COATED SILICONE MEMBER MANUFACTURING METHOD

Abstract

The purpose of the present invention is to provide a coated silicone member manufacturing method which enables, even when a highly water-repellent silicone member having a water surface contact angle of more than 110° is processed at a low temperature, formation of, on the surface, a coating having a sufficiently low surface contact angle with respect to an aqueous solution containing a salt and a protein. The present invention provides a coated silicone member manufacturing method comprising: (A) a degradative reaction step for degrading the surface of a silicone member; (B) a contact step b for bringing a solution b containing a polycarbodiimide into contact with the surface-degraded silicone member; and (C) a contact step c for bringing a solution c containing a polymer C into contact with the surface-degraded silicone member. The polymer C has an alkyl amide group and hydroxyl group.

Claims

1. A method for producing a coated silicone member comprising: (A) a decomposition reaction step of decomposing a surface of a silicone member; (B) a contact step b of bringing the silicone member whose surface is decomposed into contact with a solution b containing polycarbodiimide; and (C) a contact step c of bringing the silicone member whose surface is decomposed into contact with a solution c containing a polymer C, wherein the polymer C has an alkylamide group and a hydroxyl group.

2. The method for producing a coated silicone member according to claim 1, wherein a temperature of the solution b and/or the solution c is 50° C. to 80° C.

3. The method for producing a coated silicone member according to claim 1, wherein the solution b is an emulsion.

4. The method for producing a coated silicone member according to claim 1, wherein the solution c further contains a polymer having a carboxylic acid group.

5. A method for producing a coated silicone member comprising: (A) a decomposition reaction step of decomposing a surface of a silicone member; and (D) a contact step d of bringing the silicone member whose surface is decomposed into contact with a solution d containing polycarbodiimide and a polymer C, wherein the polymer C has an alkylamide group and a hydroxyl group.

6. The method for producing a coated silicone member according to claim 5, wherein a temperature of the solution d is 50° C. to 80° C.

7. The method for producing a coated silicone member according to claim 5, wherein the solution d is an emulsion.

8. The method for producing a coated silicone member according to claim 5, wherein the solution d further contains a polymer having a carboxylic acid group.

9. The method for producing a coated silicone member according to claim 1, wherein the polycarbodiimide has a weight average molecular weight of 45,000 to 200,000.

10. The method for producing a coated silicone member according to claim 1, wherein the polymer C further has a 2-alkoxyethyl group.

11. The method for producing a coated silicone member according to claim 1, wherein the decomposition method in the decomposition reaction step (A) is hydrolysis.

12. The method for producing a coated silicone member according to claim 1, further comprising a fixing step of fixing the silicone member to a surface of a substrate (X).

Description

EXAMPLES

[0063] Hereinafter, the present invention will be specifically described with reference to Examples and the like, but the present invention is not limited thereto.

[0064] In Examples, the following was used. [0065] MEA: 2-Methoxyethyl acrylate, manufactured by Tokyo Chemical Industry Co., Ltd. [0066] DMAA: N,N-dimethylacrylamide, manufactured by Tokyo Chemical Industry Co., Ltd. [0067] 164B: Difunctional silicone monomer, X-22-164B (α,ω-bis(3-methacryloxy-propyl)-polydimethylsiloxane), functional group equivalent: 1,600, manufactured by Shin-Etsu Chemical Co., Ltd. [0068] FM0711: Linear polymerizable silicone compound “Silaplane” (registered trademark) (polydimethylsiloxane monomethacrylate), average molecular weight: 1000, manufactured by JNC Corporation, [0069] NB: Ultraviolet absorber 2-(2′-hydroxy-5′-methacryloyloxyethylphenyl)-2H-benzotriazole, manufactured by Tokyo Chemical Industry Co., Ltd. [0070] RB: Colorant Reactive Blue 246 (1,4-bis[4-(2-methacryloxyethyl)phenylamino]anthraquinone), manufactured by Arran Chemical Co., LTD. [0071] IC-819: Photoinitiator “IRGACURE” (registered trademark) 819 (phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide) (acylphosphine oxide-based polymerization initiator), manufactured by Ciba Specialty Chemicals Inc. [0072] TAA: Non-polymerizable solvent, tert-amyl alcohol, manufactured by Tokyo Chemical Industry Co., Ltd.

[0073] <Method for Preparation of Phosphate Buffered Saline Solution (PBS)>

[0074] In a 2 L Erlenmeyer flask, 16 g of sodium chloride, 0.4 g of potassium chloride, 2.88 g of disodium hydrogen phosphate, 0.48 g of potassium dihydrogen phosphate and 2 L of RO water were weighed. A stirrer was put in the flask and the mixture was well stirred, and after confirming that the reagent is dissolved, filtration was performed using a polyether sulfone filter (EXPRESS PLUS PES 22UM 45MM, manufactured by Merck KGaA) and a vacuum pump to obtain a phosphate buffered saline solution (PBS).

[0075] <Preparation of Silicone Member A>

[0076] 2.2 g of MEA, 4.3 g of FM0711, 2.5 g of DMAA, 1.0 g of 164B, 0.05 g of NB, 0.002 g of RB, 0.02 g of IC-819 and 4.0 g of TAA were well mixed. This mixture was filtered through a membrane filter (0.45 μm) to remove an insoluble substance to obtain a monomer composition. This monomer composition was injected into molds, and polymerized by light irradiation (1.01 mW/cm.sup.2, 20 min) using a fluorescent lamp (manufactured by Toshiba Corporation, FL-6D, daylight color, 6 W, 4 fibers) under a nitrogen atmosphere. After polymerization, the molds was immersed in a mixed solution of isopropyl alcohol and water in a ratio of 55:45 (volume ratio before mixing) and heated at 60° C. for 1 hour to remove a molded body. Thereafter, the molded body thus obtained was immersed in fresh isopropyl alcohol and water in a ratio of 55:45 (volume ratio before mixing) and heated at 60° C. for 3 hours, followed by extraction.

[0077] The molded body obtained after the extraction was immersed in a mixed solution of isopropyl alcohol and water in a ratio of 3:7 (volume ratio before mixing) at room temperature for 30 minutes, and then immersed in PBS to be left standing and stored overnight, thereby obtaining a circular sheet-shaped silicone member A having a diameter of 13 mm and a thickness of about 100 μm. The surface contact angle A of the silicone member A was 115° as measured by a method to be described later, and high water repellency was exhibited.

Example 1

[0078] (A) The silicone member A was immersed in a 0.25 N aqueous sodium hydroxide solution, and heated at 60° C. for 30 minutes to perform a hydrolysis reaction. After cooling to room temperature, the silicone member A was taken out from the solution, and lightly swing-washed in PBS. (B) A 1 mass % “Carbodilite” (registered trademark) V-02 aqueous solution (polycarbodiimide, weight average molecular weight 86,000, pH=8.2, manufactured by Nisshinbo Chemical Inc.) was prepared, and the silicone member A was immersed in the aqueous solution at 60° C. for 30 minutes. After cooling, the silicone member A was taken out from the aqueous solution, and lightly swing-washed in PBS. (C) An aqueous solution was prepared by mixing 1 mass % of an aqueous solution of 2-methoxyethyl acrylate/N,N-dimethylacrylamide/acrylic acid copolymer (copolymerization ratio 2/7/1 [molar ratio], weight average molecular weight 1,040,000) and 1 mass % of an aqueous solution of polyacrylic acid (product name AC-10 H, manufactured by Toagosei Company, Limited) at a ratio of 2:1.7 (mass ratio). The polyacrylic acid is a polymer having a carboxylic acid group. The silicone member A was immersed in the mixed aqueous solution at 60° C. for 30 minutes. After cooling to room temperature, the silicone member A was taken out from the mixed aqueous solution, and lightly swing-washed in PBS. The silicone member was immersed in clean PBS, heat-sterilized at 121° C. for 30 minutes, and stored at room temperature to obtain a coated silicone member.

[0079] The weight average molecular weight of the used polymer (including polycarbodiimide) was measured under the following conditions.

[0080] (GPC Measurement Conditions) [0081] Apparatus: Prominence GPC system manufactured by Shimadzu Corporation [0082] Pump: LC-20AD, Autosampler: SIL-20AHT [0083] Column oven: CTO-20A, Detector: RID-10A [0084] Column: GMPXW, manufactured by Tosoh Corporation (7.8 mm in inner diameter×30 cm, particle diameter of 13 mm) [0085] Solvent: water/methanol=1/1 (0.1 N lithium nitrate is added) [0086] Flow rate: 0.5 mL/minute [0087] Measurement time: 30 minutes, Sample concentration: 0.1 mass %, Injection amount: 20 μL [0088] Standard sample: Polyethylene oxide standard sample, manufactured by Agilent Technologies, Inc. (100 to 1,258,000)

[0089] <(a) Measurement of Surface Contact Angle>

[0090] The coated silicone member is immersed in PBS at 25° C. for one day or more. After taking the coated silicone member out of the PBS at 25° C., the medical device was immediately sandwiched between two pieces of water absorbent gauze (for example, “Haize (registered trademark)” Gauze VP-150: manufactured by OZU CORPORATION) from above and below, and then water on the surface was removed by lightly pressing. The contact angle was measured as quickly as possible using Automatic Contact Angle Drop Master DM-500 (manufactured by Kyowa Interface Science Co., Ltd.). PBS was used as a droplet for measurement. The surface contact angle was measured 30 seconds after the droplet (1 μL) was brought into contact.

[0091] <(b) Durability Test: Surface Contact Angle>

[0092] A solution (artificial tear) was prepared by stirring and dissolving 0.06 g of lysozyme (Albumen derived, manufactured by FUJIFILM Wako Pure Chemical Corporation), 0.08 g of γ-lactoglobulin (Human serum-derived, manufactured by FUJIFILM Wako Pure Chemical Corporation), and 0.015 g of mucin (Bovine submandibular gland derived, manufactured by FUJIFILM Wako Pure Chemical Corporation) in 100 g of PBS. The coated silicone member was immersed in artificial tears in a beaker at room temperature for 24 hours or more. Subsequently, the coated silicone member was pulled up from the artificial tears, placed on the palm, and 5 to 6 drops of artificial tears were dropped onto the coated silicone member with a pipette. The surface of the coated silicone member was scrubbed and washed back and forth 200 times with the palm and the forefinger pad, and immersed in PBS. Thereafter, the surface contact angle was measured.

[0093] <(c) Hydrophilicity Evaluation>

[0094] 0.015 g of Sudan Black B (manufactured by FUJIFILM Wako Pure Chemical Corporation) and 3 g of D-alpha-Tocoferol (manufactured by Tokyo Chemical Industry Co., Ltd.) were weighed in a vial and thoroughly stirred to prepare a Sudan Black solution. The coated silicone member was removed from PBS and immersed in the Sudan Black solution for 5 minutes. The coated silicone member was swung and washed in warm water at 50° C. placed in a 100 mL beaker, and then the coated silicone member was taken out and subjected to the following visual evaluation. In the following evaluation criteria, the surface hydrophilicity of A is most maintained and is good, and the surface hydrophilicity of E is lost and is most poor. [0095] A: Dyeing is not observed on the surface of the coated silicone member. [0096] B: Dyeing is observed in a very small amount of punctate or coated silicone member ends. [0097] C: An area of 10% or more and less than 30% of the surface of the coated silicone member is dyed. [0098] D: An area of 30% or more and less than 90% of the surface of the coated silicone member is dyed. [0099] E: An area of 90% or more of the surface of the coated silicone member is dyed.

[0100] <(d) Durability Test: Hydrophilicity Evaluation>

[0101] The coated silicone member is immersed in PBS in advance. The coated silicone member was pulled up from the PBS, placed on the palm, and 5 to 6 drops of the PBS were dropped onto the coated silicone member with a pipette. The surface of the coated silicone member was scrubbed and washed back and forth 200 times with the palm and the forefinger pad, and immersed in PBS. 0.015 g of Sudan Black B (manufactured by FUJIFILM Wako Pure Chemical Corporation) and 3 g of D-alpha-Tocoferol (manufactured by Tokyo Chemical Industry Co., Ltd.) were weighed in a vial and thoroughly stirred to prepare a Sudan Black solution. The coated silicone member was removed from PBS and immersed in the Sudan Black solution for 5 minutes. The coated silicone member was swung and washed in warm water at 50° C. placed in a 100 mL beaker, and then the coated silicone member was taken out and subjected to the following visual evaluation. In the following evaluation criteria, the surface hydrophilicity of A is most maintained and is good, and the surface hydrophilicity of E is lost and is most poor. [0102] A: Dyeing is not observed on the surface of the coated silicone member. [0103] B: Dyeing is observed in a very small amount of punctate or coated silicone member ends. [0104] C: An area of 10% or more and less than 30% of the surface of the coated silicone member is dyed. [0105] D: An area of 30% or more and less than 90% of the surface of the coated silicone member is dyed. [0106] E: An area of 90% or more of the surface of the coated silicone member is dyed.

[0107] <Appearance Inspection>

[0108] The coated silicone member was immersed in PBS in a glass petri dish, and the surface was visually observed by irradiating the coated silicone member with an LED lamp from above. In the following evaluation criteria, A has the best appearance, and E has the worst appearance. [0109] A: The coated silicone member surface is uniform and transparent. [0110] B: The surface of the coated silicone member is uniform, but very little diffuse reflection of light is observed. [0111] C: The surface of the coated silicone member is uniform, but slight diffuse reflection of light is observed. [0112] D: Irregularity is observed on a part of the surface of the coated silicone member, and diffuse reflection of light is observed. [0113] E: Irregularity is observed on the entire of the surface of the coated silicone member, and diffuse reflection of light is observed.

[0114] The results of the above measurement and test are shown in Table 1.

Example 2

[0115] Except that a 1 mass % “Carbodilite” E-02 (Polycarbodiimide, pH=8.5, manufactured by Nisshinbo Chemical Inc.) aqueous solution as an emulsion was used in place of the 1 mass % “Carbodilite” V-02 aqueous solution, the same manner as in Example 1 was performed to coat and prepare a silicone member. The pH of the solution was measured at Eutech pH 2700.

Example 3

[0116] Except that a 1 mass % “Carbodilite” V-02 (polycarbodiimide, weight average molecular weight 86,000, pH=8.8, manufactured by Nisshinbo Chemical Inc.) aqueous solution was used in place of the 7 mass % “Carbodilite” V-02 aqueous solution, the same manner as in Example 1 was performed.

Example 4

[0117] Except that a 1 mass % “Carbodilite” V-02 (polycarbodiimide, weight average molecular weight 86,000, pH=8.7, manufactured by Nisshinbo Chemical Inc.) aqueous solution was used in place of the 3 mass % “Carbodilite” V-02 aqueous solution, the same manner as in Example 1 was performed.

Example 5

[0118] Except that a 1 mass % “Carbodilite” V-02 (polycarbodiimide, weight average molecular weight 86,000, pH=7.8, manufactured by Nisshinbo Chemical Inc.) aqueous solution was used in place of the 0.05 mass % “Carbodilite” V-02 aqueous solution, the same manner as in Example 1 was performed.

Example 6

[0119] Except that a 1 mass % “Carbodilite” V-02 (polycarbodiimide, weight average molecular weight 86,000, pH=7.7, manufactured by Nisshinbo Chemical Inc.) aqueous solution was used in place of the 0.03 mass % “Carbodilite” V-02 aqueous solution, the same manner as in Example 1 was performed.

Example 7

[0120] Except that a 1 mass % “Carbodilite” V-02 (Weight average molecular weight 86,000, pH=7.5, manufactured by Nisshinbo Chemical Inc.) aqueous solution was used in place of the 0.005 mass % “Carbodilite” V-02 aqueous solution, the same manner as in Example 1 was performed.

Example 8

[0121] This example was performed in the same manner as in Example 1 except that a solution at 40° C. was used in each of the steps (A), (B), and (C).

Example 9

[0122] This example was performed in the same manner as in Example 1 except that a solution at 70° C. was used in each of the steps (A), (B), and (C).

Example 10

[0123] This example was performed in the same manner as in Example 1 except that a solution at room temperature was used in each of the steps (A), (B), and (C).

Example 11

[0124] This example was performed in the same manner as in Example 5 except that a solution at 50° C. was used in each of the steps (A), (B), and (C).

Example 12

[0125] This example was performed in the same manner as in Example 1 except that a solution at 90° C. was used in each of the steps (A), (B), and (C).

Example 13

[0126] This example was performed in the same manner as in Example 1 except that a 1 mass % N,N-dimethylacrylamide/acrylic acid copolymer (copolymerization ratio 2/1 [molar ratio]) aqueous solution was used instead of the mixed aqueous solution of the 2-methoxyethyl acrylate/N,N-dimethylacrylamide/acrylic acid copolymer (copolymerization ratio 2/7/1 [molar ratio], weight average molecular weight 1,040,000) and polyacrylic acid (Product name AC-10 H, manufactured by Toagosei Co., Ltd., weight average molecular weight 380,000).

Example 14

[0127] This example was performed in the same manner as in Example 1, except that a solution in which a sodium hydroxide powder was gradually added to a 1 mass % “Carbodilite” V-02 (Polycarbodiimide manufactured by Nisshinbo Chemical Inc., weight average molecular weight: 86,000) aqueous solution to have a pH of 9.5 was used in place of a 1 mass % “Carbodilite” V-02 aqueous solution.

Example 15

[0128] This example was performed in the same manner as in Example 1, except that a solution in which a sodium hydroxide powder was gradually added to a 1 mass % “Carbodilite” V-02 (Polycarbodiimide manufactured by Nisshinbo Chemical Inc., weight average molecular weight: 86,000) aqueous solution to have a pH of 10.5 was used in place of a 1 mass % “Carbodilite” V-02 aqueous solution.

Example 16

[0129] This example was performed in the same manner as in Example 1, except that a solution was used in which citric acid was gradually added to a 1 mass % “Carbodilite” V-02 aqueous solution to have a pH of 6.5, in place of the 1 mass % “Carbodilite” V-02 aqueous solution.

Example 17

[0130] This example was performed in the same manner as in Example 5, except that (B) a 1 mass % “Carbodilite” V-02-L (polycarbodiimide, weight average molecular weight 42,000, manufactured by Nisshinbo Chemical Inc.) aqueous solution was used in place of the 1 mass % “Carbodilite” V-02 aqueous solution.

Example 18

[0131] 2.2 g of MEA, 4.3 g of FM0711, 2.5 g of DMAA, 1.0 g of 164B, 0.05 g of NB, 0.002 g of RB, 0.02 g of IC-819 and 4.0 g of TAA were well mixed. This mixture was filtered through a membrane filter (0.45 μm) to remove an insoluble substance to obtain a monomer composition. This monomer composition was injected into a pair of molds, and polymerized by light irradiation (1.01 mW/cm.sup.2, 20 min) using a fluorescent lamp (manufactured by Toshiba Corporation, FL-6D, daylight color, 6 W, 4 fibers) under a nitrogen atmosphere. Only one mold was removed. (A) An isopropyl alcohol:water=55:45 (volume ratio before mixing) solution of 0.05 N sodium hydroxide was prepared. In this solution, the silicone member A fixed to the other mold was heated at 60° C. for 1 hour to perform hydrolysis reaction of the silicone member A and peeling from the mold. Thereafter, the silicone member A thus obtained was immersed in fresh isopropyl alcohol and water in a ratio of 55:45 (volume ratio before mixing) and heated at 60° C. for 3 hours, followed by extraction. (B) A 1 mass % “Carbodilite” V-02 aqueous solution was prepared, and the silicone member A was immersed in the aqueous solution at 60° C. for 30 minutes. After cooling, the silicone member A was taken out from the aqueous solution, and lightly swing-washed in PBS. (C) An aqueous solution was prepared by mixing 1 mass % of an aqueous solution of 2-methoxyethyl acrylate/N,N-dimethylacrylamide/acrylic acid copolymer (copolymerization ratio 2/7/1 [molar ratio], weight average molecular weight 1,040,000) and 1 mass % of an aqueous solution of polyacrylic acid (product name AC-10 H, manufactured by Toagosei Company, Limited) at a ratio of 2:1.7 (mass ratio). The polyacrylic acid is a polymer having a carboxylic acid group. The mixed aqueous solution was heated at 60° C. for 30 minutes to immerse the silicone member A therein. After cooling to room temperature, the silicone member A was taken out from the mixed aqueous solution, and lightly swing-washed in PBS. The silicone member was immersed in new PBS, heat-sterilized at 121° C. for 30 minutes, and stored at room temperature to obtain a coated silicone member. The results of performing the same measurement and test as in Example 1 are shown in Table 1.

Example 19

[0132] This example was performed in the same manner as in Example 18 except that an isopropyl alcohol:water=55:45 (volume ratio before mixing) solution of 0.01 N sodium hydroxide was prepared in step of (A).

Example 20

[0133] (A) The silicone member A was immersed in a 0.25 N aqueous sodium hydroxide solution, and heated at 60° C. for 30 minutes to perform a hydrolysis reaction. After cooling to room temperature, the silicone member A was taken out from the solution, and lightly swing-washed in PBS.
(D) A mixed aqueous solution was prepared by dissolving 1 mass % of Carbodilite” (registered trademark) V-02 (polycarbodiimide, weight average molecular weight 86,000, pH=8.2, manufactured by Nisshinbo Chemical Inc.), 1 mass % of a 2-methoxyethyl acrylate/N,N-dimethylacrylamide/acrylic acid copolymer (copolymerization ratio 2/7/1 [molar ratio], weight average molecular weight 1,040,000), and 0.85 mass % of polyacrylic acid (product name AC-10 H, manufactured by Toagosei Company, Limited). The silicone member A was immersed in the mixed aqueous solution at 60° C. for 30 minutes. After cooling, the silicone member A was taken out from the mixed aqueous solution, and lightly swing-washed in PBS. The silicone member was immersed in clean PBS, heat-sterilized at 121° C. for 30 minutes, and stored at room temperature to obtain a coated silicone member. The results of performing the same measurement and test as in Example 1 are shown in Table 1.

Comparative Example 1

[0134] (B) A 1 mass % “Carbodilite” V-02 aqueous solution was prepared, and the silicone member A was immersed in the aqueous solution at 60° C. for 30 minutes. After cooling, the silicone member A was taken out from the aqueous solution, and lightly swing-washed in PBS. (C) An aqueous solution was prepared by mixing 1 mass % of an aqueous solution of 2-methoxyethyl acrylate/N,N-dimethylacrylamide/acrylic acid copolymer (copolymerization ratio 2/7/1 [molar ratio], weight average molecular weight 1,040,000) and 1 mass % of an aqueous solution of polyacrylic acid (product name AC-10 H, manufactured by Toagosei Company, Limited) at a ratio of 2:0.3 (mass ratio). The polyacrylic acid is a polymer having a carboxylic acid group. The mixed aqueous solution was heated at 60° C. for 30 minutes to immerse the silicone member A therein. After cooling to room temperature, the silicone member A was taken out from the solution, and lightly swing-washed in PBS. The silicone member was immersed in new PBS, heat-sterilized at 121° C. for 30 minutes, and stored at room temperature to obtain a coated silicone member. The results of performing the same measurement and test as in Example 1 are shown in Table 1.

Comparative Example 2

[0135] (A) The silicone member A was immersed in a 0.25 N aqueous sodium hydroxide solution, and heated at 60° C. for 30 minutes to perform a hydrolysis reaction. After cooling to room temperature, the silicone member A was taken out from the solution, and lightly swing-washed in PBS. (C) An aqueous solution was prepared by mixing 1 mass % of an aqueous solution of 2-methoxyethyl acrylate/N,N-dimethylacrylamide/acrylic acid copolymer (copolymerization ratio 2/7/1 [molar ratio], weight average molecular weight 1,040,000) and 1 mass % of an aqueous solution of polyacrylic acid (product name AC-10 H, manufactured by Toagosei Company, Limited) at a ratio of 2:0.3 (mass ratio). The polyacrylic acid is a polymer having a carboxylic acid group. The mixed aqueous solution was heated at 60° C. for 30 minutes to immerse the silicone member A therein. After cooling to room temperature, the silicone member A was taken out from the mixed aqueous solution, and lightly swing-washed in PBS. The silicone member was immersed in new PBS, heat-sterilized at 121° C. for 30 minutes, and stored at room temperature to obtain a coated silicone member. The results of performing the same measurement and test as in Example 1 are shown in Table 1.

Comparative Example 3

[0136] (A) The silicone member A was immersed in a 0.25 N aqueous sodium hydroxide solution, and heated at 60° C. for 30 minutes to perform a hydrolysis reaction. After cooling to room temperature, the silicone member A was taken out from the solution, and lightly swing-washed in PBS. (B) A 1 mass % “Carbodilite” V-02 aqueous solution was prepared, and the silicone member A was immersed in the aqueous solution at 60° C. for 30 minutes. After cooling, the silicone member A was taken out from the aqueous solution, and lightly swing-washed in PBS. The silicone member was immersed in new PBS, heat-sterilized at 121° C. for 30 minutes, and stored at room temperature to obtain a coated silicone member. The results of performing the same measurement and test as in Example 1 are shown in Table 1.

TABLE-US-00001 TABLE 1 (a) Contact (b) Durability (d) Durability angle test: Contact (c) test: (e) [º] angle [º] Hydrophilicity Hydrophilicity Appearance Example 1  45  61 B C C Example 2  58  60 A A C Example 3  55  72 A C E Example 4  55  71 A B D Example 5  60  62 A A A Example 6  72  75 A A A Example 7  80  85 C C A Example 8  45  82 A C C Example 9  72  75 B B C Example 10  68 105 A D C Example 11  74  88 B C A Example 12  85  82 B C B Example 13  62  65 B B C Example 14  65  72 A C B Example 15  72  79 A D A Example 16  48  70 B C C Example 17  75  77 B B A Example 18  41  65 B B C Example 19  45  68 B A A Example 20  62  70 B C C Comparative Example 1 112 114 E E A Comparative Example 2  87  95 C E A Comparative Example 3 115 117 E E A