Patent Publication Number: US-2010119744-A1

Title: Ophthalmic lens, culture substrate material for cell or organ, container for living thing and transparent gel obtained by polymerization of cyclic siloxane and their production method

Description:
RELATED APPLICATION 
     This is a U.S. national phase application under 35 U.S.C. §371 of International Application No. PCT/JP2006/311275 filed Jun. 6, 2006, and claiming priority of Japanese Patent Application No. 2005-200920 filed Jul. 8, 2005. 
    
    
     TECHNICAL FIELD 
     The present invention relates to an ophthalmic lens, a culture substrate material for cells or organs, a container for a living thing and a transparent gel, which are obtained by polymerizing a cyclic siloxane compound. 
     BACKGROUND ART 
     A conventional polymer obtained from siloxane monomer has been highly tacky and sticky and thus difficult to handle. Further, the resulting polymer has been necessary for a surface treatment, and this surface treatment has been accompanied with such a problem that the processes are complicated and the effect is lowered after using for a long period. 
     For instance, in Japanese Patent Publication No. 1-256537A, a contact lens comprising a cyclic or straight chained siloxane, which is wettable, rigid, gas-permeable and substantially non-expansible is disclosed. However, as the cyclic siloxane compound contains no cross-linkable unsaturated group, it is difficult to produce a transparent gel, and even when it can be produced, its transparency and mechanical strength are not practically applicable. 
     Further, in Japanese Patent Publication No. 7-149902A, a cyclic siloxane compound is disclosed, but this is for using to a silicone type releasing paper for giving hardening property and no consideration is made at all to application to a substrate material for an ophthalmic lens and other living body-related substances and to a container for living things. 
     DISCLOSURE OF INVENTION 
     The present invention provides an ophthalmic lens which is required for no surface treatment and excellent in tackiness, a culture substrate material for cells or organs, a container for living things and a transparent gel. 
     Namely, the present invention relates to an ophthalmic lens obtained by polymerizing a cyclic siloxane compound shown by the following formula (A). 
     
       
         
         
             
             
         
       
     
     (wherein Ra or Rb is a hydrogen atom or a monovalent hydrocarbon group which may be substituted by a fluorine atom, and they are same or different with each other, Rc is a C1 to C6 alkyl group or a phenyl group, X is an organic group containing an unsaturated aliphatic bond, and n is an integer of 1 to 10). 
     The cyclic siloxane compound is preferably polymerized together with a hydrophilic monomer. 
     Further, the present invention relates to a culture substrate material for cells or organs, which contains the cyclic siloxane compound shown by the following formula (A). 
     
       
         
         
             
             
         
       
     
     (wherein Ra or Rb is a hydrogen atom or a monovalent hydrocarbon group which may be substituted by a fluorine atom, and they are same or different with each other, Rc is a C1 to C6 alkyl group or a phenyl group, X is an organic group containing an unsaturated aliphatic bond, and n is an integer of 1 to 10). 
     It is preferable to polymerize a hydrophilic monomer together with the cyclic siloxane compound. 
     The present invention also relates to a container for living things, which is obtained by polymerizing the cyclic siloxane compound shown by the following formula (A). 
     
       
         
         
             
             
         
       
     
     (wherein Ra or Rb is a hydrogen atom or a monovalent hydrocarbon group which may be substituted by a fluorine atom, and they are same or different with each other, Rc is a C1 to C6 alkyl group or a phenyl group, X is an organic group containing an unsaturated aliphatic bond, and n is an integer of 1 to 10). 
     The present invention still further relates to a transparent gel obtained by polymerizing the cyclic siloxane compound shown by the following formula (A), a hydrophilic monomer and a thermosetting polyimide silicone resin soluble in organic solvents which contains a structural units shown by the following formula (B-1) and one shown by the following formula (B-2). 
     
       
         
         
             
             
         
       
     
     (wherein Ra or Rb is a hydrogen atom or a monovalent hydrocarbon group which may be substituted by a fluorine atom, and they are same or different with each other, Rc is a C1 to C6 alkyl group or a phenyl group, X is an organic group containing an unsaturated aliphatic bond, and n is an integer of 1 to 10). 
     
       
         
         
             
             
         
       
     
     [wherein X is a tetravalent organic group having 4 or more carbon atoms, providing that plural of —CO— groups are not bound to one carbon atom in X, and Y is a diamine residue shown by the general formula (1) or (2) 
     
       
         
         
             
             
         
       
     
     (wherein each of R 1  to R 6  is, same or different, a hydrogen atom or a C1 to C6 alkyl group). 
     
       
         
         
             
             
         
       
     
     (wherein R 7  and R 8  are, same or different, a hydrogen atom or a C1 to C6 alkyl group)]. 
     
       
         
         
             
             
         
       
     
     [wherein X is a tetravalent organic group having 4 or more carbon atoms, providing that plural of —CO— groups are not bound to one carbon atom in X, and Z is a diamine residue shown by the general formula (3) 
     
       
         
         
             
             
         
       
     
     (wherein R 9  to R 12  are, same or different, a substituted or unsubstituted monovalent hydrocarbon group of C1 to C8, and a is an integer of 1 to 100)]. 
     Further, the present invention relates to a method for producing a transparent gel, comprising dissolving a polyimide silicone resin containing structural units shown by the formula (B-1) and (B-2) into a mixture of a cyclic siloxane compound shown by the formula (A) and a hydrophilic monomer, followed by polymerization. 
    
    
     BEST MODE FOR CARRYING OUT THE INVENTION 
     The ophthalmic lens, a culture substrate material for cells and organs and a container for living things of the present invention is obtained by polymerizing a cyclic siloxane compound shown by the following formula (A). 
     
       
         
         
             
             
         
       
     
     (wherein Ra or Rb is a hydrogen atom or a monovalent hydrocarbon group which may be substituted by a fluorine atom, and they are same or different with each other, Rc is a C1 to C6 alkyl group or a phenyl group, X is an organic group containing an unsaturated aliphatic bond, and n is an integer of 1 to 10). 
     Ra or Rb is a hydrogen atom or a monovalent hydrocarbon group which may be substituted by a fluorine atom, and they are same or different with each other. Preferably, Ra and Rb are a C1 to C6 alkyl group and still preferably Ra is a C1 to C6 alkyl group substituted by a fluorine atom and Rb is a C1 to C6 alkyl group. The C1 to C6 alkyl group in Ra and Rb is exemplified by a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a hexyl group, etc. Among the above, one wherein Ra is —CH 3  or —CH2CH2CF3 and Rb is —CH3 is still preferable. In a case where Ra or Rb is a monovalent hydrocarbon group such as an alkyl group of 7 or more carbon atoms, the obtained lens tends to be stuck with a lipid or tends to become lowered flexible. In a case where Ra is an alkyl group substituted by a fluorine atom, Ra has preferably 3 to 6 carbon atoms, and when the carbon atom is less than 3, the compound containing an alkyl group substituted by a fluorine atom tends to be difficult to produce. 
     The X in the above formula (A) contains an unsaturated aliphatic group which is exemplified by the following 
     
       
         
         
             
             
         
       
     
     (wherein Rx 1 , Rx 2  and Rx 3  are a hydrogen atom, a C1 to C6 alkyl group or a phenyl group, which may be same or different, Q is a divalent organic group, and Z is a trivalent organic group). 
     The Q in the above formula (A) is preferably (i) a C1 to C8 straight chained or branched alkylene group or (ii) a C1 to C8 straight chained or branched alkylene group whose methylene unit is substituted by one or more members selected from the group consisting of —O—, —CO—, —COO—, —OCO—, —OCOO—, —C 6 H 4 —, —OC 6 H 4 — and —S—, including specifically a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an isobutylene group, an isopentylene group, an ethylhexylene group, etc. 
     The Z in the formula (A) is preferably (iii) a C1 to C20 trivalent hydrocarbon group forming a cyclic structure through an unsaturated aliphatic bond as the structural unit to which Rx 1  and Rx 2  are bound or (iv) a C2 to C20 trivalent hydrocarbon group whose methylene unit is substituted by one or more members selected from the group consisting of —O—, —CO—, —COO—, —OCO—, —OCOO—, —C 6 H 4 —, —OC 6 H 4 — and —S—. 
     Among the above, as the X in the formula A, the following is preferable from viewpoints of low cost in an industrial scale and availability in a large amount 
     
       
         
         
             
             
         
       
     
     wherein Rx 1 , Rx 2  and Rx 3  are a hydrogen atom or a methyl group, which may be same or different, 
     
       
         
         
             
             
         
       
     
     in the formula (4), Rx 1 , Rx 2  and Rx 3  are a hydrogen atom or a methyl group, which may be same or different, Q is a substituent shown by the formula (5) and m is an integer of 3. 
     
       
         
         
             
             
         
       
     
     wherein Rx 1  and Rx 2  are a hydrogen atom or a methyl group, which may be same or different, and Z is 
     
       
         
         
             
             
         
       
     
     Specific examples of the above substituents are as the followings, but the substituent X in the present invention is not limited thereto. 
     
       
         
         
             
             
         
       
     
     The Rc in the formula (A) is a C1 to C6 alkyl group or a phenyl group, including specifically the alkyl group mentioned in the C1 to C6 alkyl group and the phenyl group in the above Ra and Rb, among which a methyl group is preferable. 
     The n in the formula (A) of the present invention is an integer of 1 to 10, and n=3 is preferable from viewpoints of low cost in an industrial scale and availability in a large amount. 
     The ophthalmic lens and the culture substrate material for cells and organs of the present invention are preferably obtained by polymerizing the cyclic siloxane compound of the formula (A) together with a hydrophilic monomer. The hydrophilic monomer is exemplified by an alcohol and a nitrogen-containing monomer, including specifically 2-hydroxyethyl methacrylate (2-HEMA), glycerol methacrylate (GMA), N-vinyl-2-pyrrolidone (NVP), N,N-dimethyl acrylamide (DMAA), 1-methyl-3-methylene-2-pyrolidinone (NMMP) , etc. Those may be used singly or in combination of two or more thereof. Particularly a nitrogen-containing monomer is preferable from a viewpoint of suppressing turbidity of the resulting ophthalmic lens. DMAA is preferable for increasing transparency, and NVP is preferable from viewpoints of improvement of tackiness and a lipid-sticking property. The hydrophilic polymer is particularly preferably used in production of a silicone hydrogel contact lens. 
     In a case where the hydrophilic polymer is contained, a weight ratio of the cyclic siloxane compound shown by the formula (A) to the hydrophilic monomer is preferably 20:80 to 80:20. When the ratio of the cyclic siloxane compound shown by the formula (A) is less than 20% by weight, the shape-holdability of the resulting ophthalmic lens is inferior and becomes flat, and thus wearing tends to be difficult. When the ratio of the cyclic siloxane compound shown by the formula (A) is over 80% by weight, flexibility and repulsion of the produced lens tends to be lowered. 
     The cyclic siloxane compound shown by the formula (A) can be incorporated with a cross-linking agent. 
     The cross-linking agent is for giving a reinforcing effect, and exemplified by ethylene glycol dimethacrylate (EDMA), allyl methacrylate (AMA), diethylene glycol allyl ether (TRIAM), etc. Those may be used singly or in combination of two or more thereof. Among them, EDMA or a mixture of EDMA and AMA is preferably used as the cross-linking agent from a viewpoint of keeping suitable flexibility in the ophthalmic lens. 
     A content of the cross-linking agent is preferably 0.01 to 5% by weight relative to the cyclic siloxane compound shown by the formula (A). When the content of the cross-linking agent is less than 0.01% by weight, strength of the resulting ophthalmic lens becomes lower, and when over 5% by weight, flexibility of the ophthalmic lens obtained tends to be lowered because of increased cross-linked structure ratio. 
     The ophthalmic lens, and the culture substrate material for cells and organs of the present invention are preferably produced by polymerizing the cyclic siloxane compound shown by the formula (A) together with a hydrophilic polymer and a cross-linking agent. In a case of co-using the hydrophilic polymer and the cross-linking agent, a content of the cross-linking agent is preferably 0.01 to 3% by weight relative to the cyclic siloxane compound shown by the formula (A). 
     When the content of the cross-linking agent is less than 0.01% by weight, shape-holdability of the resulting ophthalmic lens and the culture substrate material tends to be inferior and become flat. Further, mounting of the ophthalmic lens tends to be difficult. When the content of the cross-linking agent is over 3% by weight, though the shape-holdability becomes good, the lens becomes rigid (hard) and thus resulting ophthalmic lens and the culture substrate material tend to be fragile. Further, wearing of the ophthalmic lens tends to be difficult. 
     The method for polymerizing the cyclic siloxane compound shown by the formula (A) is not specifically restricted, and the polymerization can be conducted be a generally used polymerization method such as photo-polymerization and heat polymerization. 
     The ophthalmic lens of the present invention preferably has a Young&#39;s Modulus of 0.1 to 5 MPa, still preferably 0.2 to 1.1 MPa. When the Young&#39;s Modulus is less than 0.1 MPa, strength of the resulting ophthalmic lens tends to be lowered, and when it is over 5 MPa, on the other hand, the lens tends to be rigid and its wearing feeling tends to be inferior. 
     Further, the ophthalmic lens of the present invention preferably shows an oxygen-permeation coefficient (Dk) of 40×10 −11  (cm 2 /sec)·(mLO 2 /(mL×mmHg)) or more. When it is less than 40×10 −11  (cm 2 /sec)·(mLO 2 /(mL×mmHg)), the resultant tends to unsuitable to an ophthalmic lens. 
     A water content of the ophthalmic lens of the present invention is preferably not more than 90%, still preferably 20 to 80%. When it is over 90%, strength of the resulting ophthalmic lens tends to be lowered. 
     The ophthalmic lens obtained in the present invention includes a contact lens, an intraocular lens, a corneal inlay, etc. The culture substrate material for cells and organs includes a substrate material used in production of a culture skin, a substrate material used as a skeleton of an artificial bone, etc. and the material is for seeding cells on or in the said substrate material. The container for living things means a general culture container used in cultivation of cells. 
     Still further, the present invention relates to a transparent gel obtained by polymerizing the cyclic siloxane compound shown by the formula (A) and a thermosetting polyimide silicone resin soluble in an organic solvent which contains structural units shown by the following formula (B-1) and (B-2). 
     
       
         
         
             
             
         
       
     
     (wherein Ra or Rb is a hydrogen atom or a monovalent hydrocarbon group which may be substituted by a fluorine atom, and they are same or different with each other, Rc is a C1 to C6 alkyl group or a phenyl group, X is an organic group containing an unsaturated aliphatic bond, and n is an integer of 1 to 10). 
     
       
         
         
             
             
         
       
     
     [wherein X is a tetravalent organic group having 4 or more carbon atoms, providing that plural of —CO— groups are not bound to one carbon atom in X, and Y is a diamine residue shown by the general formula (1) or (2) 
     
       
         
         
             
             
         
       
     
     (wherein R 1  to R 6  are a hydrogen atom or a C1 to C6 alkyl group, which may be same or different) 
     
       
         
         
             
             
         
       
     
     (wherein R 7  and R 8  are a hydrogen atom or a C1 to C6 alkyl group, which may be same or different)] 
     
       
         
         
             
             
         
       
     
     [wherein X is a tetravalent organic group having 4 or more carbon atoms, providing that plural of —CO— groups are not bound to one carbon atom in X, and Z is a diamine residue shown by the general formula (3) 
     
       
         
         
             
             
         
       
     
     (wherein R 9  to R 12  are a C1 to C8 substituted or unsubstituted monovalent hydrocarbon group, which may be same or different, and a is an integer of 1 to 100)]. 
     The cyclic siloxane compound shown by the formula (A) can be used within preferable fields of embodiments such as an ophthalmic lens, a culture substrate material for cells and organs and a container for living things. 
     The hydrophilic monomer is exemplified by a monomer used in an ophthalmic lens, a culture substrate for cells and organs, etc. 
     The transparent polyimide silicone resin is not specifically restricted so far as it contains the above structure (the transparent polyimide silicone resin disclosed in Japanese Patent Publication No. 2004-149777A), and one having the structure of the formula (6) is preferably used from viewpoints of transparency, flexibility and surface properties. 
     
       
         
         
             
             
         
       
     
     wherein X is 
     
       
         
         
             
             
         
       
     
     Y is 
     
       
         
         
             
             
         
       
     
     Z is 
     
       
         
         
             
             
         
       
     
     To a mixture of the cyclic siloxane compound shown by the formula (A), the hydrophilic monomer and the polyimide silicone resin may be added other ingredients including a silicone-containing monomer such as tris(trimethyl siloxy)silyl propyl methacrylate and tris(trimethyl siloxy)silyl styrene, a silicone-containing macromonomer such as polysiloxane macromonomer disclosed in International Patent Publication No. WO 01/071415, and the like. 
     The transparent gel of the present invention is preferably obtained by dissolving a polyimide silicone resin shown by the formula (B-1) or (B-2) into a mixture of the cyclic siloxane compound shown by the formula (A) and the hydrophilic monomer, followed by polymerizing. 
     A mixed ratio of the cyclic siloxane compound shown by the formula (A) to the hydrophilic monomer is preferably 90:10 to 10:90 by weight. When it is less than 10% by weight, a mechanical strength of the resulting polymer tends to be lowered, and when it is over 90% by weight, the resultant tends to be rigid and lowered flexible. 
     A content of the polyimide silicone resin is preferably not more than 50 parts by weight relative to the above mixture. When it is over 50 parts by weight, the resultant tends to be rigid. 
     The polymerization reaction is conducted by a conventional manner such as heat polymerization, photo polymerization and mold polymerization (e.g. resin mold). The polymerization is conducted appropriately with the addition of a conventional polymerization initiator such as a heat polymerization initiator and a photo polymerization initiator. A solution polymerization under addition of a solvent may also be conducted. The solvent is not specifically restricted, and use can be made of THF, isopropyl alcohol, acetone, hexane, etc. 
     A polymerization temperature can be set forth according to the polymerization method, and in a case of heat polymerization, it is in a range of 60 to 120° C., preferably 80 to 100° C. In a case of polymerization at lower than 60° C., no polymerization proceeds and non-polymerized monomer amount increases, and when over 120° C., polymerization does not proceed, and an amount of non-polymerized monomer is increased, and also a mold tends to be deformed because of poor heat resistance, when a mold made of polypropylene (PP) is used. 
     The resulting transparent gel shows transparency and suitable flexibility, and thus it can be applied to an ophthalmic lens, a culture substrate for cells and organs, and a container for living things without surface treatment. 
     Example  
     Mixed solutions were prepared according to Tables 2 to 7, and filled in a plate mold made of polypropylene, and UV polymerization was conducted for 30 minutes using a UV-ray curing machine (EYE GRAPHICS CO., LTD.) to give polymer samples. The samples were subjected to elution treatment with distilled water, and distilled water was replaced with saline, followed by sterilizing with an autoclave. 
     (Wettability, Stickiness and Tackiness) 
     Wettability, stickiness and tackiness of the plate surface of the resultant were evaluated by sensory test based upon feeling (wettability, stickiness, tackiness) after rubbing by fingers. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 1 
               
               
                   
                   
               
               
                   
                 ⊚ 
                 ◯ 
                 Δ 
                 X 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 Wettability 
                 very good 
                 good 
                 slightly 
                 inferior 
               
               
                   
                   
                   
                 inferior 
               
               
                 Stickiness 
                 completely 
                   
                 observed 
                 observed 
               
               
                   
                 none 
                   
                 slightly 
               
               
                 Tackiness 
                 completely 
                   
                 observed 
                 observed 
               
               
                   
                 none 
                   
                 slightly 
               
               
                   
               
            
           
         
       
     
     (Lipid Adhesion) 
     After the resulting plates were immersed in an artificial lacrimal fluid (0.7% aqueous lysozyme solution) for 16 hours or 40 hours, an amount of lipid adhered to the plates was analyzed using GC/MSD (5973N MSD system, Agilent Technologies). 
     (Refraction Index Na-D) 
     A refraction index at 20° C. (Na-D line) of the resulting lenses was measured by an Abbe refractometer (1-T, Atago Co., Ltd.). 
     (Oxygen Permeability (Oxygen Permeation Index) Dk) 
     Dk of the resulting lenses were measured after an electrode method by an oxygen permeation measurement machine (Rikagaku Seiki Kogyo K.K.). 
     (Water Content) 
     The plates were immersed in a saline for 16 hours to hydrate, and the surfaces were rightly wiped and the weights were measured (W1: g). Then the plates were placed in a drier at 105° C. for 16 hours, and then cooled to a room temperature in a desiccator, and weights of the dried plates were measured (W2: g). The water contents were calculated by the following equation: 
       (W1−W2)/W1×100(%) 
     (Young&#39;s Modulus) 
     Tensile test was conducted using a multi-role tester (Model 4301, Instron Japan Co., Ltd.), and an average value of each 5 plates was calculated to give Young&#39;s Modulus. Young&#39;s Modulus shows extension, and a large value means short extension and a small value means long extension. 
     (Stress Relaxation Rate) 
     Using a punch through tester, around 20 g load was given to the plates, and the stress after 30 and 60 seconds was measured, and the relaxation rate was calculated according the following equation compared with the initial load. An average value of each 3 plates was referred to the relaxation rate. The stress is an index of repulsion and as its value becomes large, the article becomes difficult to reform to the original form, and a small value means easy reform. 
       Relaxation rate (%)={(initial load (g))−(stress after predetermined time (g))}/initial load (g)×100 
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 (Dimension of components: % by weight) 
               
            
           
           
               
               
               
            
               
                   
                 Ex. 
                 Com. Ex. 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                   
                 1 
                 2 
                 3 
                 4 
                 5 
                 6 
                 1 
                 2 
               
               
                   
                   
               
            
           
           
               
            
               
                 Formula (A) 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 S-502FCT 
                 50 
                   
                 50 
                 50 
                   
                   
                   
                   
               
               
                 S-502CT 
                   
                 50 
                   
                   
                 50 
                 50 
               
               
                 SK-5001 
                   
                   
                   
                   
                   
                   
                 50 
                 50 
               
            
           
           
               
            
               
                 Hydrophilic monomer 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 NVP 
                   
                   
                 50 
                   
                 50 
                   
                 50 
                   
               
               
                 DMAA 
                   
                   
                   
                 50 
                   
                 50 
                   
                 50 
               
            
           
           
               
            
               
                 Cross-linking agent 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 EDMA 
                 1 
                 1 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
               
            
           
           
               
            
               
                 Photo polymerization initiator 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 D1173 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
               
            
           
           
               
            
               
                 Physical properties 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Wettability 
                 ◯ 
                 ◯ 
                 ⊚ 
                 ◯ 
                 ◯ 
                 ◯ 
                 X 
                 X 
               
               
                 Stickiness 
                 ◯ 
                 ◯ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 X 
                 X 
               
               
                 Lipid-adhesion property 
                 1.26 
                 1.30 
                 0.13 
                 0.77 
                 — 
                 1.11 
                 — 
                 4.61 
               
               
                 (immersion for 16 hours) 
               
               
                 (μg/cm 2 ) 
               
               
                 Lipid-adhesion property 
                 — 
                 — 
                 0.25 
                 0.74 
                 — 
                 3.56 
                 — 
                 2.41 
               
               
                 (immersion for 40 hours) 
               
               
                 (μg/cm 2 ) 
               
               
                 Refractive index 
                 1.42 
                 1.45 
                 1.40 
                 1.40 
                 — 
                 1.41 
                 — 
                 1.42 
               
               
                 Dk 
                 58 
                 55 
                 46 
                 44 
                 — 
                 59 
                 — 
                 77 
               
               
                 Thickness of sample (mm) 
                 0.286 
                 0.285 
                 0.293 
                 0.304 
                 — 
                 0.297 
                 — 
                 0.299 
               
               
                 Water content (%) 
                 0 
                 0 
                 45 
                 52 
                 47 
                 53 
                 51 
                 50 
               
               
                   
               
               
                 —: not measured 
               
               
                 Dk: ×10 −11  (cm 2 /sec) · (mLO 2 /(mL × mmHg)) 
               
            
           
         
       
         
         S-502CT (3-methacryloxypropyl)heptamethyl cyclotetrasiloxane 
       
    
     
       
         
         
             
             
         
       
         
         S-502FCT (3-methacryloxypropyl)tris(3,3,3-trifluoropropyl)tetramethyl cyclotetrasiloxane 
       
    
     
       
         
         
             
             
         
       
         
         SK-5001: tris(trimethyl siloxy)silyl propyl methacrylate (MW: 422.82, Shin-Etsu Chemical Co., Ltd.) 
         NVP: N-vinyl-2-pyrrolidone 
         DMAA: N,N-dimethylacrylamide 
         NMMP: 1-methyl-3-methylene-2-pyrrolidinone 
         EDMA: ethylene glycol dimethacrylate 
         D1173: 2-hydroxy-2-methyl-1-phenyl-propan-1-on (Darocure (registered trade mark) 1173) 
       
    
     
       
         
           
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                 (Dimension of components: % by weight) 
               
            
           
           
               
               
               
            
               
                   
                 Ex. 
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 7 
                 8 
                 9 
                 10 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 S-502FCT 
                 50 
                 50 
                 50 
                 50 
               
               
                   
                 S-502CT 
               
               
                   
                 SK-5001 
               
               
                   
                 NVP 
                 45 
                 40 
                 35 
                 25 
               
               
                   
                 DMAA 
                 5 
                 10 
                 15 
                 25 
               
               
                   
                 EDMA 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
               
               
                   
                 D1173 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
               
            
           
           
               
            
               
                 Physical properties 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 Wettability 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ◯ 
               
               
                   
                 Stickiness 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
               
               
                   
                 Lipid-adhesion property 
                 0.53 
                 0.86 
                 0.80 
                 0.73 
               
               
                   
                 (immersion for 16 hours) 
               
               
                   
                 (μg/cm 2 ) 
               
               
                   
                 Lipid-adhesion property 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 (immersion for 40 hours) 
               
               
                   
                 (μg/cm 2 ) 
               
               
                   
                 Refractive index 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 Dk 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 Thickness of sample (mm) 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 Water content (%) 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                   
               
               
                   
                 —: not measured 
               
               
                   
                 Dk: ×10 −11  (cm 2 /sec) · (mLO 2 /(mL × mmHg)) 
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 4 
               
             
            
               
                   
               
               
                 (Dimension of components: % by weight) 
               
            
           
           
               
               
            
               
                   
                 Ex. 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 11 
                 12 
                 13 
                 14 
                 15 
                 16 
                 17 
                 18 
                 19 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 S-502FCT 
                 10 
                 20 
                 30 
                 40 
                 50 
                 60 
                 70 
                 80 
                 90 
               
               
                 NVP 
                 90 
                 80 
                 70 
                 60 
                 50 
                 40 
                 30 
                 20 
                 10 
               
               
                 EDMA 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
               
               
                 D1173 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
               
            
           
           
               
            
               
                 Physical properties 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 Wettability 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
               
               
                 Stickiness 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
               
               
                 Tackiness 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 5 
               
             
            
               
                   
               
               
                 (Dimension of components: % by weight) 
               
            
           
           
               
               
            
               
                   
                 Ex. 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 20 
                 21 
                 22 
                 23 
                 24 
                 25 
                 26 
                 27 
                 28 
                 29 
                 30 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 S-502FCT 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
               
               
                 NVP 
                 50 
                 45 
                 40 
                 35 
                 30 
                 25 
                 20 
                 15 
                 10 
                 5 
                 0 
               
               
                 DMAA 
                 0 
                 5 
                 10 
                 15 
                 20 
                 25 
                 30 
                 35 
                 40 
                 45 
                 50 
               
               
                 EDMA 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
               
               
                 D1173 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
               
            
           
           
               
            
               
                 Physical properties 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 Wettability 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ◯ 
                 ◯ 
                 ◯ 
                 ◯ 
                 Δ 
                 Δ 
                 Δ 
                 Δ 
               
               
                 Stickiness 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
               
               
                 Tackiness 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
               
               
                 Young&#39;s Modulus (MPa) 
                 4.961 
                 1.047 
                 0.427 
                 0.320 
                 0.394 
                 0.346 
                 0.305 
                 0.268 
                 0.197 
                 0.136 
                 0.192 
               
               
                 Stress relaxation rate 
                 38.5 
                 28.6 
                 22.5 
                 20.7 
                 19.6 
                 22.5 
                 23.2 
                 23.1 
                 23.9 
                 25.7 
                 23.7 
               
               
                 after 30 seconds (%) 
               
               
                 Stress relaxation rate 
                 41.9 
                 31.6 
                 26.3 
                 24.5 
                 23.3 
                 25.9 
                 27.3 
                 27.6 
                 28.1 
                 30.1 
                 28.1 
               
               
                 after 60 seconds (%) 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 6 
               
             
            
               
                   
               
               
                 (Dimension of components: % by weight) 
               
            
           
           
               
               
            
               
                   
                 Ex. 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                   
                 31 
                 32 
                 33 
                 34 
                 35 
                 36 
                 37 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 S-502FCT 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
               
               
                 NMMP 
                 0 
                 0 
                 0 
                 0 
                 30 
                 20 
                 10 
               
               
                 NVP 
                 30 
                 20 
                 10 
                 0 
                 0 
                 0 
                 0 
               
               
                 DMAA 
                 20 
                 30 
                 40 
                 50 
                 20 
                 30 
                 40 
               
               
                 EDMA 
                 1 
                 1 
                 1 
                 1 
                 1 
                 1 
                 1 
               
               
                 D1173 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
               
            
           
           
               
            
               
                 Physical properties 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 Wettability 
                 ◯ 
                 ◯ 
                 Δ 
                 Δ 
                 Δ 
                 Δ 
                 Δ 
               
               
                 Stickiness 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
               
               
                 Tackiness 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
               
               
                 Young&#39;s Modulus (MPa) 
                 0.516 
                 0.415 
                 0.446 
                 0.418 
                 0.463 
                 0.559 
                 0.380 
               
               
                 Stress relaxation rate 
                 22.3 
                 20.9 
                 20.8 
                 22.2 
                 24.1 
                 23.5 
                 25.1 
               
               
                 after 30 seconds (%) 
               
               
                 Stress relaxation rate 
                 24.4 
                 23.3 
                 24.6 
                 26.2 
                 29.0 
                 26.4 
                 29.7 
               
               
                 after 60 seconds (%) 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 7 
               
             
            
               
                   
               
               
                 (Dimension of components: % by weight) 
               
            
           
           
               
               
            
               
                   
                 Ex. 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 38 
                 39 
                 40 
                 41 
                 42 
                 43 
                 44 
                 45 
                 46 
                 47 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 S-502FCT 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
               
               
                 NVP 
                 40 
                 30 
                 20 
                 10 
                 40 
                 30 
                 20 
                 10 
                 0 
                 0 
               
               
                 DMAA 
                 10 
                 20 
                 30 
                 40 
                 10 
                 20 
                 30 
                 40 
                 50 
                 50 
               
               
                 EDMA 
                 0.25 
                 0.25 
                 0.25 
                 0.25 
                 0.75 
                 0.75 
                 0.75 
                 0.75 
                 0.75 
                 1 
               
               
                 D1173 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
               
            
           
           
               
            
               
                 Physical properties 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 Wettability 
                 ⊚ 
                 ⊚ 
                 ◯ 
                 Δ 
                 ⊚ 
                 ◯ 
                 Δ 
                 Δ 
                 Δ 
                 Δ 
               
               
                 Stickiness 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
               
               
                 Tackiness 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
                 ⊚ 
               
               
                 Young&#39;s Modulus (MPa) 
                 0.289 
                 0.280 
                 0.331 
                 0.278 
                 0.444 
                 0.385 
                 0.334 
                 0.371 
                 0.334 
                 0.441 
               
               
                 Stress relaxation rate 
                 25.4 
                 21.3 
                 22.0 
                 23.0 
                 20.1 
                 20.2 
                 22.8 
                 23.6 
                 23.0 
                 23.3 
               
               
                 after 30 seconds (%) 
               
               
                 Stress relaxation rate 
                 30.2 
                 25.1 
                 25.5 
                 27.1 
                 23.8 
                 23.2 
                 26.6 
                 27.2 
                 27.0 
                 26.5 
               
               
                 after 60 seconds (%) 
               
               
                   
               
            
           
         
       
     
     As result from Comparative Examples 1 and 2 of Table 2, when a conventional silicone-containing monomer was used, surface wettability was inferior and tackiness was observed even using with a hydrophilic monomer. On the other hand, when the cyclo siloxane compound of the present invention shown by the formula (A) was used, surface wettability was good and plates having no tackiness were obtained even without using a hydrophilic monomer. Further, it was result from Examples 3 to 6, tackiness was improved by co-using a hydrophilic monomer. 
     Also regarding the lipid adhesion amount, as result from Comparative Example 2, the amount was large when a conventional silicone-containing monomer was used, while the amount was considerably reduced when the cyclic siloxane compound of the present invention shown by the formula (A) was used. 
     Among the Examples, one wherein surface wettability was good, no tackiness was observed and lipid was difficult to adhere was Example 3 wherein a hydrophilic monomer was co-used. 
     From the evaluation of the refractive index, the oxygen-permeation index, the water content, the Young&#39;s Modulus and the stress relaxation rate, they were understood to be within a range sufficiently capable of applying to a contact lens. 
     INDUSTRIAL APPLICABILITY 
     According to the present invention, an ophthalmic lens, a culture substrate material for cells and organs and a container for living things wherein tackiness and stickiness are reduced, lipid adhesion ability is excellent and surface wettability is also excellent can be provided.