WO2013024800A1

WO2013024800A1 - Low-moisture-content soft device and method for producing same

Info

Publication number: WO2013024800A1
Application number: PCT/JP2012/070436
Authority: WO
Inventors: 北川瑠美子; 中村正孝
Original assignee: 東レ株式会社
Priority date: 2011-08-17
Filing date: 2012-08-10
Publication date: 2013-02-21
Also published as: JP6338263B2; TWI535743B; TW201319098A; JPWO2013024800A1

Abstract

This low-moisture-content soft device is provided with a soft member where a layer comprising an acidic polymer and a basic polymer has been formed on at least a part of the surface of a low-moisture-content soft base material. This method for producing the low-moisture-content soft device comprises, in the stated order: a step (1) for polymerizing a mixture including a compound (A), which is a polysiloxane compound having a plurality of polymerizable functional groups per molecule and having a number-average molecular weight of 6,000 or higher, and a compound (B), which is a polymerizable monomer having a fluoroalkyl group, to obtain a molded body of a desired shape; a step (2) for bringing the molded body into contact with a basic polymer solution and thereafter rinsing out and removing the surplus basic polymer solution; and a step (3) for bringing the molded body into contact with an acidic polymer solution and thereafter rinsing out and removing the surplus acidic polymer solution. The present invention provides a low-moisture-content soft device that is hydrophilic in addition to being favorably lubricious, is less prone to drying out even when used for a long period of time, can retain softness, and will have little change in shape, as well as a method for producing the same.

Description

Low hydrous soft device and manufacturing method thereof

The present invention relates to a low hydrous soft device and a method for producing the same.

Conventionally, in various fields, resinous soft materials such as silicone rubber, PVC, nylon elastomer, LDPE, and hydrogel (hydrogel) have been used for various applications. For example, as a use of a soft base material, a biotechnology device such as a medical device introduced into a living body or covering a living body surface, a cell culture sheet, a scaffold material for tissue regeneration, a facial pack, etc. Examples include beauty devices and daily necessities such as insoles.

By the way, for example, a hydrogel material may be used as a skin covering material that is one of medical devices. This hydrogel material contains a large amount of water (water content is about 25% to 80%). For this reason, when a skin covering material is applied to the skin, a phenomenon occurs in which moisture evaporates from the covering material, and the user may feel dry and feel uncomfortable. Moreover, since the hydrogel material contains a large amount of water, there is a concern about the risk of bacterial propagation.

In recent years, a medical device using a soft material (low water content) having a lower water content is also known. For example, Patent Document 1 discloses a contact lens material made of a low water-containing silicone-containing elastomer. In

Patent Documents

2 and 3, a surface treatment for improving hydrophilicity is performed on a medical device made of silicone or a silicone hydrogel having a water content of about 10% by mass to about 80% by mass. A silicone medical device is disclosed.

A soft device that is introduced into a living body or attached to the surface of a living body can be used by a user (patient, etc.) if it can give better properties such as hydrophilicity, slipperiness, and flexibility. ) Is more preferable because the feeling of use (wearing feeling) is improved and pain can be reduced.

Various methods for modifying the surface of a soft substrate are known, and among them, a method of coating and laminating two or more layers of polymer materials one by one is known (for example, Patent Documents). (See 4-6). 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. However, the soft substrate for which the usefulness of this method is clearly specified is only of a silicone hydrogel material, and the utility for other low hydrous soft substrates has not been known. In addition, the conventional LbL coating is performed in multiple layers of about 4 to 20 layers, which may increase the manufacturing process and increase the manufacturing cost.

JP-T-2001-527141 Special table 2003-500686 gazette Special table 2003-529419 gazette Japanese translation of PCT publication No. 2002-501211 JP 2005-538418 A Special table 2009-540369

Among soft devices formed of soft materials, soft devices that are used by being directly attached to the surface of a living body or inserted into a living body, in addition to hydrophilicity, can be easily slipped and used for a long time. It is difficult to dry, it is possible to maintain flexibility, and the shape change is small (that is, it is difficult to shrink). A soft device that is introduced into a living body or attached to the surface of a living body can be used by a user (patient, etc.) if it can give better properties such as hydrophilicity, slipperiness, and flexibility. ) Is more preferable because the feeling of use (wearing feeling) is improved and pain can be reduced.

The present invention has been made in view of the above, and has good slipperiness in addition to hydrophilicity, and is difficult to dry even when used for a long time, and can maintain flexibility, and An object of the present invention is to provide a low hydrous soft device with little change in shape. Another object of the present invention is to provide a method for producing a low hydrous soft device, which can produce a low hydrous soft device comprising the low hydrous soft substrate having the above-mentioned properties at a low cost by a simple process. And

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

The low hydrous soft device of the present invention comprises a soft member in which a layer made of an acidic polymer and a basic polymer is formed on at least a part of the surface of the low hydrous soft substrate.

The low hydrous soft device of the present invention is preferable for an embodiment used in a wet state (or a wet state) because the surface is provided with good wettability and slipperiness while being low hydrous soft. Applicable.

In a preferred embodiment of the present invention, the soft member may have a tube shape. The low hydrous soft device having such a shape can be suitably used as a medical device, for example.

Specifically, the medical device is an infusion tube, a gas transport tube, a drainage tube, a blood circuit, a coated tube, a catheter, a stent, a sheath, a tube connector, an access port, an endoscope coating material, or the like.

In another preferred embodiment of the present invention, the soft member may be in the form of a sheet or a film. The low hydrous soft device having such a shape can be suitably used as, for example, any one of a medical device, a biotechnology device, an agricultural / gardening device, a filtration device, an antifouling device, and a beauty device. .

Specifically, the medical device preferably includes a skin covering material, a wound covering material, a skin protecting material, or a skin drug carrier.

The biotechnology device is a cell culture sheet or a tissue regeneration scaffold.

Also, the agriculture / gardening device is a moisturizing sheet.

The filtration device is a gas-liquid separation membrane or the like.

In still another preferred embodiment of the present invention, the soft member may have a storage container shape. The low hydrous soft device having such a shape can be suitably used as a medical device, for example.

Specifically, the medical device is a drug carrier, a cuff, or a drainage bag.

In still another preferred embodiment of the present invention, the soft member may have a granular shape. The low hydrous soft device having such a shape can be suitably used as, for example, an agricultural / gardening device. Specifically, the agriculture / gardening device is a granular moisturizing material for agriculture / gardening.

In the above, it is preferable that the low hydrous soft 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 a number average molecular weight of 6000 or more Component B: a polymerizable monomer having a fluoroalkyl group In the present specification, a polysiloxane compound is Si— It is a compound having an O—Si—O—Si bond.

The present invention is also a method for producing a low hydrous soft device comprising the following steps 1 to 3 in this order;
<Step 1>
Polymerizing a mixture containing 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 and component B which is a polymerizable monomer having a fluoroalkyl group Obtaining a molded body having a shape of
<Step 2>
A step of washing and removing excess basic polymer solution after contacting the molded body 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.

According to the present invention, a low hydrous soft device with a low dry feeling and a low risk of bacterial propagation, in addition to hydrophilicity, it is difficult to dry even when used for a long time, can maintain flexibility, and The characteristic that there is little change of a shape can be provided. In addition, according to the present invention, a low hydrous soft device having the above characteristics can be manufactured at a low cost by a simple process.

FIG. 1 is a perspective view showing an infusion tube as an example of the low hydrous soft device of the present invention. FIG. 2 is a perspective view showing a distal end portion of a catheter which is an example of the low hydrous soft device of the present invention. FIG. 3 is a perspective view showing a part of a stent which is an example of the low hydrous soft device of the present invention. FIG. 4 is a perspective view showing a distal end portion of an endoscope which is an example of the low hydrous soft device of the present invention. FIG. 5 is a perspective view showing a part of a gas-liquid separation membrane which is an example of the low hydrous soft device of the present invention. FIG. 6 is a schematic view showing a moisturizing sheet as an example of the low hydrous soft device of the present invention. FIG. 7 is a perspective view showing a drug carrier which is an example of the low hydrous soft device of the present invention. FIG. 8 is a schematic view showing a granular moisturizing material which is an example of the low water content device of the present invention. FIG. 9 is a schematic diagram of an apparatus for measuring the dynamic friction force between a sample film and artificial leather.

The low hydrous soft device of the present invention is, for example, a tube or circuit that is introduced into a living body to perform infusion, gas transportation, drainage, etc., and a tube that is introduced into the living body by enclosing a therapeutic instrument or observation instrument. A coating material that covers the surface of the living body to protect or treat the surface of the living body, a carrier that is encapsulated with a drug, etc., and is introduced into the living body, and a part of the carrier is introduced into the living body to accommodate drainage from the living body Medical devices such as bags; biotechnological devices such as cell culture sheets and scaffolds for tissue regeneration; agricultural / gardening devices such as moisturizing sheets and moisturizing materials; filtration devices; biofouling prevention materials, protein adhesion prevention materials, lipid attachments Antifouling devices such as the amount of inhibitor; beauty devices such as facial bags. The low hydrous soft device of the present invention has various forms such as a tube shape, a sheet shape, a film shape, a spherical crown shape, a storage container shape, and a granular shape, depending on applications.

In the present invention, 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, from the dry mass of the film-shaped test piece and the wet mass by the borate buffer, {(mass in the wet state) − (mass in the dry state) / Wet mass}.

In the present specification, the wet state means a state in which the sample is immersed in pure water or borate buffer at room temperature (25 ° C.) for 24 hours or more. The measurement of physical properties in a wet state is carried out as soon as possible after removing the sample from pure water or borate buffer and wiping the surface moisture.

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

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.

Since the low hydrous soft device of the present invention is low hydrous, when the low hydrous soft device of the present invention is, for example, a medical device used by being applied to the surface of a living body, it is applied to the surface of the living body. The user feels that the feeling of dryness is small and that the feeling of wearing is excellent. In addition, since the low hydrous soft device of the present invention is low hydrous, when the low hydrous soft device of the present invention is a biotechnology device such as a medical device or a cell culture sheet that can directly contact a living body, for example, It has the advantage that the risk of bacterial growth is low. The moisture content is more preferably 5% or less, further preferably 2% or less, and most preferably 1% or less. If the water content is too high, there is a concern that the feeling of dryness may increase and the risk of bacterial growth increases, which is not preferable.

The tensile elastic modulus of the low hydrous soft device of the present invention is preferably 0.01 to 5 MPa, more preferably 0.1 to 3 MPa, still more preferably 0.1 to 2 MPa, even more preferably 0.1 to 1 MPa, Most preferred is 0.1 to 0.6 MPa. If the tensile modulus is too small, it tends to be too soft and difficult to handle. If 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 is 2 MPa or less, good wearing feeling is obtained, and when it is 1 MPa or less, further wearing feeling is obtained, which is preferable. The tensile modulus is measured on a sample in a wet state with a borate buffer.

The tensile elongation of the low hydrous soft device of the present invention is preferably 100% to 1000%, more preferably 200% to 700%. If the tensile elongation is small, the low hydrous soft device is easily broken, which is not preferable. When the tensile elongation is too large, the low hydrous soft device tends to be deformed, which is not preferable. Tensile elongation is measured on samples wet with borate buffer.

It is preferable that the low hydrous soft device of the present invention has sufficient water retention and has the same softness and dryness as before storage even after storage for a predetermined time. Water retention is evaluated by touching with a finger and observing the state before and after storage in a predetermined temperature and humidity environment for a predetermined time.

In the low hydrous soft device of the present invention, the dynamic contact angle with respect to the borate buffer (during advance, immersion speed: 0.1 mm / sec) is preferably 100 ° or less, more preferably 90 ° or less, and 80 ° or less. Further preferred. The dynamic contact angle is preferably lower, preferably 65 ° or less, more preferably 60 ° or less, further preferably 55 ° or less, still more preferably 50 ° or less, and most preferably 45 ° or less. The dynamic contact angle is measured on a sample wet with borate buffer.

In addition, when the low hydrous soft device of the present invention is a medical device that is used by being applied to the surface of a living body, for example, in order to prevent sticking to the skin of the wearer, the surface of the low hydrous soft device is used. It is preferable that the liquid film retention time is long. Here, the liquid film holding time is the liquid film on the surface of the low hydrous soft device when the low hydrous soft device immersed in the borate buffer is pulled up from the liquid and held so that the surface is vertical in the air. It is the time that is kept 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.

In addition, when the low hydrous soft device of the present invention is a medical device used by being inserted into a living body, for example, it is preferable that the surface of the low hydrous soft device has excellent slipperiness. 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, more preferably 10 gf (0.098 N) or more. Friction is measured on samples wet with borate buffer.

The antifouling property of the low hydrous soft device 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.

When the low hydrous soft device of the present invention is, for example, a medical device used by being attached to the surface of a living body, the low hydrous soft device preferably has high oxygen permeability. The oxygen permeability coefficient [× 10 ⁻¹¹ (cm ² / sec) mLO ₂ / (mL · hPa)] is preferably 50 to 2000, more preferably 100 to 1500, still more preferably 200 to 1000, and most preferably 300 to 700. . If the oxygen permeability is excessively increased, other physical properties such as mechanical properties may be adversely affected, which is not preferable. The oxygen permeability coefficient is measured on a dry sample.

The low hydrous soft device of the present invention includes a molded body (hereinafter referred to as a base material) having a desired shape (for example, a tube shape, a sheet shape, a film shape, a storage container shape, a granular shape, etc.). A layer made of an acidic polymer and a basic polymer is formed on at least a part of the surface.

The base material is preferably composed mainly of a polymer of the following component A or a copolymer of the following component A and component B;
Component 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 Component B: Polymerizable monomer having a fluoroalkyl group Means a component 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 in this range, a low hydrous soft device excellent in mechanical properties such as flexibility, excellent wearing feeling and bending resistance can be obtained. The number average molecular weight of the component A polysiloxane compound is preferably 8000 or more because a low hydrous soft device having excellent mechanical properties such as bending resistance can be obtained. The number average molecular weight of component A is preferably in the range of 8000 to 100,000, more preferably in the range of 9000 to 70000, and still more preferably in the range of 10,000 to 50000. 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.

In the present invention, the number average molecular weight of component A is a polystyrene-equivalent number average molecular weight 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 addition, in this specification, a mass average molecular weight may be represented by Mw and a 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 per molecule. The number of polymerizable functional groups of component A may be two or more per molecule, but from the viewpoint that a softer (low elastic modulus) low hydrous soft device can be easily obtained, two per functional molecule. Is preferred. 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, isocrotonic acid 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 the structure of 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, isocrotonic acid Examples include acid residues and citraconic acid residues. Of these, a (meth) acryloyl group is most preferred because of its high polymerizability.

Preferred examples of R ¹ to R ⁸ include hydrogen; a C 1-20 carbon atom such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, decyl group, dodecyl group, octadecyl group, etc. Alkyl group: phenyl group, trifluoromethyl group, trifluoroethyl group, trifluoropropyl group, tetrafluoropropyl group, hexafluoroisopropyl group, pentafluorobutyl group, heptafluoropentyl group, nonafluorohexyl group, hexafluorobutyl group , Heptafluorobutyl group, octafluoropentyl group, nonafluoropentyl group, dodecafluoroheptyl group, tridecafluoroheptyl group, dodecafluorooctyl group, tridecafluorooctyl group, hexadecafluorodecyl group, heptadecafluorodecyl group, Tetrafluorop Propyl group, a pentafluoropropyl group, tetradecanoyl 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 giving good mechanical properties and high oxygen permeability to a low hydrous soft 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 each repeating unit. a and b each independently preferably ranges from 0 to 1500. The total value of a and b (a + b) is preferably 80 or more, more preferably 100 or more, more preferably 100 to 1400, more preferably 120 to 950, and still more preferably 130 to 700.

When R ¹ to R ⁸ are all methyl groups, b = 0, and a is preferably 80 to 1500, more preferably 100 to 1400, more preferably 120 to 950, and still more preferably 130 to 700. In this case, the value of a is determined by the molecular weight of the polysiloxane compound of component A.

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

As another compound to be copolymerized with Component A, Component B which is a polymerizable monomer having a fluoroalkyl group is preferable. Component B has water- and oil-repellent properties due to a decrease in critical surface tension due to the fluoroalkyl group, and thereby the surface of a low hydrous soft device is contaminated by components such as proteins and lipids in body fluids of living organisms. There is an effect to suppress that. In addition, Component B has an effect of giving a low hydrous soft 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, most preferably trifluoroethyl group It is a group.

The polymerizable functional group of Component B is preferably a radical polymerizable functional group, more preferably a carbon-carbon double bond. 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, isocrotonic acid 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 is highly effective in obtaining a low hydrous soft device excellent in mechanical properties such as bending resistance and flexibility. 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 weight, more preferably 20 to 400 parts by weight, and still more preferably 20 to 200 parts by weight with respect to 100 parts by weight of Component A. When the amount of component B used is too small, the resulting low hydrous soft device tends to become cloudy or mechanical properties such as bending resistance tend to be insufficient.

In addition to the 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 below 0 ° C. Since these reduce the cohesive energy, they have the effect of imparting rubber elasticity and softness to the copolymer.

The polymerizable functional group of Component C is preferably a radical polymerizable functional group, and more preferably has a carbon-carbon double bond. 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, isocrotonic acid 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) Examples include acrylate, 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. Of these, (meth) acrylic acid alkyl esters having an alkyl group with 1 to 10 carbon atoms are more preferred. If the carbon number of the alkyl group is too large, the transparency of the resulting low hydrous soft device may be lowered, which is not preferable.

Furthermore, in order to improve mechanical properties, surface wettability, dimensional stability of a low hydrous soft 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, 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 low hydrous soft devices include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, Bisphenol A dimethacrylate, vinyl methacrylate, acrylic methacrylate and acrylates corresponding to these methacrylates, divinylbenzene, triallyl isocyanurate and the like can be mentioned.

Component C may be used alone or in combination of two or more.

Component C is preferably used in an amount of 0.001 to 400 parts by weight, more preferably 0.01 to 300 parts by weight, still more preferably 0.01 to 200 parts by weight, and most preferably 0 to 100 parts by weight of Component A. 0.01 to 30 parts by mass. 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 low hydrous soft device tends to become cloudy or mechanical properties such as bending resistance tend to be insufficient.

Furthermore, a copolymer obtained by further copolymerizing component M in addition to component A may be used as the copolymer used for the substrate. 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 resulting low hydrous soft device is improved. Here, the term “linear” refers to a structure represented by a single linearly connected Si— (O—Si) _n−1 —O—Si bond starting from a silicon atom bonded to a group having a polymerizable group. (Where n represents an integer of 2 or more). In order for the obtained low hydrous soft device to obtain sufficient shape recoverability, n is preferably an integer of 3 or more, more preferably 4 or more, further 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.

The base material is preferably composed mainly of a copolymer containing the component M having a number average molecular weight of 300 to 120,000. 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 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.

As the polymerizable functional group of Component M, a radical polymerizable functional group 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, isocrotonic acid 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, isocrotonic acid Examples include acid residues and citraconic acid residues. Of these, a (meth) acryloyl group is most preferred because of its high polymerizability.

The polymerizable functional group of Component M is more preferably copolymerizable with the polymerizable functional group of Component A, since a low hydrous soft device with good mechanical properties can be easily obtained. Since it is easy to obtain a low hydrous soft device having good surface characteristics when A is uniformly copolymerized, it is more preferably the same as the polymerizable functional group of Component A.

Preferred examples of R ¹¹ to R ¹⁹ are hydrogen; those having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, decyl group, dodecyl group, octadecyl group and the like. Alkyl group: phenyl group, trifluoromethyl group, trifluoroethyl group, trifluoropropyl group, tetrafluoropropyl group, hexafluoroisopropyl group, pentafluorobutyl group, heptafluoropentyl group, nonafluorohexyl group, hexafluorobutyl group , Heptafluorobutyl group, octafluoropentyl group, nonafluoropentyl group, dodecafluoroheptyl group, tridecafluoroheptyl group, dodecafluorooctyl group, tridecafluorooctyl group, hexadecafluorodecyl group, heptadecafluorodecyl group, Tetrafluo Propyl group, a pentafluoropropyl group, tetradecanoyl 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 giving good mechanical properties and high oxygen permeability to a low hydrous soft 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 of being 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 the formula (ML1), the total value of c and d (c + d) is preferably 3 or more, more preferably 10 or more, more preferably 10 to 500, more preferably 30 to 300, and still more preferably 50 to 200.

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

In the substrate of the low hydrous soft 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 low hydrous soft device of the present invention contains an appropriate amount of the 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 is realized. be able to. 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 not preferable.

In the substrate of the low hydrous soft device of the present invention, the mass ratio of the component M and the component A is such that the component M 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. The most preferred is 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 substrate contains 5% by mass or more of silicon atoms in order to obtain strong adhesion without using a covalent bond with the polymer coated on the surface and to have good oxygen permeability. preferable. 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.

When the low hydrous soft device of the present invention is a medical device used, for example, on the surface of an optical product inserted into a living body (for example, a camera provided at the distal end of an endoscope), 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, when the low hydrous soft device is observed with a projector, it is preferable that little or no turbidity is observed, and most preferable that no turbidity is observed.

The dispersity (the value obtained by dividing the mass average molecular weight by the number average molecular weight) is preferably 6 or less, more preferably 3 or less, still more preferably 2 or less, and most preferably 1.5 or less. When the dispersion degree of component A is small, the compatibility with other components is improved, the transparency of the resulting low hydrous soft device is improved, and the extractable components contained in the resulting low hydrous soft device are reduced. Advantages such as reduction in shrinkage due to molding of the base material of the low hydrous soft device occur.

The shrinkage rate associated with the molding of the base material is evaluated by, for example, the average value of the molding ratios of the corresponding four sides calculated by the following equation when the base material is in the form of a film and the base material is molded by inter-plate polymerization. .

Molding ratio of one side = (length of one side after molding) / (length of one side of the cavity of the mold)
Here, the “mold cavity” is a cavity having a shape corresponding to the shape of the film, which is used for molding a film, and is usually a cavity composed of two plates and a gasket. is there.

Further, for example, when the base material has a spherical crown shape (a shape obtained by cutting off a part of the spherical surface with a flat surface), and the base material is molded by mold polymerization, the shrinkage rate accompanying the molding is: molding ratio = [diameter] / [ The diameter of the void portion of the mold] can be evaluated. Here, the diameter is the diameter of a circle formed by the edge of the spherical crown.

As the molding ratio is closer to 1, it becomes easier to stably produce a high-quality, low hydrous soft device. 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.

Moreover, the shrinkage ratio (hereinafter referred to as shrinkage ratio) due to drying of the low hydrous soft device of the present invention is, for example, when the substrate is in a film shape, on the four sides of the test piece in a wet state (before storage) with a borate buffer solution. The length and the length of the four sides of the test piece after storing the test piece in a predetermined environment for a predetermined time are measured and evaluated by the average value of the shrinkage rate of each corresponding side calculated by the following equation.
Shrinkage rate of one side (%) = {(length of one side before storage) − (length of one side after storage)}
/ (Length of one side before storage) x 100
Furthermore, for example, when the base material has a spherical crown shape (a shape obtained by cutting a part of a spherical surface with a flat surface), the shrinkage rate is evaluated by shrinkage rate (%) = [diameter after storage] / [diameter before storage]. can do. Here, the diameter is the diameter of a circle formed by the edge of the spherical crown.

The shrinkage ratio is preferably 20 or less, more preferably 10 or less, even more preferably 5 or less, and most preferably less than 1 because the shape change of the molded body is small.

The low hydrous soft 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 pharmaceutical and nutritional supplement component, a compatibilizing component, an antibacterial component, and a release agent. Good. Any of the above-described components can be contained in a non-reactive form or a copolymerized form.

In the case of containing an ultraviolet absorber, the skin of the wearer can be protected from harmful ultraviolet rays by using a low hydrous soft device as a skin covering material. Moreover, when a coloring agent is included, a low hydrous soft device is colored, identification becomes easy, and the convenience at the time of handling improves.

Any of the above-described components can be contained in a non-reactive form or a copolymerized form. 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 base material is preferably composed of a component selected from an ultraviolet absorber and a colorant, and two or more other components C (hereinafter referred to as component Ck). In this case, it is preferable that the component Ck is selected from at least one kind of (meth) acrylic acid alkyl ester having 1 to 10 carbon atoms and at least one kind from the monomer 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 an ultraviolet absorber is used, the preferred amount to be used is 0.01 to 20 parts by weight, more preferably 0.05 to 10 parts by weight, and even more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of Component A. It is. When a colorant is used, the preferred amount of use is 0.00001 to 5 parts by weight, more preferably 0.0001 to 1 part by weight, and still more preferably 0.0001 to 0.5 parts by weight with respect to 100 parts by weight of Component A Part. 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 amount of component Ck used is preferably 0.1 to 100 parts by weight, more preferably 1 to 80 parts by weight, and still more preferably 2 to 50 parts by weight with respect to 100 parts by weight of component A. 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 component Ck used is too large, the resulting low hydrous soft device tends to be cloudy or has insufficient mechanical properties such as bending resistance, which is not preferable.

Further, the substrate of the low hydrous soft device of the present invention preferably has a degree of crosslinking in the range of 2.0 to 18.3. The degree of crosslinking is represented by the following formula (Q1).

In the formula (Q1), Qn represents the total millimolar amount of monomers having n polymerizable groups per molecule, and Wn represents the 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 base material 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 base material of a low hydrous soft device, for example, a known method can be used as a method for producing a molded body such as a tube shape, a sheet shape, a film shape, a spherical crown shape (lens shape), a storage container shape, or a granular shape 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 a low hydrous soft device is obtained by cutting, freezing cutting at a low temperature is suitable.

As an example, a method for producing a sheet-like or film-like low hydrous soft 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 certain thickness to the low hydrous soft device 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. In 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). In the case of performing thermal polymerization, the temperature of the composition is gradually raised from around room temperature, and the temperature is raised to a temperature of 60 ° C. to 200 ° C. over several hours to several tens of hours. In order to maintain uniform uniformity and quality and improve 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.

When polymerizing, 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 chill ether, 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.

The low hydrous soft device of the present invention requires that a layer made of an acidic polymer and a basic polymer (hereinafter referred to as a coating layer) is formed on at least a part of the substrate surface. By having the coating layer, good wettability and easy slipperiness are imparted to the surface of the low hydrous soft device, and an excellent wearing feeling can be imparted or an unpleasant feeling of use can be suppressed.

The inventors of the present invention provide a coating layer comprising an acidic polymer and a basic polymer on the surface even when the low hydrous soft device of the present invention is low hydrous and soft and the substrate is neutral. It has been found that it is possible to impart sufficient wettability, slipperiness and antifouling property to the surface of a low hydrous soft device by forming the film.

The coating layer of the low hydrous soft 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 can be formed by treating the substrate surface with an acidic polymer solution and a basic polymer solution described in detail below. Here, the solution is preferably an aqueous solution. An aqueous solution is a solution containing water as a main component.

The coating layer is preferably composed of one or more kinds of acidic polymers and one or more kinds of basic polymers. 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 slipperiness and antifouling properties are easily expressed on the surface of a low hydrous soft 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.

Here, one type of polymer means a group of polymers produced by one synthesis reaction. In addition, even if the constituent monomer species are the same, the number of polymers synthesized by changing the compounding ratio is not one.

In addition, the coating layer is preferably treated 1 to 5 times, more preferably 1 to 3 times, and still more preferably 1 each of the treatment with one or more acidic polymer solutions and the treatment with one or more basic polymer solutions. 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 present invention, the treatment with the acidic polymer solution and the treatment with the basic polymer solution can impart excellent wettability and slipperiness with a very small number of times of 2 or 3 times in total. This is very important industrially from the viewpoint of shortening the manufacturing process. In that sense, in the low hydrous soft device of the present invention, the treatment with the acidic polymer solution is performed once or twice, and the treatment with the basic polymer solution is performed once or twice, for a total of two or three times. It is preferable that it is formed by performing.

It is particularly preferable that the coating layer is formed by performing the treatment with two kinds of acidic polymer solutions once and the treatment with the basic polymer solution once, for a total of three times.

In addition, the inventors have also confirmed that the wettability and the slipperiness are hardly observed when the coating layer contains only one of the acidic polymer and the 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 Amino group-containing (meth) acrylate polymers such as -dialkylaminoethyl methacrylate), amino group-containing (meth) acrylamide polymers such as poly (N, N-dimethylaminopropylacrylamide), and salts thereof. The above 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 coating of a low hydrous soft device, it can impart antimicrobial properties to the low hydrous soft device.

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 It is salt. Of these, (meth) acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, and salts thereof are more preferable, and (meth) acrylic acid and salts thereof are most preferable.

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 can be formed. When the basic polymer and / or the acidic polymer has a hydroxyl group, it is preferable because a surface excellent in not only wettability but also antifouling property against body fluids can be formed.

More preferably, at least two of the acidic polymer and the basic polymer are polymers having a group selected from a hydroxyl group and an amide group. That is, it is preferable that the low hydrous soft device 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 body fluids 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 body fluids can be exhibited.

Examples of the basic polymer having an amide group include polyamides having an amino group, partially hydrolyzed chitosan, and a copolymer of a basic monomer and a monomer having an amide group.

Examples of the acidic polymer having an amide group include a polyamide having a carboxyl group and a copolymer of an acidic monomer and a monomer having an amide group.

Examples of the basic polymer having a hydroxyl group include an aminopolysaccharide such as chitin, a copolymer of a basic monomer and a monomer having a hydroxyl group, and the like.

Examples of the acidic polymer having a hydroxyl group include polysaccharides having acidic groups such as hyaluronic acid, chondroitin sulfate, carboxymethylcellulose, and carboxypropylcellulose, 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 N-vinylcarboxylic acid amide (including cyclic ones) are preferable from the viewpoint of ease of polymerization. Preferable examples of such monomers include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylacetamide, N-methyl-N-vinylacetamide, N-vinylformamide, N, N-dimethylacrylamide, N, N-diethyl Mention may be made of acrylamide, N-isopropylacrylamide, N- (2-hydroxyethyl) acrylamide, acryloylmorpholine, and acrylamide. Among these, N-vinylpyrrolidone and N, N-dimethylacrylamide are preferable from the viewpoint of slipperiness, and N, N-dimethylacrylamide is most preferable.

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.

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- Acrylamide-2-methylpropanesulfonic acid / N-vinylpyrrolidone copolymer and 2-acrylamido-2-methylpropanesulfonic acid / N, N-dimethylacrylamide copolymer. Most preferred is a (meth) acrylic acid / N, N-dimethylacrylamide copolymer.

Specific 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 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 -Acrylamido-2-methylpropanesulfonic acid / hydroxyethyl (meth) acrylate copolymer and 2-acrylamido-2-methylpropanesulfonic acid / glycerol (meth) acrylate copolymer. Most preferred is a (meth) acrylic acid / hydroxyethyl (meth) acrylate copolymer.

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

The molecular weight of the acidic polymer and the basic polymer can be changed to change various properties of the coating layer, such as thickness. Specifically, increasing the molecular weight generally increases the thickness of the coating layer. However, if the molecular weight is too large, handling may increase due to increased viscosity. Therefore, the acidic polymer and basic polymer used in the present invention preferably have a molecular weight of 2000 to 150,000. More preferably, the molecular weight is 5000 to 100,000, and even more preferably 75,000 to 100,000. The molecular weight of the acidic polymer and the basic polymer is a mass average molecular weight in terms of polyethylene glycol measured by a gel permeation chromatography method (aqueous solvent).

Application of the coating layer can be accomplished in a number of ways, as described, for example, in WO 99/35520, WO 01/57118 or US Patent Publication No. 2001-0045676.

In the low hydrous soft device of the present invention, a layer composed of an acidic polymer and a basic polymer (hereinafter referred to as a coating layer) is formed on at least a part of the substrate surface. May be cross-linked. Moreover, in the low hydrous soft 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 an acidic polymer and a basic 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 low hydrous soft device is imparted with good wettability and easy slipperiness, giving an excellent wearing feeling. be able to. On the other hand, there is a case where cross-linking occurs inside the base material due to irradiation and the low hydrous soft 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, a method for producing a low hydrous soft device of the present invention will be described. The low hydrous soft device of the present invention is formed on the surface of a molded body (base material) having a desired shape (for example, tube shape, sheet shape, film shape, spherical crown shape (lens shape), storage container shape, granular shape, etc.). One or more acidic polymer solutions and one or more basic polymer solutions are applied 1 to 5 times, more preferably 1 to 3 times, and more preferably 1 to 2 times, respectively, to form a coating layer. Is obtained. The number of application steps of the acidic polymer solution and the application step of the basic polymer solution may be different.

The inventors of the present invention have a very small number of coating steps of one or more acidic polymer solutions and one or more basic polymer solutions in total or twice or three times in the method for producing a low hydrous soft device of the present invention. It has been found that excellent wettability and slipperiness can be imparted by the number of times. This is very important industrially from the viewpoint of shortening the manufacturing process.

In addition, in the low hydrous soft device of the present invention, the inventors developed wettability and slipperiness only by performing only one of the application step of the acidic polymer solution or the application step of the basic solution once. It is confirmed at the same time that almost no is seen.

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 Application 4: Application of acidic polymer solution / Application of basic polymer solution / Application of acidic polymer solution Among these structures, the low hydrous soft devices obtained by the structures 1 and 4 have particularly excellent wettability. More preferred to show.

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 preferred embodiment of the method for producing a low hydrous soft device of the present invention comprises the following steps 1 to 3 in this order.
<Step 1>
Polymerizing a mixture containing 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 and component B which is a polymerizable monomer having a fluoroalkyl group A step of obtaining a molded body having a shape (eg, tube shape, sheet shape, film shape, spherical crown shape, storage container shape, granular shape).
<Step 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 the molded body into contact with the acidic polymer solution and the basic polymer solution, a layer composed of the acidic polymer and the basic polymer can be formed on the molded body. Thereafter, it is preferable to sufficiently wash away excess polymer.

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

When the contact of the solution is performed by an immersion method, the immersion time can be changed according to many factors. The immersion of the shaped body in the acidic polymer solution or the basic polymer solution is preferably performed for 1 to 30 minutes, more preferably 2 to 20 minutes, and most preferably 1 to 5 minutes.

The concentration of the acidic polymer solution and the basic polymer solution can be varied depending on the nature of the acidic polymer or basic polymer, the desired coating layer thickness, and many other factors. The concentration of the preferred acidic polymer or basic polymer is 0.001 to 10% by mass, more preferably 0.005 to 5% by mass, and most preferably 0.01 to 3% by mass.

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

The washing and removal of excess acidic polymer and basic polymer is generally performed by rinsing the molded body after coating with clean water or an organic solvent. The rinsing is preferably performed by immersing the molded body in water or an organic solvent, or by exposing it to a water flow or an organic solvent flow. Although rinsing may be completed in one step, it has been found that it is more efficient to perform the rinsing step multiple times. Rinsing is preferably performed in steps 2-5. It is preferred to spend 1-3 minutes for each immersion in the rinse solution.

Pure water is also preferred as the rinsing solution, but is preferably buffered to a pH of 2-7, more preferably 2-5, and even more preferably 2.5-4.5 to increase the adhesion of the coating layer. An aqueous solution is also preferably used.

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.

It is preferable to apply the acidic polymer and the basic polymer alternately. By alternately applying, it is possible to obtain a low hydrous soft device having excellent wettability and slipperiness that cannot be obtained by only one of them, and also excellent wear feeling or use feeling.

The coating layer can be asymmetric. Here, “asymmetric” means having a different coating layer on the first surface of the low hydrous soft 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 to 2.0% by mass. As the salt concentration increases, the polyelectrolyte takes a more spherical conformation. However, if the concentration is too high, the polymer electrolyte does not deposit well even if it is deposited on the surface of the molded body. A more preferable salt concentration is 0.7 to 1.3% by mass.

Another preferred embodiment of the method for producing a low hydrous soft device of the present invention further includes the following step 4.
<Step 4>
A step of irradiating a molded body 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 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 radiation is performed in a state where the molded body is immersed in an aqueous liquid, as the aqueous liquid, in addition to pure water, physiological saline, phosphate buffer (preferably pH 7.1 to 7.3). ) And boric acid buffer solutions (preferably pH 7.1 to 7.3) are suitable.

If the molded body is irradiated with radiation in a sealed state, the molded body can be sterilized at the same time.

Γ rays are preferably used as radiation. 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 lowered, so 0.1 to 100 kGy is preferable, and 15 to 50 kGy is more preferable, and 20 to 40 kGy is most preferable. 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.

The low hydrous soft device of the present invention includes, for example, a soft member molded into a tube shape. Specifically, as a low hydrous soft device of the present invention, an infusion tube, a gas transport tube, a drainage tube, a blood circuit, a coated tube covering various members, a catheter, and a stent that are inserted into a living body and used. , A medical device such as a sheath, a tube connector, an access port, or an endoscope covering material.

FIG. 1 is a perspective view showing a part of an infusion tube which is an example of a low hydrous soft device (medical device) of the present invention. This infusion tube 10 main body is formed by the low hydrous soft base material mentioned above.

FIG. 2 is a perspective view showing a distal end portion of a catheter which is an example of the low hydrous soft device (medical device) of the present invention. This catheter 20 main body is formed by the low hydrous soft base material mentioned above.

FIG. 3 is a perspective view showing a part of a stent which is an example of the low hydrous soft device (medical device) of the present invention. The stent 30 has a structure in which a stent body 31 is covered with the low hydrous soft base material 32 described above.

FIG. 4 is a perspective view showing a distal end portion of an endoscope to which an endoscope covering material that is an example of the low hydrous soft device (medical device) of the present invention is applied. The endoscope 40 includes an insertion tube 41 that is made of a soft material and is deformable, and a distal end portion 42 of the insertion tube. An optical system 43 including a camera and illumination is provided inside the distal end portion 42. Further, the end surface 44 of the distal end portion 42 is formed of a material (glass or the like) that can transmit illumination light and reflected light thereof. The entire insertion tube 41 and the distal end portion 42 are covered with the low hydrous soft base material 45 described above.

The low hydrous soft device of the present invention includes a soft member having a sheet shape or a film shape, for example. Specifically, as a low hydrous soft 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 used by being attached to the surface of a living body, or a cell culture sheet Or biotechnology devices such as scaffolds for tissue regeneration, filtration devices such as separation membranes (gas-liquid separation membranes), antifouling devices such as coating materials used to prevent biological adhesion on ship bottoms, etc., moisturizing sheets that prevent soil drying Agricultural / gardening devices such as, cosmetic devices such as facial packs (a low hydrous soft base material containing a cosmetic liquid), daily goods such as wigs, insoles, and hygiene products.

When the low hydrous soft device of the present invention is used as an ophthalmic lens, it is preferable that the low hydrous soft device is used for applications other than ophthalmic lenses because there is no possibility that a wearer who feels sticking to the cornea will occur. .

FIG. 5 is a perspective view showing a part of a gas-liquid separation membrane which is an example of the low hydrous soft device (filtration device) of the present invention. The gas-liquid separation membrane 50 shown in FIG. 5 forms at least one surface of a container that can store a liquid. This gas-liquid separation membrane 50 is formed by the low hydrous soft base material described above. When, for example, a liquid in which oxygen is dissolved is injected into a container having such a gas-liquid separation membrane 50, the gas-liquid separation membrane 50 allows only oxygen therein to permeate. Thereby, the liquid and oxygen can be separated.

FIG. 6 is a schematic view showing a moisturizing sheet as an example of the low hydrous soft device (agriculture / gardening device) of the present invention. A moisturizing sheet 60 shown in FIG. 6 is formed by the low hydrous soft base material described above. The moisturizing sheet 60 is covered with the soil 62 such that an opening 61 is provided in the moisturizing sheet 60 and the plant 63 planted in the soil 62 is passed through the opening 61. Thereby, drying of the soil 62 can be prevented.

Further, the medical device of the present invention includes a member having a spherical crown shape, for example. Specifically, examples of the low hydrous soft device of the present invention include ophthalmic medical devices such as soft ophthalmic lenses (soft contact lenses), intraocular lenses, artificial corneas, corneal inlays, corneal onlays, and eyeglass lenses. .

Also, the low hydrous soft device of the present invention includes a soft member molded into a storage container shape, for example. Specifically, as a low hydrous soft device of the present invention, a drug carrier introduced into the living body, a cuff used by being inserted into the living body, or connected to the drainage tube inserted into the living body Medical devices such as drainage bags.

FIG. 7 is a perspective view showing a drug carrier which is an example of the low hydrous soft device (medical device) of the present invention. The main body of the drug carrier 70 is formed by the low hydrous soft base material described above.

Moreover, the low hydrous soft device of the present invention includes, for example, a granular member. Specifically, the low hydrous soft device of the present invention includes an agricultural / gardening device such as a granular moisturizing material arranged in place of the soil surface or soil.

FIG. 8 is a schematic view showing a granular moisturizing material which is an example of the low hydrous soft device (agricultural / gardening device) of the present invention. A granular moisturizing material 80 shown in FIG. 8 is formed by the low hydrous soft base material described above. When potted plants 81 or the like are potted, by placing the moisture-containing granular moisturizing material 80 instead of soil, the roots 82 can be prevented from drying and the plants can be cultivated hygienically.

In addition, the low hydrous soft device of the present invention is not limited to the above exemplified low hydrous soft device, and can be used by molding into various shapes.

Hereinafter, examples of the present invention will be specifically described, but the present invention is not limited thereto.

Analysis method and evaluation method (1) Molecular weight The polystyrene-equivalent mass average molecular weight and number average molecular weight were measured by the GPC method under the following conditions.

Pump Tosoh DP-8020
Detector Tosoh RI-8010
Column oven Shimadzu CTO-6A
Autosampler Tosoh AS-8010
Column: Tosoh TSKgel GMHHR-M
(Inner diameter 7.8 mm × 30 cm, particle diameter 5 μm) × 2 Column temperature: 35 ° C.
Mobile phase: Chloroform Flow rate: 1.0 mL / min Sample concentration: 0.4% by mass
Injection volume: 100 μL
Standard sample: polystyrene (molecular weight 1010 to 1.09 million).

(2) Elongation Using a specified punching die from a sample having a spherical crown shape (a shape obtained by cutting a part of a spherical surface with a plane, a diameter of a circle formed by an edge of about 14 mm, a thickness of about 0.1 mm), the width ( (Minimum portion) A test piece having a length of about 5 mm, a length of 14 mm, and a thickness of about 0.2 mm was cut out, and the test piece was pulled by hand to 1.5 times the initial size (50% elongation). Five test pieces were tested, and the number of test pieces that were not cut was indicated.

(3) Bending resistance A test piece having a spherical crown shape (edge diameter: about 14 mm, thickness: about 0.1 mm) was bent in two with a finger, and then it was strongly pinched with the finger. Five test pieces were tested and judged according to the following criteria.

A: All specimens are not damaged B: Some specimens are not damaged C: All specimens are damaged, but the degree of damage is minor D: All specimens are damaged, and the degree of damage is C Between E and E. E: All specimens break into pieces.

(4) Transparency A test piece having a spherical crown shape (edge diameter: about 14 mm, thickness: about 0.1 mm) was visually observed, and transparency was evaluated according to the following criteria:
A: Transparent with no turbidity B: Intermediate turbidity between A and C C: White turbidity and translucent D: Intermediate turbidity between C and E E: White turbidity and no transparency.

(5-1) Moisture content A test piece having a spherical crown shape (edge diameter: about 14 mm, thickness: about 0.1 mm) was used. The test piece was dried in a vacuum dryer at 40 ° C. for 16 hours, and the mass (Wd) was measured. Then, after immersing in pure water and allowing it to remain in a 40 ° C constant temperature bath overnight, wipe the surface moisture with a wiping cloth (“Kimwipe (registered trademark)” manufactured by Nippon Paper Crecia) and measure the mass (Ww). did. The water content was determined by the following formula. When the obtained value was less than 1%, it was judged to be below the measurement limit, and was expressed as “less than 1%”.
Water content (%) = 100 × (Ww−Wd) / Ww (1).

(5-2) Moisture content A film-shaped test piece was prepared, and the test piece was immersed in a borate buffer solution and allowed to stand at room temperature for 24 hours or more. Then, the surface moisture was wiped off (“Kimwipe” manufactured by Nippon Paper Crecia) (Registered trademark) ") and wiped off to measure the mass (Ww). Then, it dried at 40 degreeC for 16 hours with the vacuum dryer, and mass (Wd) was measured. From these masses Wd and Ww, the water content was calculated by the above formula (1). When the obtained value was less than 1%, it was judged to be below the measurement limit, and was expressed as “less than 1%”.

(6) Water retention The test piece in the form of a film wet with borate buffer solution was stored in a desiccator at a temperature of 33.1 ° C. and a humidity of 90% for 48 hours. Based on the following criteria:
A: There is no difference in softness and dryness of the test piece before and after storage. B: After storage for 48 hours, the hardness of the test piece increases slightly compared with before storage, and a little dryness C: After storage for 48 hours Compared with before storage, the hardness of the test piece is remarkably increased and the dryness is high.

(7) Water wettability A test piece having a spherical crown shape (edge diameter: about 14 mm, thickness: about 0.1 mm) was immersed in a borate buffer in a beaker at room temperature for 24 hours or more. The beaker containing the test piece and borate buffer was put on an ultrasonic cleaner (1 minute). The test piece was pulled up from the borate buffer solution, and the state of the surface when held in the air so that the diameter direction of the circle formed by the edge of the test piece was vertical was visually observed and judged according to the following criteria:
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. C: The liquid film on the surface is cut in 5 seconds or more and less than 10 seconds. D: The liquid film on the surface is 1 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) Dynamic contact angle measurement As a dynamic contact angle sample, a film-shaped test piece having a size of about 5 mm × 10 mm × 0.1 mm cut out from a sample molded into a film shape, or a spherical crown shape (edge diameter) A strip-shaped test piece having a width of 5 mm cut out from a sample having a thickness of about 14 mm and a thickness of about 0.1 mm was used in a wet state with a borate buffer solution, and a dynamic contact angle at the time of advance with respect to the borate buffer solution was measured. . As a measuring device, a dynamic wettability tester WET-6000 manufactured by RESCA Co., Ltd. was used, the immersion speed was 0.1 mm / sec, and the immersion depth was 7 mm.

(9) Tensile modulus, breaking elongation Width (minimum portion) using a prescribed punching die from a sample of a crown shape wetted with borate buffer (diameter of the edge is about 14 mm, thickness is about 0.1 mm) ) A test piece having a length of 5 mm, a length of 14 mm and a thickness of 0.2 mm was cut out. Using the test piece, a tensile test was carried out using Tensilon (registered trademark) RTM-100 manufactured by Orientec. The tensile speed was 100 mm / min, and the distance between grips (initial) was 5 mm.

(10) Easiness of sliding A sample having a spherical crown shape (edge diameter: about 14 mm, thickness: about 0.1 mm) was used. The slipperiness was evaluated by a sensitivity evaluation when a sample wet with borate buffer was rubbed with a finger five times:
A: Very good slipperiness B: Easy slipperiness between A and C C: Moderate slipperiness D: No slipperiness (intermediate between C and E) )
E: There is no slipperiness.

(11) Mucin adhesion Mucin, Bovine Submaxillary Gland (Catalog No. 499643) from CALBIOCHEM was used as mucin. A sample having a spherical crown shape (edge diameter: about 14 mm, thickness: about 0.1 mm) was immersed in a 0.1% mucin aqueous solution at 37 ° C. for 20 hours, and then BCA (bicinchoninic acid) protein assay method Was used to quantify the amount of mucin attached to the sample.

(12) Lipid adhesion A stirrer (36 mm) was placed in a 500 ml beaker, and 1.5 g of methyl palmitate and 500 g of pure water were added. The temperature of the water bath was set to 37 ° C., the aforementioned beaker was placed in the center of the water bath, and the mixture was stirred for 1 hour with a magnetic stirrer. The rotation speed was 600 rpm. Samples having a spherical crown shape (edge diameter: about 14 mm, thickness: about 0.1 mm) were put in a basket one by one, put into the above-described beaker, and stirred as it was. After 1 hour, stirring was stopped and the sample in the basket was rubbed with 40 ° C. tap water and household liquid detergent (“Mama Lemon®” manufactured by Lion). The washed sample was placed in a screw tube containing borate buffer (pH 7.1 to 7.3) and immersed in an ice bath for 1 hour. After removing the screw tube from the ice bath, the sample was visually observed for cloudiness, and the amount of methyl palmitate adhering to the sample was determined according to the following criteria:
A: Transparent with no white turbidity B: Slightly cloudy portion C: Some white cloudy portion D: Mostly cloudy E: Whole cloudy.

(13) Artificial tear immersion test A sample having a spherical crown shape (edge diameter: about 14 mm, thickness: about 0.1 mm) was used. Tear buffer (TLF) buffer prepared according to the method described in WO2008 / 127299, page 32, lines 5 to 36 except that oleic acid is used in place of propyl oleate as an artificial tear. The liquid was used. 2 mL of artificial tears was placed in one well of a culture multiplate (24-well type, material polystyrene, radiation sterilized), and one sample 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 buffer (PBS), 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 based on the following criteria:
A: No white turbidity is observed B: There are a few white turbid parts (less than 10% in area)
C: There is a considerable degree of cloudiness (10% to 50% in area)
D: Most part (50 to 100% in area) is cloudy but the back side is transparent. E: The whole is dark and cloudy and the back side is transparent and difficult to see.

(14) Transparency (projector)
A borate buffer solution was placed in a glass petri dish, and a sample having a spherical crown shape (edge diameter: about 14 mm, thickness: about 0.1 mm) was placed. Using a universal projector (Model V-10A manufactured by Nikon), the transparency when light was applied to the sample in the petri dish from above and below was visually observed and evaluated according to the following criteria:
A: Transparent with no white turbidity B: Slightly cloudy portion C: Some white cloudy portion D: Mostly cloudy E: Whole cloudy.

(15) Degree of coloration The degree of coloration (blueness) of a sample having a spherical crown shape (edge diameter: about 14 mm, thickness: about 0.1 mm) was visually observed and evaluated according to the following criteria:
A: Coloration is recognized at first glance B: Coloration degree intermediate between A and C C: Coloration is slightly recognized D: Coloration degree intermediate between C and D E: Coloration is not recognized.
(16) Shrinkage The film-shaped test piece was stored in a desiccator with a temperature of 33.1 ° C. and a humidity of 90% for 48 hours, and the size shrinkage before and after storage was calculated. After immersing the test piece in boric acid buffer solution and leaving it at room temperature for 24 hours or more, wipe the surface moisture with a wiping cloth ("Kimwipe (registered trademark)" manufactured by Nippon Paper Crecia) and length of the four sides of the rectangular test piece (L1 to L4) were measured. Thereafter, the test piece was stored in a desiccator at a temperature of 33.1 ° C. and a humidity of 90% for 48 hours. The lengths of the four sides of the test piece after storage (L5 to L8, corresponding to L1 to L4 in ascending order of numbers) were measured. First, the shrinkage of one side was obtained by the following formula:
Shrinkage rate on one side (%) = (L1-L5) / L1 × 100
Shrinkage rate of one side (%) = (L2−L6) / L2 × 100
Shrinkage rate of one side (%) = (L3−L7) / L3 × 100
Shrinkage rate of one side (%) = (L4−L8) / L4 × 100
Furthermore, the average of the shrinkage ratios on one side was taken as the shrinkage ratio of the test piece.

(17) Molding ratio The molding ratio was obtained by dividing the diameter of the sample (spherical crown shape) by the diameter of the cavity (having a shape corresponding to the sample shape) of the mold used to mold it. Here, the diameter is the diameter of a circle formed by the edge of the spherical crown.

(18) Friction Using the apparatus shown in FIG. 9, the dynamic friction force between the sample film and the artificial leather was measured. Artificial leather 1 (“Supprare (registered trademark)” manufactured by Idemitsu Techno Fine Co., Ltd., model number PBZ13001) was attached to one side of a glass plate of 26 mm × 26 mm × 1.4 mm to which a fishing line for pulling in the lateral direction was attached. The artificial leather was pasted so that the back side was the outside. The film 2 in a wet state with 60 mm × 60 mm × 0.25 mm borate buffer was placed on a horizontal rubber plate 3 and the surface of the film was sufficiently wetted with borate buffer. The above glass plate was placed thereon so that the artificial leather was on the film side, and a plastic container 4 containing a small iron ball (total weight of iron ball and container 50 g) was further placed thereon. The fishing line attached to the glass plate is pulled horizontally at a speed of 100 mm / min with a tensile tester (Orientec RTM-100) through a pulley, and the artificial leather ( The dynamic friction force between the back surface) and the film was measured.

(19) Boiling durability A sample having a crown shape (edge diameter of about 14 mm, thickness of about 0.1 mm) was used. The sample was placed in a sealed vial soaked in clean pure water. 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 (6) was performed.

(20) Rubbing durability A
A sample with a spherical crown shape (edge diameter of about 14 mm, thickness of about 0.1 mm) was used. Make a dent in the center of the palm, place the sample there, add a cleaning solution (manufactured by Nippon Alcon Co., Ltd., “Optifree (registered trademark)”), 10 times on the front and back of the index finger of the other hand After rubbing, it was placed in a screw tube containing clean “Optifree (registered trademark)” and allowed to stand for 4 hours or more. The above operation was set as one cycle and repeated 15 cycles. Thereafter, the sample was washed with pure water and immersed in a borate buffer. Then, the water wettability evaluation of the above (7) was performed.

(21) Rubbing durability B
The same procedure as in (20) above was performed using “Renew (registered trademark)” (Bochrom) instead of “Optifree (registered trademark)”.
(Reference Example 1)
Polydimethylsiloxane having methacryloyl groups at both ends as component A (DMS-R31, Gelest, Inc., compound of formula (M2) described later, mass average molecular weight 30,000, number average molecular weight 13,000) (20 Parts by mass), trifluoroethyl acrylate (Biscoat 3F, Osaka Organic Chemical Co., Ltd.) (80 parts by mass), Irgacure (registered trademark) 1850 (Ciba Specialty Chemicals, 2 parts by mass) and tetrahydrolinalol (20 parts by mass) Parts by mass) were mixed and stirred. A uniform and transparent monomer mixture was obtained. 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. The monomer mixture is injected into a mold made of transparent resin (poly-4-methylpentene-1) in a glove box in a nitrogen atmosphere, and a fluorescent lamp (Toshiba Corporation, FL-6D, daylight color, 6W, 4 pieces) is used. Polymerization was performed by light irradiation (8000 lux, 20 minutes). After the polymerization, the mold was immersed in a 60% by mass isopropyl alcohol aqueous solution, and a spherical crown-shaped molded body (edge diameter: about 14 mm, thickness: about 0.1 mm) was peeled from the mold. The obtained molding was immersed in a large excess of 80% by mass isopropyl alcohol aqueous solution at 60 ° C. for 2 hours. Further, the molded body was immersed in a large excess amount of 50 mass% isopropyl alcohol aqueous solution at room temperature for 30 minutes, then immersed in a large excess amount of 25 mass% isopropyl alcohol aqueous solution at room temperature for 30 minutes, and then a large excess amount of pure water. It was immersed in water at room temperature for 30 minutes. Finally, the molded body was placed in a sealed vial bottle soaked in clean pure water, and autoclaved at 121 ° C. for 30 minutes. The water content of the obtained molded body was less than 1%. The evaluation results of the obtained molded body are shown in Table 1.
(Reference Examples 2 to 12)
A molded body was obtained in exactly the same manner as in Reference Example 1, except that the amounts used of Component A and Component B were changed to the amounts described in Table 1. The water content of the obtained molded body was less than 1%. The evaluation results of the obtained molded body are shown in Table 1.

(Reference Examples 13 to 19)
Polydimethylsiloxane having methacryloyl groups at both ends as component A (DMS-R22, Gelest, Inc., compound of formula (M2) described later, mass average molecular weight 8.3,000, number average molecular weight 7.4,000) The molded product was used in the same manner as in Reference Example 1 except that the amount described in 2 was used and trifluoroethyl acrylate (Biscoat 3F, Osaka Organic Chemical Industry Co., Ltd.) was used as Component B in the amount described in Table 2. Obtained. The water content of the obtained molded body was less than 1%. The evaluation results of the obtained molded body are shown in Table 2.

(Reference Examples 20 to 24)
As component A, polydimethylsiloxane having methacryloyl groups at both ends (X-22-164C, Shin-Etsu Chemical Co., Ltd., mass average molecular weight 7.2,000, number average molecular weight 4.8,000) (50 parts by mass) was used. A molded product was obtained in the same manner as in Reference Example 1 except that the monomer (50 parts by mass) having a fluoroalkyl group described in Table 3 was used as Component B. The evaluation results of the obtained molded body are shown in Table 3.

Biscoat 3FM: Trifluoroethyl methacrylate (Osaka Organic Chemical Industry)
Biscoat 8F: Octafluoropentyl acrylate (Osaka Organic Chemical Industry)
Biscote 3F: Trifluoroethyl acrylate (Osaka Organic Chemical Industry)
Biscote 17F: Heptadecafluorodecyl acrylate (Osaka Organic Chemical Industry)
HFIP-M: Hexafluoroisopropyl methacrylate (Central Glass).
(Reference Examples 25 to 37)
As component A, polydimethylsiloxane having a methacryloyl group at both ends described in Table 4 (compound of formula (M2) described later) is used in the amount described in Table 4, Component B is not used, and Component C is used. A molded body was obtained in exactly the same manner as in Reference Example 1 except that the monomer (50 parts by mass) described in Table 4 was used in the amount described in Table 4. Table 4 shows the evaluation results of the obtained molded body.

Synthetic products 1 and 2 (compounds of formula (M2) described later) were synthesized with the molecular weights shown in Table 4 by a known method.
<Synthesis example>
The synthesis example of the copolymer used for coating in the examples is shown. In this synthesis example, the molecular weight of the copolymer was measured under the following conditions.
(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)
<CPVPA: N-vinylpyrrolidone / acrylic acid (molar ratio 2/1)>
In a 500 mL three-necked flask, N-vinylpyrrolidone (66.68 g, 0.60 mol), acrylic acid (21.62 g, 0.30 mol), dimethyl sulfoxide (353.96 g), polymerization initiator VA-061 (Wako Pure Chemical Industries, Ltd.) Company, 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 cooled to room temperature, 100 mL of water was added, and then poured into 400 mL of acetone and allowed to stand overnight. The next day, 200 mL of acetone was further added and allowed to stand, and the supernatant was removed by decantation. The obtained solid content was washed 7 times with acetone / water = 400 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: 46 kD, Mw: 180 kD (Mw / Mn = 3.9).
(Synthesis Example 2)
<CPVPA: N-vinylpyrrolidone / acrylic acid (molar ratio 1/2)>
In a 500 mL three-necked flask, N-vinylpyrrolidone (33.34 g, 0.30 mol), acrylic acid (43.24 g, 0.60 mol), dimethyl sulfoxide (307.08 g), polymerization initiator VA-061 (Wako Pure Chemical Industries, Ltd.) Company, 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 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 was added, and the supernatant was removed by decantation. The obtained solid content was washed 7 times with acetone / water = 700 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: 65 kD, Mw: 202 kD (Mw / Mn = 3.1).
(Synthesis Example 3)
<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.) Industrial Co., 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, 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 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 4)
<CPVPA: N-vinylpyrrolidone / acrylic acid (molar ratio 80/20)>
The same procedure as in Synthesis Example 3 was conducted except that 0.72 mol of N-vinylpyrrolidone and 0.18 mol of acrylic acid were used. The molecular weight of the copolymer thus obtained was Mn: 45 kD, Mw: 193 kD (Mw / Mn = 4.4).
(Synthesis Example 5)
<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.) Kogyo Co., 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 6)
<CPDA: N, N-dimethylacrylamide / acrylic acid (molar ratio 1/2)>
In a 500 mL three-necked flask, N, N-dimethylacrylamide (29.70 g, 0.300 mol), acrylic acid (43.20 g, 0.600 mol), pure water (292.40 g), polymerization initiator VA-061 (Wako Pure Chemical Industries, Ltd.) Kogyo Co., 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 350 g with an evaporator, poured into 2-propanol / n-hexane = 500 mL / 500 mL, allowed to stand, and 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: 87 kD, Mw: 235 kD (Mw / Mn = 2.7).
(Synthesis Example 7)
<CPDA: N, N-dimethylacrylamide / acrylic acid (molar ratio 90/10)>
In a 500 mL three-necked flask, N, N-dimethylacrylamide (DMA, 80.30 g, 0.810 mol), acrylic acid (6.49 g, 0.090 mol), pure water (347.90 g), polymerization initiator VA-061 (Japanese) Mitsuru Pure Chemical Industries, Ltd., 0.1408 g, 0.562 mmol), 2-mercaptoethanol (2-ME, 43.8 μL, 0.63 mmol) was 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 470 g with an evaporator, poured into 2-propanol / n-hexane = 500 mL / 500 mL, allowed to stand, and the supernatant was removed by decantation. The obtained solid content was washed 5 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: 54 kD, Mw: 162 kD (Mw / Mn = 3.0).
(Synthesis Example 8)
<CPDA: N, N-dimethylacrylamide / acrylic acid (molar ratio 95/5)>
In a three-necked flask, N, N-dimethylacrylamide (DMA, 0.19 mol), acrylic acid (AA, 0.01 mol), pure water, polymerization initiator VA-061 (Wako Pure Chemical Industries, Ltd., 0.093 mmol), 2 -Mercaptoethanol (2-ME, 0.07 mmol) was 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 350 g with an evaporator, poured into 2-propanol / n-hexane = 200 mL / 200 mL and allowed to stand, and then the supernatant was removed by decantation. The obtained solid content was washed three times with 2-propanol / n-hexane = 100 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: 77 kD and Mw: 229 kD.
(Synthesis Examples 9 to 16)
<CPDA: N, N-dimethylacrylamide / acrylic acid>
The amounts of N, N-dimethylacrylamide (DMA), acrylic acid (AA), polymerization initiator VA-061 and 2-mercaptoethanol (2-ME) used, and the monomer concentrations are the values described in Table 5. The same procedure as in Synthesis Example 8 was performed.

(Synthesis Example 17)
<CPDEAC: N, N-diethylacrylamide / acryloylmorpholine>
In a 300 mL three-necked flask, N, N-diethylacrylamide (12.71 g, 0.100 mol), N-acryloylmorpholine (14.12 g, 0.100 mol), t-amyl alcohol (63.20 g), polymerization initiator VA-061 (Wako Pure Chemical Industries, Ltd., 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 70 ° C. for 1 hour, then heated to 75 ° C. and stirred for 4 hours. After completion of the polymerization, the reaction solution was cooled to room temperature, and the solvent was distilled off with an evaporator, followed by washing once each with n-hexane / methanol = 300 mL / 80 mL, 130 mL / 35 mL, 100 mL / 20 mL, 100 mL / 10 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: 49 kD, Mw: 162 kD (Mw / Mn = 3.3).
(Synthesis Example 18)
<CPACDM: acryloylmorpholine / N, N-dimethylacrylamide />
In a 300 mL three-necked flask, N-acryloylmorpholine (14.20 g, 0.101 mol), N, N-dimethylacrylamide (DMA, 9.92 g, 0.100 mol), t-amyl alcohol (96.63 g), polymerization initiator VA -061 (Wako Pure Chemical Industries, Ltd., 0.0310 g, 0.124 mmol) and 2-mercaptoethanol (86 μL, 1.23 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 70 ° C. for 1 hour, then heated to 75 ° C. and stirred for 4 hours. After completion of the polymerization, the mixture was cooled to room temperature, and the solvent was distilled off with an evaporator, followed by washing once each with n-hexane / methanol = 400 mL / 30 mL, 500 mL / 40 mL, 130 mL / 3 mL, and 200 mL / 7 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: 4.3 kD, Mw: 17 kD (Mw / Mn = 4.1).
(Synthesis Example 19)
<CPDEDM: N, N-diethylacrylamide / N, N-dimethylacrylamide>
In a 300 mL three-necked flask, N, N-diethylacrylamide (DEAA, 19.22 g, 0.151 mol), N, N-dimethylacrylamide (DMA, 14.88 g, 0.150 mol), TAA (104.65 g), polymerization initiator VA-061 (Wako Pure Chemical Industries, Ltd., 0.0465 g, 0.186 mmol) was added, and a three-way cock, reflux condenser, thermometer, and mechanical stirrer were attached. The monomer concentration was 25% 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 70 ° C. for 1.5 hours, then heated to 75 ° C. and stirred for 3.5 hours. After completion of the polymerization, the reaction mixture was cooled to room temperature, and the solvent was distilled off with an evaporator, followed by washing once each with n-hexane / methanol = 500 mL / 0 mL, 250 mL / 25 mL, 200 mL / 30 mL, and 200 mL / 3 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: 90 kD, Mw: 327 kD (Mw / Mn = 3.7).
(Synthesis Example 20)
<CPHEDM: N- (2-hydroxyethyl) acrylamide / N, N-dimethylacrylamide>
In a 300 mL three-necked flask, N- (2-hydroxyethyl) acrylamide (15.04 g, 0.100 mol), N, N-dimethylacrylamide (9.96 g, 0.100 mol), t-amyl alcohol (99.80 g), polymerization Initiator VA-061 (Wako Pure Chemical Industries, Ltd., 0.0310 g, 0.124 mmol) was 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 70 ° C. for 1 hour, then heated to 75 ° C. and stirred for 4 hours. After completion of the polymerization, the reaction mixture was cooled to room temperature, and then washed once each with n-hexane / methanol = 200 mL / 100 mL, 200 mL / 100 mL, 100 mL / 40 mL, and 100 mL / 60 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: 109 kD, Mw: 660 kD (Mw / Mn = 6.1).
(Synthesis Example 21)
<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 Industries, Ltd., 0.0310 g, 0.124 mmol) was added, and a three-way cock, reflux condenser, thermometer, and 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).
(Synthesis Example 22)
<CPHA: 2-hydroxyethyl methacrylate / acrylic acid (molar ratio 3/1)>
In a 300 mL three-necked flask, 2-hydroxyethyl methacrylate (HEMA, 10.3 g, 0.09 mol), acrylic acid (AA, 2.2 g, 0.03 mol), dimethyl sulfoxide (49.7 g), polymerization initiator VA-061 ( Wako Pure Chemical Industries, Ltd., 0.009 g, 0.038 mmol), 2-mercaptoethanol (2-ME, 2.6 μL, 0.038 mmol) are added, and a three-way cock, reflux condenser, thermometer, and mechanical stirrer are installed. did. 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 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, 20 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: 83 kD, Mw: 188 kD (Mw / Mn = 2.3).
(Synthesis Example 23)
<CPHA: 2-hydroxyethyl methacrylate / acrylic acid (molar ratio 3/1)>
In a 300 mL three-necked flask, 2-hydroxyethyl methacrylate (HEMA, 10.3 g, 0.09 mol), acrylic acid (AA, 2.2 g, 0.03 mol), dimethyl sulfoxide (49.8 g), polymerization initiator VA-061 ( Wako Pure Chemical Industries, Ltd., 0.009 g, 0.038 mmol), 2-mercaptoethanol (2-ME, 7.8 μL, 0.111 mmol) are added, and a three-way cock, reflux condenser, thermometer, and mechanical stirrer are attached. did. 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 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, 20 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: 50 kD, Mw: 96 kD (Mw / Mn = 1.9).
(Synthesis Example 24)
<CPHA: 2-hydroxyethyl methacrylate / acrylic acid (molar ratio 1/1)>
In a 200 mL three-necked flask, 2-hydroxyethyl methacrylate (HEMA, 11.4 g, 0.10 mol), acrylic acid (AA, 7.21 g, 0.10 mol), dimethyl sulfoxide (74.5 g), polymerization initiator VA-061 ( Wako Pure Chemical Industries, Ltd., 0.016 g, 0.062 mmol) was 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 60 ° 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, poured into 1000 mL of water / 10 mL of ethanol, and allowed to stand overnight. On the next day, the supernatant was discarded, and the obtained solid content was further washed twice with 700 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: 79 kD, Mw: 226 kD (Mw / Mn = 2.9).
(Synthesis Example 25)
Hereinafter, pure water refers to water purified by filtration through a reverse osmosis membrane.
<P (DMAA / AA): 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.) Kogyo Co., 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).
(Reference Example 38)
Preparation of coating solution <PEI solution A>
Polyethyleneimine (P3143, Sigma-Aldrich, molecular weight 750,000) was dissolved in pure water to give a 1% by mass aqueous solution.
<PEI solution B>
Polyethyleneimine (P-70, 167-1951, Wako Pure Chemical Industries, Ltd., molecular weight 70,000) was dissolved in pure water to give a 1% by mass aqueous 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.
<PAAM solution A>
Polyallylamine (PAA-15C, Nitto Boseki Co., Ltd., molecular weight 15,000) was dissolved in pure water to give a 1% by mass aqueous solution.
<PAAM solution B>
Polyallylamine (PAA-25, Nitto Boseki Co., Ltd., molecular weight 25,000) was dissolved in pure water to give a 1% by mass aqueous solution.
<PAS solution>
A diallyldimethylammonium chloride polymer (PAS-H-10L, Nitto Boseki Co., Ltd., molecular weight 200,000) was dissolved in pure water to give a 1% by mass aqueous solution.
<Copolymer solution>
Each of the copolymers obtained in the synthesis examples shown in Table 6 was dissolved in the solvent shown in Table 6 to obtain solutions having the concentrations shown in Table 6.

NVP: N-vinylpyrrolidone DMA: N, N-dimethylacrylamide DEAA: N, N-diethylacrylamide ACMO: acryloylmorpholine HEAA: N- (2-hydroxyethyl) acrylamide HEMA: 2-hydroxyethyl methacrylate AA: acrylic acid <others Solution>
Each of the substances shown in Table 7 was dissolved in pure water to obtain aqueous solutions having the concentrations shown in Table 7.

Hyaluronic acid Na: sodium hyaluronate (CHA) (Chisso Corporation)
Kimika Argin I-3: Sodium Alginate (Kimika Co., Ltd.)
Kimiloid HV: propylene glycol alginate (Kimika Co., Ltd.)
NS-300 (Carmellose): Carboxymethylcellulose (Gotoku Pharmaceutical Co., Ltd.)
Sunrose (registered trademark) (APP-84): Carboxymethylcellulose (Nippon Paper Chemical Co., Ltd.)
Chondroitin sulfate Na: Chondroitin sodium sulfate (Seikagaku Corporation)
Griroid 6C: Tamarind gum (Dainippon Sumitomo Pharma Co., Ltd.)
Labor gum CG-SFT: Xanthan gum (Dainippon Sumitomo Pharma Co., Ltd.)
(Examples 1 to 3)
The molded bodies obtained in the respective reference examples shown in Table 8 were immersed in the PEI solution A for 30 minutes and then immersed in three pure water baths for 5 minutes. Next, the molded body was immersed in a PAA solution for 30 minutes, and then immersed in three pure water baths for 5 minutes. The wettability and dynamic contact angle of the obtained low hydrous soft substrate sample were evaluated. The results are shown in Table 8. -In the table means that the coating operation with the solution is not performed.
(Examples 4 to 6)
The molded body obtained in each reference example shown in Table 8 was immersed in a PAA solution for 30 minutes, and then immersed in three pure water baths for 5 minutes. Next, after being immersed in the PEI solution A for 30 minutes, each was immersed in three pure water baths for 5 minutes. Next, the molded body was immersed in a PAA solution for 30 minutes, and then immersed in three pure water baths for 5 minutes. The wettability and dynamic contact angle of the obtained low hydrous soft substrate sample were evaluated. The results are shown in Table 8.
(Examples 7 to 14)
The molded body obtained in each reference example shown in Table 8 was immersed in the first solution shown in Table 8 for 30 minutes, and then immersed in three pure water baths for 5 minutes. Next, after being immersed in the second solution shown in Table 8 for 30 minutes, each was immersed in three pure water baths for 5 minutes. Next, the molded body was immersed in the third solution shown in Table 8 for 30 minutes, and then immersed in three pure water baths for 5 minutes. The wettability and dynamic contact angle of the obtained low hydrous soft substrate sample were evaluated. The results are shown in Table 8.
(Comparative Examples 1 to 3)
The wettability and dynamic contact angle of the molded body obtained in each reference example shown in Table 8 were evaluated. The results are shown in Table 8. -In the table means that the coating operation with the solution is not performed.
(Comparative Examples 4 to 6)
The molded bodies obtained in the respective reference examples shown in Table 8 were immersed in the PEI solution A for 30 minutes, and then the molded bodies were immersed in three pure water baths for 5 minutes. The wettability and dynamic contact angle of the obtained low hydrous soft substrate sample were evaluated. The results are shown in Table 8. -In the table means that the coating operation with the solution is not performed.
(Comparative Examples 7 to 9)
The molded body obtained in each reference example shown in Table 8 was immersed in a PAA solution for 30 minutes, and then immersed in three pure water baths for 5 minutes. The wettability and dynamic contact angle of the obtained low hydrous soft substrate sample were evaluated. The results are shown in Table 8. -In the table means that the coating operation with the solution is not performed.

(Reference Examples 39 to 42)
As component A, polydimethylsiloxane having methacryloyl groups at both ends (DMS-R31, Gelest, Inc., compound of formula (M2) described later, number average molecular weight 13,000) (50 parts by mass), A low hydrous soft base material sample was obtained in the same manner as in Reference Example 1 except that the monomer (50 parts by mass) having a fluoroalkyl group described in Table 9 was used as Component B. The evaluation results of the obtained low hydrous soft base material sample are shown in Table 9.

Biscoat 3FM: trifluoroethyl methacrylate (Osaka Organic Chemical Co., Ltd.)
Biscote 8F: Octafluoropentyl acrylate (Osaka Organic Chemical Co., Ltd.)
Biscote 17F: Heptadecafluorodecyl acrylate (Osaka Organic Chemical Industry Co., Ltd.)
HFIP-M: Hexafluoroisopropyl methacrylate (Central Glass Co., Ltd.)
(Reference Example 43)
Polydimethylsiloxane having methacryloyl groups at both ends as component A (DMS-R31, Gelest, Inc., mass average molecular weight 30,000, compound of formula (M2) described later, number average molecular weight 13,000) (50 Part by mass), trifluoroethyl acrylate (Biscoat 3F, Osaka Organic Chemical Co., Ltd.) (46 parts by mass) as component B, methyl methacrylate (3 parts by mass) as component C, and UV absorber having a polymerizable group as component C (RUVA-93, compound represented by formula (M1), Otsuka Chemical Co., Ltd.) (1 part by mass), polymerization initiator “Irgacure (registered trademark)” 1850 (Ciba Specialty Chemicals, 2 parts by mass) and t -Amyl alcohol (10 parts by weight) was mixed and stirred. A uniform and transparent monomer mixture was obtained. This monomer mixture was put into a test tube, deaerated while being stirred with a touch mixer at a reduced pressure of 20 Torr (27 hPa), and then returned to atmospheric pressure with argon gas. This operation was repeated three times. A monomer mixture is injected into a mold made of transparent resin (poly-4-methylpentene-1) in a glove box in a nitrogen atmosphere, and light is emitted using a fluorescent lamp (Toshiba Corporation, FL-6D, daylight color, 6W, 4). Polymerization by irradiation (8000 lux, 20 minutes). After the polymerization, the mold was immersed in a 60% by mass isopropyl alcohol aqueous solution, and a spherical crown-shaped molded body (edge diameter: about 14 mm, thickness: about 0.1 mm) 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 It was immersed in pure water at room temperature for 30 minutes. Finally, the molded body was placed in a sealed vial bottle soaked in clean pure water, and autoclaved at 121 ° C. for 30 minutes. The water content of the obtained molded body was less than 1%. Moreover, the same operation was performed using two glass plates and a gasket as a mold to obtain a film-like sample of 60 mm × 60 mm × 0.25 mm.

(Reference Examples 44 to 47 and 70 to 75)
Using the components shown in Table 10, the same procedure as in Reference Example 43 was performed to obtain a spherical crown-shaped molded body and a film sample of 60 mm × 60 mm × 0.25 mm. In the table, “-” means that the component is not used.

DMS-R31: compound of formula (M2) Mw 30 kD, Mn 13 kD,
Gelest, Inc.
FM-7726: Compound of formula (M2) Mw 29 kD, Mn 26 kD,
Chisso Corporation FM-7726L: Compound of formula (M2) Mw 31 kD, Mn 20 kD,
Chisso Corporation X-22-164C: Compound of formula (M2) Mw 7.2 kD, Mn 4.8 kD, Shin-Etsu Chemical Co., Ltd. DMS-R22: Compound of formula (M2) Mw 8.3 kD, Mn 7.4 kD,
Gelest, Inc.
In the formula (M2), n represents the number of repeating units and is determined by the molecular weight of the compound.

Biscoat 3F: trifluoroethyl acrylate MMA: methyl methacrylate EHMA: 2-ethylhexyl acrylate DMAA: N, N-dimethylacrylamide DMAEA: N, N-dimethylaminoethyl acrylate DMAPAA: N, N-diethylaminopropylacrylamide DEAEMA: N, N- Diethylaminoethyl methacrylate TAA: t-amyl alcohol AA: Acrylic acid MAA: Methacrylic acid (Reference Example 48)
Polydimethylsiloxane having methacryloyl groups at both ends as component A (FM7726, Chisso Corporation, compound of formula (M2), mass average molecular weight 29 kD, number average molecular weight 26 kD) (49 parts by mass), component B trifluoro Ethyl acrylate (Biscoat 3F, Osaka Organic Chemical Co., Ltd.) (45 parts by mass), Component C as 2-ethylhexyl acrylate (5 parts by mass), Component C as N, N-dimethylacrylamide (1 part by mass), Component C as Ultraviolet absorber having a polymerizable group (RUVA-93, Otsuka Chemical Co., Ltd.) (1 part by mass), Colorant having a polymerizable group as Component C [(Uniblue A, Sigma-Aldrich, Formula (M3)] (0. 1 part by mass), polymerization initiator “Irgacure (registered trademark)” 819 (Ciba Specialty Ke) Mikals, 0.75 parts by mass) and t-amyl alcohol (10 parts by mass) were mixed and stirred, filtered through a membrane filter (0.45 μm) to remove insolubles, and a monomer mixture was obtained. The sample was put into a test tube, deaerated while being stirred with a touch mixer and reduced in pressure to 20 Torr (27 hPa), and then returned to atmospheric pressure with argon gas.This operation was repeated three times. The monomer mixture is injected into a mold made of (poly-4-methylpentene-1) and irradiated with light (8000 lux, 20 minutes) using a fluorescent lamp (Toshiba Corporation, FL-6D, daylight color, 6W, 4 tubes). After the polymerization, the mold is immersed in a 60% by mass isopropyl alcohol aqueous solution, and a spherical crown-shaped molded body (edge The resulting molded body was immersed in a large excess of 80% by weight isopropyl alcohol aqueous solution at 60 ° C. for 2 hours. Soaked in a 50% by weight isopropyl alcohol aqueous solution at room temperature for 30 minutes, then soaked in a large excess of 25% by weight isopropyl alcohol aqueous solution at room temperature for 30 minutes, and then soaked in a large excess of pure water at room temperature for 30 minutes. Finally, the molded body was immersed in clean pure water in a sealed vial and autoclaved for 30 minutes at 121 ° C. The water content of the obtained molded body was less than 1%. Moreover, the same operation was performed using two glass plates and a gasket as a mold to obtain a film sample of 60 mm × 60 mm × 0.25 mm.

(Reference Examples 49-69)
Using the components shown in Table 10, the same procedure as in Reference Example 48 was performed to obtain a crown-shaped molded body and a film sample of 60 mm × 60 mm × 0.25 mm. In the table, “-” means that the component is not used.
(Examples 15 to 183, Comparative Examples 10 to 30, and Control Examples 1 and 2)
The molded bodies or commercially available contact lenses obtained in the respective reference examples shown in Tables 11 to 16 were immersed in the first solutions shown in Tables 11 to 30 for 30 minutes, and then immersed in three pure water baths for 5 minutes. Next, the molded body or the commercially available contact lens was immersed in the second solution shown in Tables 11 to 30 for 30 minutes, and then immersed in three pure water baths for 5 minutes. The above operation was similarly repeated for the third to fifth solutions. Evaluation of the obtained low hydrous soft base material was implemented. The results are shown in Tables 11-16. In the table, “-” means that the coating operation with the solution is not performed or the evaluation is not performed.

In the control example, a commercially available soft contact lens formed of silicone hydrogel as a soft substrate was used.

SHG-A: Commercially available silicone hydrogel soft contact lens A
SHG-B: Commercially available silicone hydrogel soft contact lens B

* 1: 1: 1 (mass) mixture of CPHA solution E and CPDA solution A * 2: 1: 1 (mass) mixture of CPHA solution A and CPDA solution A

(Example 184)
<Oxygen permeability measurement>
A film (thickness 0.19 mm) prepared in the same manner as in Example 62 was cut into a size of 20 mm × 20 mm to prepare a sample. Oxygen permeability was measured using an oxygen permeability measuring device OX-TRAN 2/21 (Hitachi High-Technologies Corporation). A mixed gas of 98% nitrogen / 2% hydrogen was used as the carrier gas, and a mixed gas of 79.3% nitrogen / 20.7% oxygen was used as the measurement gas. The gas was not humidified. The oxygen permeability of the sample was 390 × 10 ⁻¹¹ (cm ² / sec) (mLO ₂ ) / (mL · hPa). The oxygen permeability of the gas permeable hard contact lens “Menicon Z (registered trademark)” manufactured by Menicon Co., Ltd. measured under the same conditions with the same apparatus is 150 × 10 ⁻¹¹ (cm ² / sec) (mLO ₂ ) / ( mL · hPa), a gas permeable hard contact lens “breath ohard (registered trademark)” manufactured by Toray Industries, Inc. has an oxygen permeability of 120 × 10 ⁻¹¹ (cm ² / sec) (mLO ₂ ) / (mL · hPa) Met.
(Reference Example 81)
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 it was confirmed that the pH was about 1-2 with a pH test paper. 24 g of ethyl acetate was added and lightly stirred. The mixture was transferred to a 100 mL Nasralasco and allowed to stand. 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 was made to dry at 40 degreeC for 16 hours with a vacuum dryer, and acid type UniBlue A was obtained [estimated structural formula (M4)].

(Reference Example 82)
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.
<P (DMAA / AA) solution>
The N, N-dimethylacrylamide / acrylic acid copolymer of Synthesis Example 25 synthesized by the inventors in the laboratory was dissolved in pure water to give a 1% by mass aqueous solution.
<PAMPS solution>
A 2-acrylamido-2-methylpropanesulfonic acid polymer (Sigma Aldrich, molecular weight 2 million, 15% by weight aqueous solution) was dissolved in pure water to give a 1.5% by weight aqueous solution.
(Reference Example 83)
Polydimethylsiloxane having methacryloyl groups at both ends as component A (FM7726, JNC, compound of formula (M5), 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 Co., Ltd.) (45 parts by mass), Component C as 2-ethylhexyl acrylate (3 parts by mass), Component C as dimethylaminoethyl acrylate (1 part by mass), Component C as an ultraviolet ray having a polymerizable group Absorber (RUVA-93, Otsuka Chemical Co., Ltd.) (1 part by mass), colorant of Reference Example 81 having a polymerizable group as component C, acid type UniBlue A (0.04 parts by mass), polymerization initiator “Irgacure (Registered trademark) "819 (Ciba Specialty Chemicals, 0.75 parts by mass) and And t-amyl alcohol (10 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. The monomer mixture was degassed under an argon atmosphere. In the glove box under a nitrogen atmosphere, between the two 10 cm square and 3 mm thick glass plates (one of which is affixed with an aluminum seal to make it easy to peel off) A film-like molded body is obtained by filling a gap between two cutouts as spacers with a monomer mixture and curing by light irradiation (Toshiba FL6D, 1.01 mW / cm ² , 20 minutes). It was.

The obtained molded body (film) was immersed in a 60% by mass isopropanol (IPA) aqueous solution at 60 ° C. for 30 minutes, peeled off from the glass plate, and further immersed in an 80% by mass IPA aqueous solution at 60 ° C. for 2 hours to leave residual monomers, etc. The impurities were extracted, immersed in a 50% by mass IPA aqueous solution and a 25% by mass IPA aqueous solution in a stepwise decrease in IPA concentration for about 30 minutes, and finally immersed in water for 2 hours or longer to be hydrated.
(Reference Example 84)
Silicone monomer represented by formula (M6) (13.4 parts by mass), N, N-dimethylacrylamide (37.0 parts by mass), silicone monomer represented by formula (M7) (36.6 parts by mass), Photoinitiator Irgacure 1850 (1.26 parts by mass), UV absorber (RUVA-93, Otsuka Chemical Co., Ltd.) (1.26 parts by mass) 2-hydroxyethyl methacrylate (9.2 parts by mass), triethylene Glycol dimethacrylate (1.26 parts by mass), UniBlue A (0.02 parts by mass) represented by the formula (M8), and tetrahydrolinalool (23.9 parts by mass) were mixed and stirred. Thereafter, the same operation as in Reference Example 83 was performed to produce a film.

(Reference Example 85)
Silicone monomer represented by formula (M6) (13.4 parts by mass), N, N-dimethylacrylamide (28.0 parts by mass), silicone monomer represented by formula (M7) (36.6 parts by mass), Polyvinylpyrrolidone (Mw about 500,000, 12.0 parts by mass), photoinitiator Irgacure 1850 (1.0 part by mass), ultraviolet absorber (RUVA-93, Otsuka Chemical Co., Ltd.) (1.0 part by mass) methacrylic acid -2-hydroxyethyl (7.0 parts by mass), triethylene glycol dimethacrylate (1.0 parts by mass), a dye monomer represented by the formula (M8) (0.02 parts by mass), tetrahydrolinalool (32.0 parts) Parts by mass) were mixed and stirred. Thereafter, the same operation as in Reference Example 83 was performed to produce a film.
(Reference Example 86)
Silicone monomer represented by formula (M6) (13.4 parts by mass), N, N-dimethylacrylamide (22.2 parts by mass), silicone monomer represented by formula (M7) (36.6 parts by mass), Polyvinylpyrrolidone (Mw about 500,000, 20.0 parts by mass), photoinitiator Irgacure 1850 (0.76 parts by mass), UV absorber (RUVA-93, Otsuka Chemical Co., Ltd.) (0.76 parts by mass) methacrylic acid -2-hydroxyethyl (5.5 parts by mass), triethylene glycol dimethacrylate (0.76 parts by mass), a dye monomer represented by the formula (M8) (0.02 parts by mass), tetrahydrolinalol (50.0 parts) Parts by mass) were mixed and stirred. Thereafter, the same operation as in Reference Example 83 was performed to produce a film.
(Reference Example 87)
A film was prepared in the same manner as in Reference Example 83 using polydimethylacrylamide (Mw: about 500,000, 12.0 parts by mass) instead of the polyvinyl pyrrolidone of Reference Example 85.
(Reference Example 88)
A film was produced in the same manner as in Reference Example 83 using polydimethylacrylamide (Mw: about 500,000, 20.0 parts by mass) instead of the polyvinyl pyrrolidone of Reference Example 86.
<Evaluation of water retention>
(Example 191)
The film obtained in Reference Example 83 was immersed in a PAA solution at room temperature for 30 minutes, and then lightly rinsed with pure water in a beaker. The film 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 p (DMAA / AA) solution. After finishing the coating operation, the coated film was immersed in a borate buffer solution (pH 7.1 to 7.3) in a UM sample bottle and autoclaved at 121 ° C. for 30 minutes. The sterilized film was stored in a desiccator at a temperature of 33.1 ° C. and a humidity of 90% for 48 hours to evaluate water retention. The film had water retention and softness even after storage for 48 hours. The evaluation results are shown in Table 17.

(Example 192)
The film obtained in Reference Example 83 was immersed in a PAA solution at room temperature for 30 minutes, and then lightly rinsed with pure water in a beaker. The film 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 film was immersed in a borate buffer solution (pH 7.1 to 7.3) in a UM sample bottle and autoclaved at 121 ° C. for 30 minutes. The sterilized film was stored in a desiccator at a temperature of 33.1 ° C. and a humidity of 90% for 48 hours to evaluate water retention. The film had water retention and softness even after storage for 48 hours. The evaluation results are shown in Table 17.
(Comparative Examples 31 to 35)
The film obtained in each reference example shown in Table 17 was immersed in a borate buffer solution (pH 7.1 to 7.3) in a UM sample bottle, and autoclaved at 121 ° C. for 30 minutes. went. The sterilized film was stored in a desiccator at a temperature of 33.1 ° C. and a humidity of 90% for 48 hours to evaluate water retention. When the film after storage for 48 hours was placed on the skin, it was dry and hard. The evaluation results are shown in Table 17.

The present invention relates to a low hydrous soft device, and is useful in medical devices, biotechnology devices, agricultural / gardening devices, filtration devices, antifouling devices, beauty devices, and other daily necessities.

DESCRIPTION OF SYMBOLS 1 Artificial leather 2 Sample film 3 Rubber plate 4 Plastic container containing iron ball 10 Infusion tube 20 Catheter 30 Stent 31 Stent main body 32 Low hydrous soft base material 40 Endoscope 41 Insertion tube 42 Tip part 43 Optical system 44 End face 45 Low hydrous soft substrate 50 Gas-liquid separation membrane 60 Moisturizing sheet 61 Opening 62 Soil 63 Plant 70 Pharmaceutical carrier 80 Granular moisturizing material 81 Houseplant 82 Root

Claims

A low hydrous soft device comprising a soft member in which a layer made of an acidic polymer and a basic polymer is formed on at least a part of the surface of a low hydrous soft substrate.
The low hydrous soft device according to claim 1, wherein the soft member has a tube shape.
The low hydrous soft device according to claim 1, wherein the soft member is in the form of a sheet or a film.
The low hydrous soft device according to claim 3, which is any one of a medical device, a biotechnology device, an agricultural / gardening device, a filtration device, an antifouling device, and a beauty device.
The low hydrous soft device according to claim 4, wherein the medical device includes a skin covering material, a wound covering material, a skin protecting material, or a skin drug carrier.
The low hydrous soft device according to claim 1, wherein the soft member has a storage container shape.
The low hydrous soft device according to claim 1, wherein the soft member has a granular shape.
The low hydrous soft substrate according to any one of claims 1 to 7, wherein the low hydrous soft base material is mainly composed of a polymer of the following component A or a copolymer of the following component A and component B. device;
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 low hydrous soft device according to claim 8, wherein the component A is a polysiloxane compound having two polymerizable functional groups per molecule.
The layer composed of the acidic polymer and the basic polymer is formed by performing the treatment with one or more acidic polymer solutions once or more and the treatment with one or more basic polymer solutions once or more. 10. The low hydrous soft device according to any one of 1 to 9.
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 low hydrous soft device according to claim 10.
The low water content according to claim 10, wherein the layer composed of the acidic polymer and the basic polymer is formed by performing the treatment with two kinds of acidic polymer solutions twice and the treatment with the basic polymer solution once. Soft device.
13. The polymer according to claim 1, wherein at least one of the acidic polymer and the basic polymer forming the layer composed of the acidic polymer and the basic polymer is a polymer having a group selected from a hydroxyl group and an amide group. The low hydrous soft device according to claim 1.
A method for producing a low hydrous soft device comprising the following steps 1 to 3 in this order;
<Step 1>
Polymerizing a mixture containing 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 and component B which is a polymerizable monomer having a fluoroalkyl group Obtaining a molded body having a shape of
<Step 2>
A step of washing and removing excess of the basic polymer solution after contacting the molded body 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.