferably 10,000 or less, more preferably 1000 or less, and most preferably 300 or less per 10 cm ² of the surface area of the soft resin device. In addition, “per 10 cm ² surface area of the soft resin device” means “the surface of the soft resin device, and a portion having an arbitrary continuous area of 10 cm ² among the portions having a layer made of an acidic polymer and a basic polymer. It means "when observed." Moreover, in the case of the soft resin device whose applicable surface area is less than 10 cm < ² >, the surface (total area 10 cm < ² >) of arbitrary soft resin devices shall be observed. Here, the “arbitrary plural” is more preferably “random plural”.

  Such a soft resin device of the present invention includes a soft member having, for example, a sheet shape or a film shape. Specifically, as the soft resin device of the present invention, a medical device such as a skin covering material, a wound covering material, a skin protecting material, or a skin drug carrier that is used by being attached to the surface of a living body, a cell culture sheet or tissue Biotechnology devices such as regenerative scaffolding materials, separation membrane devices such as gas-liquid separation membranes and liquid-liquid separation membranes, image forming devices such as printing materials, stamps and stamp stands (red meat), and facial packs (soft substrates) Beauty devices such as those containing a cosmetic liquid in a material), daily necessities such as a freshness-keeping sheet for seafood, and a heat-cooled sheet.

  Moreover, the soft resin device of this invention is provided with the member which makes a spherical crown shape, for example. Specifically, examples of the soft resin device of the present invention include ophthalmic medical devices such as a soft ophthalmic lens (soft contact lens), an intraocular lens, an artificial cornea, a corneal inlay, a corneal onlay, and an eyeglass lens.

  In addition, the soft resin device of the present invention is not limited to the above-exemplified soft resin device, and can be used by being molded into various shapes.

  Examples of the present invention will be specifically described below, but the present invention is not limited thereto.

Analysis method and evaluation method (1) Moisture content A contact lens-shaped test piece was used. After immersing the test piece in a borate buffer solution and leaving it at room temperature 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. From these masses Ww and Wd, the water content was determined by the following equation. When the obtained value was less than 1%, it was judged to be below the measurement limit, and was expressed as “less than 1%”.

Moisture content (%) = 100 × (Ww−Wd) / Ww
(2) Number of recesses A contact lens-shaped test piece in a wet state T with a borate buffer solution was immersed in a borate buffer solution in a beaker at room temperature. The beaker containing the test piece and borate buffer was put on an ultrasonic cleaner (30 seconds). The test piece was pulled up from the borate buffer solution, and the state of the surface within 3 minutes at which water was completely cut when held in the air so that the diametrical direction was vertical was visually observed, and the number of appearing recesses was measured. Hereinafter, in the case of a spherical crown shape (contact lens shape), the diameter refers to the diameter of a circle formed by the edge.
(3) Size and depth of recess Using a color 3D laser microscope (KEYENCE), the size and depth of the recess were measured at a magnification of 10 times. Remove the contact lens-shaped test piece soaked in borate buffer solution in a beaker for 24 hours or more, place the test piece in a convex state on the preparation, and show the concave portion that appeared within 3 minutes when the water was completely cut. Size and depth were measured. When a plurality of recesses appeared, an arbitrary recess was selected and the size and depth were measured.
(4) Easy slip The contact lens-shaped test piece was immersed in a borate buffer 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 (30 seconds). The test piece was pulled up from the borate buffer and was subjected to a sensitivity evaluation when rubbed with a finger for 5 times.

      A: There is very excellent slipperiness.

      B: Easily slippery between A and C.

      C: Medium slipperiness.

      D: There is almost no slipperiness (about the middle of C and E).

E: There is no slipperiness.
(5) Durability of scrubbing Make a dimple in the center of the palm and place a wet sample (contact lens shape) with borate buffer, and add the washing solution (Boschrom, “Renew®”) to it. Then, it was rubbed 10 times on the front and back with the index finger of the other hand. Thereafter, the sample was further sandwiched between the thumb and forefinger, and both sides were rubbed 20 times while the cleaning solution was applied to the sample. The sample after scrubbing was immersed in a borate buffer. Then, (4) easy slipperiness evaluation was performed.
(6) Tensile modulus, tensile elongation (breaking elongation)
The measurement was carried out using a test piece in a wet state T with borate buffer. A test piece having a width (minimum portion) of 5 mm, a length of 14 mm, and a thickness of 0.2 mm was cut out from the contact lens-shaped sample using a prescribed punching die. Using the test piece, a tensile test was performed using Tensilon RTM-100 manufactured by Orientec. The tensile speed was 100 mm / min, and the distance between grips (initial) was 5 mm.
(7) Water wettability The sample was immersed in a borate buffer 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 is pulled up from the borate buffer solution, and the state of the surface is visually observed when held in the air so that the surface of the sample (diameter direction of the circle formed by the edge in the case of a contact lens) is vertical. Judged by the criteria of.

A: The liquid film on the surface is held for 20 seconds or more. B: The liquid film on the surface is cut in 10 seconds or more and less than 20 seconds. Cut in 5 seconds or more and less than 5 seconds E: The liquid film on the surface cuts instantaneously (less than 1 second).
(8) Boiling durability A sample (contact lens shape) was placed in a closed vial soaked in borate buffer. After autoclaving at 121 ° C. for 30 minutes, the mixture was cooled to room temperature. This was defined as one cycle, and 5 cycles were repeated. Then, the water wettability evaluation of the above (7) was performed.
(9) Mucin adhesion Mucin, Bovine Submaxillary Gland (Catalog No. 499643) of CALBIOCHEM was used as mucin. After the contact lens-shaped sample was immersed in a 0.1% strength mucin aqueous solution for 20 hours at 37 ° C., the amount of mucin adhering to the sample was quantified by BCA (bicinchoninic acid) protein assay.
(10) Artificial tear immersion test Prepared according to the method described in International Publication No. 2008/127299 pamphlet, page 32, lines 5 to 36, except that oleic acid is used as an artificial tear instead of oleic acid propyl ester. A tear-like liquid (TLF) buffer solution was used. 2 mL of artificial tears was placed in one well of a culture multi-plate (24-well type, material polystyrene, radiation sterilized), and one sample (contact lens shape) was immersed therein. The mixture was shaken at 100 rpm and 37 ° C. for 24 hours. Thereafter, the sample was taken out, washed lightly with a phosphate buffered salt solution (PBS; pH about 7.2), and then immersed in a well in which 2 mL of artificial tear was replaced. Furthermore, after shaking at 100 rpm and 37 ° C. for 24 hours, the sample was lightly washed with PBS, and the amount of deposits was observed by visually evaluating the degree of white turbidity of the sample. Evaluation was performed according to the following criteria.

      A: No cloudiness is observed.

      B: There is a slight cloudy part (less than 10% in area).

      C: There is a considerable amount of cloudy parts (10% to 50% in area).

      D: Most (50 to 100% in area) is cloudy but the back side is seen through.

      E: The whole is dark and cloudy, and the back side is difficult to see through.

(11) Transparency A contact lens-shaped test piece in a wet state with a borate buffer was visually observed, and transparency was evaluated according to the following criteria.

      A: Transparent with no turbidity.

      B: White turbidity between A and C.

      C: Translucent and translucent.

      D: White turbidity between C and E.

E: White turbidity and no transparency.
(12) Wearing feeling A contact lens-shaped sample in a wet state with a borate buffer solution was worn by two subjects for 6 hours. Evaluation was made according to the following criteria. The feeling of dryness included the feeling of foreign matter accompanying the drying (so-called groovy feeling).

      A: Neither of them felt dry.

      B: Only one person felt dry.

      C: Both felt dry.

      D: One person strongly felt dryness or sticking to the eyes, so wearing was discontinued.

E: Since two people strongly felt a feeling of dryness or sticking to the eyes, wearing was discontinued.
<Synthesis example>
Although the synthesis example of the copolymer used for the coating in an Example is shown, the molecular weight of the copolymer in this synthesis example was measured on the conditions shown below.
(GPC measurement conditions)
Equipment: Prominence GPC system manufactured by Shimadzu Corporation Pump: LC-20AD
Autosampler: SIL-20AHT
Column oven: CTO-20A
Detector: RID-10A
Column: GMPWXL manufactured by Tosoh Corporation (inner diameter 7.8 mm × 30 cm, particle diameter 13 μm)
Solvent: Water / methanol = 1/1 (0.1N lithium nitrate added)
Flow rate: 0.5 mL / min Measurement time: 30 minutes Sample concentration: 0.1% by mass
Injection volume: 100 μL
Standard sample: Standard polyethylene oxide sample (0.1 kD to 1258 kD) manufactured by Agilent.
(Synthesis Example 1)
Hereinafter, pure water refers to water purified by filtration through a reverse osmosis membrane.
<CPDA: N, N-dimethylacrylamide / acrylic acid (molar ratio 2/1)>
In a 500 mL three-necked flask, N, N-dimethylacrylamide (59.50 g, 0.600 mol), acrylic acid (21.62 g, 0.300 mol), pure water (325.20 g), polymerization initiator VA-061 (Wako Pure Chemical Industries, Ltd.) 0.1408 g, 0.562 mmol) and 2-mercaptoethanol (43.8 μL, 0.63 mmol) were added, and a three-way cock, reflux condenser, thermometer, and mechanical stirrer were attached. The monomer concentration was 20% by mass. The inside of the three-necked flask was evacuated with a vacuum pump, and after argon substitution was repeated three times, the mixture was stirred at 50 ° C. for 0.5 hour, then heated to 70 ° C. and stirred for 6.5 hours. After completion of the polymerization, the polymerization reaction solution was concentrated to 400 g with an evaporator, poured into 2-propanol / n-hexane = 500 mL / 500 mL, allowed to stand, and then the supernatant was removed by decantation. The obtained solid content was washed three times with 2-propanol / n-hexane = 250 mL / 250 mL. 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. The molecular weight of the copolymer thus obtained was Mn: 55 kD, Mw: 192 kD (Mw / Mn = 3.5).
(Synthesis Example 2)
<CPVPA: N-vinylpyrrolidone / acrylic acid (molar ratio 90/10)>
In a 500 mL three-necked flask, N-vinylpyrrolidone (NVP, 90.02 g, 0.81 mol), acrylic acid (6.49 g, 0.09 mol), dimethyl sulfoxide (386.8 g), polymerization initiator VA-061 (Wako Pure Chemical Industries, Ltd.) 0.1408 g, 0.562 mmol) and 2-mercaptoethanol (2-ME, 43.8 μL, 0.63 mmol) were added, and a three-way cock, a reflux condenser, a thermometer, and a mechanical stirrer were attached. The monomer concentration was 20% by mass. The inside of the three-necked flask was evacuated with a vacuum pump, and after argon substitution was repeated three times, the mixture was stirred at 50 ° C. for 0.5 hour, then heated to 70 ° C. and stirred for 6.5 hours. After completion of the polymerization, the polymerization reaction solution was cooled to room temperature, 100 mL of water was added, and then poured into 500 mL of acetone and left overnight. The next day, 200 mL of acetone and 100 mL of hexane were added, and the supernatant was removed by decantation. The obtained solid content was washed 7 times with acetone / water = 500 mL / 100 mL. 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. The molecular weight of the copolymer thus obtained was Mn: 35 kD, Mw: 130 kD (Mw / Mn = 3.8).
(Synthesis Example 3)
<CPHA: 2-hydroxyethyl methacrylate / acrylic acid (molar ratio 3/1)>
In a 300 mL three-necked flask, 2-hydroxyethyl methacrylate (HEMA, 17.1 g, 0.15 mol), acrylic acid (AA, 3.6 g, 0.05 mol), dimethyl sulfoxide (48.4 g), polymerization initiator VA-061 ( Wako Pure Chemical, 0.0310 g, 0.124 mmol) was added, and a three-way cock, a reflux condenser, a thermometer, and a mechanical stirrer were attached. The monomer concentration was 30% by mass. The inside of the three-necked flask was evacuated with a vacuum pump, and after argon substitution was repeated three times, the mixture was stirred at 60 ° C. for 0.5 hour, then heated to 70 ° C. and stirred for 4.5 hours. After completion of the polymerization, the polymerization reaction solution was cooled to room temperature, 100 mL of ethanol was added, and then poured into 500 mL of water and allowed to stand overnight. On the next day, the supernatant was discarded, and the obtained solid content was further washed twice with 500 mL of water. 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. The molecular weight of the copolymer thus obtained was Mn: 61 kD, Mw: 267 kD (Mw / Mn = 4.4).
(Reference Example 1)
Preparation of coloring agent 20 g pure water was put into a 50 mL screw bottle. 0.5 g of UniBlue A (product number 298409, Sigma-Aldrich) was added and dissolved in an incubator at 37 ° C. After dissolution, 4 g of 1N hydrochloric acid was added, and a pH of about 1-2 was confirmed with a pH test paper. 24 g of ethyl acetate was added and lightly stirred. It moved to 100 mL Nasralasco and left still. Since UniBlue A moved to the ethyl acetate side, the lower aqueous layer was discarded. The ethyl acetate layer was transferred to a 100 mL eggplant flask and evaporated with a 20 ° C. evaporator. Then, it dried at 40 degreeC with the vacuum dryer for 16 hours, and acid type UniBlue A [presumed structural formula (M3)] was obtained.

(Reference Example 2)
Preparation of coating solution <PAA solution>
Polyacrylic acid (169-18591, Wako Pure Chemical Industries, Ltd., molecular weight 250,000) was dissolved in pure water to give a 1.2% by mass aqueous solution.
<PEI solution>
Polyethyleneimine (P3143, Sigma-Aldrich, molecular weight 750,000) was dissolved in pure water to give a 1% by mass aqueous solution.
<PAAM solution>
Polyallylamine (PAA-25, Nittobo, molecular weight 25,000) was dissolved in pure water to give a 1% by mass aqueous solution.
<CPDA solution>
CPDA of Synthesis Example 1 was dissolved in pure water to make a 1% by mass aqueous solution.
<CPVPA solution>
CPVPA of Synthesis Example 2 was dissolved in pure water to make a 1% by mass aqueous solution.
<CPHA solution>
CPHA of Synthesis Example 3 was dissolved in a 0.5 mass% methanol aqueous solution to obtain a CPHA concentration of 0.1 mass%.
<PAMPS solution>
A 2-acrylamido-2-methylpropanesulfonic acid polymer (Sigma Aldrich, molecular weight 2 million, 15% by mass aqueous solution) was dissolved in pure water to give a 1.5% by mass aqueous solution.
(Reference Example 3)
Polydimethylsiloxane having a methacryloyl group at both ends as component A (FM7726, JNC, compound of formula (M4), mass average molecular weight 29 kD, number average molecular weight 26 kD) (50 parts by mass), component B is trifluoroethyl acrylate (biscort 3F, Osaka Organic Chemical Industry (45 parts by mass), 2-ethylhexyl acrylate (3 parts by mass) as component C, dimethylaminoethyl acrylate (1 part by mass) as component C, and UV absorber having a polymerizable group as component C (RUVA-93, Otsuka Chemical) (1 part by mass), as component C, acid type UniBlue A (Reference Example 1) (0.04 part by mass), polymerization initiator “Irgacure (registered trademark)” 819 (Ciba Specialty) Chemicals, 0.75 parts by mass) and t-amyl alcohol (10 parts by mass) Combined and stirred. The monomer mixture was obtained by filtering with a membrane filter (0.45 μm) 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 (base curve side polypropylene, front curve side ZEONOR) in a nitrogen atmosphere glove box, and use fluorescent lamps (Toshiba, FL-6D, daylight color, 6W, 4). And polymerized by light irradiation (1.01 mW / cm ² , 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. 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 2 hours or more. The diameter of the edge part of the obtained lens was about 14 mm, and the thickness of the center part was about 0.07 mm.
(Reference Example 4)
Polydimethylsiloxane having a methacryloyl group at both ends as component A (FM7726, JNC, compound of formula (M4), mass average molecular weight 29 kD, number average molecular weight 26 kD) (50 parts by mass), component B is trifluoroethyl acrylate (biscort 3F, Osaka Organic Chemical Industry) (48.5 parts by mass), methyl methacrylate (0.5 parts by mass) as component C, ultraviolet absorber having a polymerizable group as component C (RUVA-93, Otsuka Chemical) (1 Part by mass), a polymerization initiator “Irgacure (registered trademark)” 819 (Ciba Specialty Chemicals, 0.75 part by mass) and t-amyl alcohol (10 parts by mass) were mixed and stirred. Thereafter, the same operation as in Reference Example 3 was performed to produce a lens. The diameter of the edge part of the obtained lens was about 14 mm, and the thickness of the center part was about 0.07 mm.
(Reference Example 5)
Silicone monomer represented by formula (M5) (13.4 parts by mass), N, N-dimethylacrylamide (37.0 parts by mass), silicone monomer represented by formula (M6) (36.6 parts by mass), Photoinitiator Irgacure 1850 (1.26 parts by mass), UV absorber (RUVA-93, Otsuka Chemical) (1.26 parts by mass) -2-hydroxyethyl methacrylate (9.2 parts by mass), triethylene glycol di Methacrylate (1.26 parts by mass), UniBlue A (product number 298409, Sigma-Aldrich, structure of formula (M7), 0.02 parts by mass), tetrahydrolinalool (23.9 parts by mass) were mixed and stirred. The monomer mixture was obtained by filtering with a membrane filter (0.45 μm) 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 (base curve side polypropylene, front curve side ZEONOR) in a nitrogen atmosphere glove box, and use fluorescent lamps (Toshiba, FL-6D, daylight color, 6W, 4). And polymerized by light irradiation (1.01 mW / cm ² , 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. 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 2 hours or more. The diameter of the edge part of the obtained lens was about 14 mm, and the thickness of the center part was about 0.07 mm.

Example 1
The lens obtained in Reference Example 3 was immersed in a PAMPS solution at room temperature for 30 minutes, and then lightly rinsed with pure water in a beaker. The lens was transferred to a beaker containing fresh pure water and placed in an ultrasonic cleaner (30 seconds). Furthermore, it was rinsed lightly in a beaker containing fresh pure water. Subsequently, the same operation was repeated in the order of the PEI solution and the CPDA solution. After finishing the coating operation, the coated lens was immersed in a borate buffer solution in a sealed vial, autoclaved at 121 ° C. for 30 minutes, and then allowed to stand at room temperature for 24 hours or more. When the lens was lifted from the borate buffer and held in the air so that the diameter direction was vertical, the concave portion was visually observed. Furthermore, the appearing concave portion could not be visually confirmed after at least 3 minutes had elapsed. Accordingly, it was confirmed that a concave portion appeared while the lens was moistened (while it was in a semi-moist state), and that the concave portion disappeared when the moisture on the lens surface was cut (when it was in a dry state). The evaluation results are shown in Table 1.

(Example 2)
The lens obtained in Reference Example 4 was immersed in a PAMPS solution at room temperature for 30 minutes, and then lightly rinsed with pure water in a beaker. The lens was transferred to a beaker containing fresh pure water and placed in an ultrasonic cleaner (30 seconds). Furthermore, it was rinsed lightly in a beaker containing fresh pure water. Subsequently, the same operation was repeated in the order of the PEI solution and the CPDA solution. After finishing the coating operation, the coated lens was immersed in a borate buffer solution in a sealed vial, autoclaved at 121 ° C. for 30 minutes, and then allowed to stand at room temperature for 24 hours or more. When the lens was lifted from the borate buffer and held in the air so that the diameter direction was vertical, the concave portion was visually observed. Furthermore, the appearing concave portion could not be visually confirmed after at least 3 minutes had elapsed. Accordingly, it was confirmed that a concave portion appeared while the lens was moistened, and that the concave portion disappeared when the moisture on the lens surface was cut. The evaluation results are shown in Table 1.
(Example 3)
The lens obtained in Reference Example 3 was immersed in a PAMPS solution at room temperature for 30 minutes, and then lightly rinsed with pure water in a beaker. The lens was transferred to a beaker containing fresh pure water and placed in an ultrasonic cleaner (30 seconds). Furthermore, it was rinsed lightly in a beaker containing fresh pure water. Subsequently, the same operation was repeated in the order of the PEI solution and the PAMPS solution. After finishing the coating operation, the coated lens was immersed in a borate buffer solution in a sealed vial, autoclaved at 121 ° C. for 30 minutes, and then allowed to stand at room temperature for 24 hours or more. When the lens was lifted from the borate buffer and held in the air so that the diameter direction was vertical, the concave portion was visually observed. Furthermore, the appearing concave portion could not be visually confirmed after at least 3 minutes had elapsed. Accordingly, it was confirmed that a concave portion appeared while the lens was moistened, and that the concave portion disappeared when the moisture on the lens surface was cut. The evaluation results are shown in Table 1.
Example 4
The lens obtained in Reference Example 4 was immersed in a PAMPS solution at room temperature for 30 minutes, and then lightly rinsed with pure water in a beaker. The lens was transferred to a beaker containing fresh pure water and placed in an ultrasonic cleaner (30 seconds). Furthermore, it was rinsed lightly in a beaker containing fresh pure water. Subsequently, the same operation was repeated in the order of the PEI solution and the PAMPS solution. After finishing the coating operation, the coated lens was immersed in a borate buffer solution in a sealed vial, autoclaved at 121 ° C. for 30 minutes, and then allowed to stand at room temperature for 24 hours or more. When the lens was lifted from the borate buffer and held in the air so that the diameter direction was vertical, the concave portion was visually observed. Furthermore, the appearing concave portion could not be visually confirmed after at least 3 minutes had elapsed. Accordingly, it was confirmed that a concave portion appeared while the lens was moistened, and that the concave portion disappeared when the moisture on the lens surface was cut. The evaluation results are shown in Table 1.
(Comparative Example 1)
A commercially available soft contact lens “Acuvue Oasis (registered trademark)” (manufactured by Johnson & Johnson Vision Care Incorporated) was lightly rinsed with pure water in a beaker. Next, the sample was transferred to a beaker containing fresh pure water and subjected to an ultrasonic cleaner (30 seconds). Furthermore, it was rinsed lightly in a beaker containing fresh pure water. The lens was immersed in borate buffer at room temperature for 24 hours or more. When the lens was pulled up from the borate buffer solution and held in the air so that the diameter direction was vertical, the concave portion was not visually observed. Accordingly, it has not been possible to determine whether the lens is in a semi-moist state or a dry state. The evaluation results are shown in Table 1.
(Comparative Example 2)
A commercially available soft contact lens “FOCUS DAILIES AQUA®” (manufactured by CIBA Vision) was lightly rinsed with pure water in a beaker. Next, the sample was transferred to a beaker containing fresh pure water and subjected to an ultrasonic cleaner (30 seconds). Furthermore, it was rinsed lightly in a beaker containing fresh pure water. The lens was immersed in borate buffer at room temperature for 24 hours or more. When the lens was pulled up from the borate buffer solution and held in the air so that the diameter direction was vertical, the concave portion was not visually observed. Accordingly, it has not been possible to determine whether the lens is in a semi-moist state or a dry state. The evaluation results are shown in Table 1.
(Comparative Example 3)
The lens obtained in Reference Example 3 was immersed in a 1% by mass 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. was there. 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.
(Examples 5 to 19 and Comparative Examples 4 to 8)
The molded body obtained in each reference example shown in Table 2 was immersed in the first solution shown in Table 2 for 30 minutes at room temperature, rinsed lightly with pure water in a beaker, and then freshly purified. The sample was transferred to a beaker containing water, placed in an ultrasonic cleaner for 30 seconds, and rinsed lightly in a beaker containing fresh pure water. Next, the molded body was immersed in the second solution shown in Table 2 for 30 minutes at room temperature, rinsed lightly with pure water in a beaker, then transferred to a beaker containing fresh pure water, and subjected to ultrasonic cleaning. It was placed in a vessel for 30 seconds and then rinsed lightly in a beaker containing fresh pure water. The same operation was repeated until the fifth solution (however,-in the first solution to fifth solution column in Table 2 means that no operation with the solution was performed). The obtained molded body is immersed in a borate buffer solution in a sealed vial, autoclaved at 121 ° C. for 30 minutes, and then allowed to stand at room temperature for 24 hours or more to maintain a low water content soft contact. I got a lens.

When the low hydrous soft contact lenses obtained in Examples 5 to 19 were pulled up from the borate buffer solution and held so that the diameter direction was vertical in the air, initially, the concave portion was not visually observed, but 5 seconds to 1 minute. The concave portion was visually observed before the passage. Furthermore, the appearing concave portion could not be visually confirmed after at least 3 minutes had elapsed. Accordingly, it was confirmed that a concave portion appeared while the lens was moistened (while it was in a semi-moist state), and that the concave portion disappeared when the moisture on the lens surface was cut (when it was in a dry state). On the other hand, the low hydrous soft contact lenses obtained in Comparative Examples 4 to 8 were pulled up from the borate buffer solution and held so that the diameter direction was vertical in the air. A concave portion appeared and was not visually observed. The other evaluation results of the low hydrous soft contact lens are shown in Table 2. However,-in the evaluation result column in Table 2 means that the evaluation is not performed.
(Comparative Example 9)
The coating A described in Example 3 of JP-T-2005-538418 was applied to the molded body obtained in the reference example. The obtained molded body is immersed in a borate buffer solution in a sealed vial, autoclaved at 121 ° C. for 30 minutes, and then allowed to stand at room temperature for 24 hours or more to maintain a low water content soft contact. I got a lens. The obtained low hydrous soft contact lens was pulled up from the borate buffer solution and held in the air so that the diametrical direction was vertical, but a recess appeared immediately after the lifting and after 30 minutes, and is visually observed. It never happened.

  TECHNICAL FIELD The present invention relates to a soft resin device formed of a soft substrate, and is a coating used for ophthalmic lenses, intraocular lenses, artificial corneas, corneal inlays, corneal onlays, and the like, or affixed to a biological surface It is useful in medical devices such as materials, biotechnology devices, or beauty devices.

DESCRIPTION OF SYMBOLS 10 Soft resin device 11 Base material 12 Coating layer 13 Recessed part

Claims (16)

A substrate;
Consisting of a hydrophilic polymer formed on at least a part of the surface of the substrate, the thickness varies in the atmosphere, and in accordance with the thickness, a fully wet state and a semi-wet in order from the larger thickness range And a layer that takes a dry state,
A concave part is formed in the layer in the quasi-wet state.   2. The soft resin device according to claim 1, wherein the concave portion appears when the layer shifts from the completely wet state to the quasi-wet state. 3.   The soft resin device according to claim 1, wherein the concave portion disappears when the layer moves from the semi-wet state to the dry state.   The soft resin device is characterized in that a diameter of the recess is 0.1 μm or more and 200 μm or less, and a depth of the recess is 1 μm or more and 1000 μm or less.   A soft resin device, wherein the hydrophilic polymer comprises an acidic polymer and a basic polymer. The soft resin device according to any one of claims 1 to 5, wherein the base material is mainly composed of a polymer of the following component A or a copolymer of the following component A and component B. ;
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 soft resin device according to claim 6, wherein the component A is a polysiloxane compound having two polymerizable functional groups per molecule. The soft resin device according to claim 7, wherein the component A is a polysiloxane compound represented by the following formula (A1).

In the formula, 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.   The soft resin device according to any one of claims 6 to 8, wherein the base material contains 5 mass% or more of silicon atoms.   The soft resin device according to claim 6, wherein the component B is a fluoroalkyl ester of (meth) acrylic acid.   The layer composed of the acidic polymer and the basic polymer is formed by performing treatment with one or more acidic polymer solutions once or more, and performing treatment with one or more basic polymer solutions once or more. The soft resin device according to claim 5, wherein   The layer composed of the acidic polymer and the basic polymer is formed by performing the treatment with the acidic polymer solution once or twice and the treatment with the basic polymer solution once or twice for a total of three times. The soft resin device according to claim 11, wherein the soft resin device is formed.   The layer composed of the acidic polymer and the basic polymer is formed by performing treatment with two kinds of acidic polymer solutions twice and treatment with the basic polymer solution once. The soft resin device described.   2. The polymer having a group selected from a hydroxyl group and an amide group, wherein at least one of the acidic polymer and the basic polymer forming a layer composed of the acidic polymer and the basic polymer is a polymer. The soft resin device according to any one of 1 to 13.   It is a soft ophthalmic lens, The soft resin device of any one of Claims 1-14 characterized by the above-mentioned. A substrate;
A layer made of a hydrophilic polymer formed on at least a part of the surface of the substrate;
A soft resin device comprising:
When the soft resin device is taken out from the state immersed in pure water or borate buffer,
In at least a part of the time range from 5 seconds to 30 minutes after removal, a concave portion that can be visually observed is formed on the surface,
And after 5 seconds from the removal, and after 30 minutes from the removal, the concave portion disappears to such an extent that it is at least not visually observed.
A soft resin device characterized by that.

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