JPH08245652A - Polyfunctional organic siloxane macromer and soft material for ophthalmic medical use using the same - Google Patents

Abstract

PURPOSE: To obtain a new polyfunctional organic siloxane macromer hardly attaching stain and useful as a raw material for soft materials for ophthalmic medical use having high oxygen permeability. CONSTITUTION: This compound is expressed by formula I [R1 is H or methyl; R2 to R5 are each independently a 1-12C hydrocarbon, etc.; Y is a structural unit of formulas II to IV (R6 and R7 are independently a 1-12C hydrocarbon; at least one of R8 and R9 may be F-substituted 1-12C hydrocarbon and other may be a 1-12C hydrocarbon; at least one of R10 and R11 may be vinyl, etc., and other may be a 1-12C hydrocarbon) constituted so that formula II/formula III is 0.1-10, (formulas II+III)/formula IV is 100-5 and formulas II+III is 7-300; m and n are each independently 1-20; p is 0-20; l is 0 when m is 0 or 1 when m>=1; X is NHCOO, etc.]. The compound of formula I is obtained by reacting a ring opening insertion reaction product of 1,3-bis-(4-hydroxyalkyl)tetra-methyl disiloxane with octamethylcyclotetrasiloxane, 1,3,5- trimethyltrimethyltrifluoropropylcyclotrisiloxane with tetravinyltetramethylcyclotetrasiloxane with a diisocyanate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polyfunctional organosiloxane macromer and a soft ophthalmic soft material using the macromer. More specifically, the present invention has little adhesion of stains such as proteins in tears, and has a good balance of physical properties such as oxygen permeability and shape retention, and as a soft contact lens, a soft intraocular lens, an artificial cornea, etc. A suitable substantially non-hydrated ophthalmic material.

[0002]

2. Description of the Related Art Conventionally, polysiloxane compounds, as represented by dimethyl silicone compounds, have unique functions such as heat resistance, chemical stability, electrical insulation, flexibility, lubricity, and water repellency. It is industrially widely used alone or for modifying other materials. For example, polydimethylsiloxane having a 3-methacryloxypropyl group at both ends, which is a polymerizable siloxane compound, is used for modifying various polymers such as acrylic polymer and polystyrene by utilizing its polymerizability. Further, since siloxane polymers have high gas permeability, they are also used as gas selective permeable membranes, and because they have little effect on living bodies, they are widely used as biomaterials and medical materials. For example, taking advantage of its excellent oxygen permeability, flexibility, and optical transparency, application to contact lenses is also under consideration, and many patents have been proposed (for example, Japanese Patent Publication No. 62-36046, JP-A-63-29741, JP-A-63-85
No. 719, JP-A-2-188717). Among the contact lenses, soft contact lenses are classified into hydrous soft contact lenses and non-hydrous soft contact lenses.

Hydrous soft contact lenses are composed of a copolymer obtained by polymerizing a hydrophilic monomer such as hydroxyethylmethacrylate or N-vinylpyrrolidone as a main component, and a lens is prepared by cutting or casting to prepare the lens in physiological saline. It is a swelled lens having a water content of about 40 to 70%. As a non-hydrous soft contact lens, for example, a platinum-based catalyst is added to a mixture of polydimethylsiloxane whose molecular chain ends are blocked with vinyldimethylsilyl groups and methylhydrogenpolysiloxane, and the mixture is heated and cured by a molding method. The elastic modulus between the soft contact lens and the hard contact lens, which are made of a polymer mainly composed of polyperfluoroether with a polymerizable group such as methacryloxy group added to both ends of the silicone rubber lens obtained by A flexible lens having the same is known (Japanese Patent Laid-Open Nos. 54-81363 and 58-127914).

Further, a hard substrate obtained by copolymerizing (meth) acrylic acid and (meth) acrylic acid ester is cut to form a lens, which is subjected to esterification and / or transesterification treatment to give a feeling of wearing. A non-hydrous soft contact lens having good properties is also manufactured (Japanese Patent Laid-Open No. 487504/1978).
7 publication). Hydrous contact lenses have the advantages that they are comfortable to wear and have high oxygen permeability when they are of a high water content type, but they are easily damaged, have poor durability, and are easily contaminated with components in tear fluid. Since there is a risk of bacterial growth, it is often inconvenient to handle, such as having to regularly sterilize by boiling.

The non-hydrous contact lenses also have the following problems. First, with regard to silicone lenses, at the beginning of development, there were drawbacks such as the peeling of the hydrophilic undertreatment layer applied to improve the hydrophobicity of the lens surface and the adhesion to the cornea due to its excessive elasticity. Although it has not been widely put into practical use, recently, surface hydrophilic surface treatment technology has progressed, lens design changes,
Moreover, although the drawbacks in the previous period have been considerably improved by the improvement of mechanical properties and the like, they are not yet sufficiently satisfactory, and it is the fact that they are not widely used.

[0006] Next, since the non-hydrous lens containing polyperfluoroether as a main component is closer to a semi-hard type than a soft contact lens, it does not give a feeling of wearing like a soft contact lens, and it does not come out on the cornea. The movement of the lens is not satisfactory either. Further, a soft contact lens mainly composed of (meth) acrylic acid ester is inferior in oxygen permeability and is not suitable for wearing for a long time. None of the materials mainly composed of polyfunctional polysiloxane is a material closer to a silicone lens, considering the contamination property due to the components in tear fluid.

[0007]

Under the circumstances described above, the present invention has substantially no stain adhesion, high oxygen permeability, and excellent optical, mechanical and shape retention properties. It is an object of the present invention to provide a non-hydrated ophthalmic medical soft material and a polyfunctional organosiloxane macromer for producing the same.

[0008]

The medical soft material of the present invention comprises a novel polyfunctional organosiloxane macromer having a specific structure and molecular weight, and a copolymer obtained by polymerizing the macromonomer as a main component. It can achieve its purpose. That is, the present invention is as follows. 1. A polyfunctional organosiloxane macromer represented by the following chemical formula 7.

[0009]

[Chemical 7]

[Wherein R₁Is hydrogen or a methyl group, R₂~ R
_FiveIs a hydrocarbon group having 1 to 12 carbon atoms or trimethyl group, respectively.
Roxy group. Y is a structural unit (I) shown in Chemical Formula 2 below.
(III), (I) / (II) = 1/10 to 1
0/1, [(I) + (II)] / (III) = 100 /
1 to 100/20 and (I) + (II) = 7 to 3
00. m and n are the same or different 1-2
An integer of 0, p is an integer of 0 to 20, l is 0 when m is 0
And is 1 when m is 1 or more. X is -NHCOO
-Group or -OOCHN-R_Ten-NHCOO- group (R_TenIs
A hydrocarbon group having 4 to 13 carbon atoms). ]

[0011]

Embedded image

[R ₆ and R ₇ are each a hydrocarbon group having 1 to 12 carbon atoms, R ₈ and R ₉ are each a hydrocarbon group having 1 to 12 or a fluorine-substituted hydrocarbon group, and at least one of them is It is a fluorine-substituted hydrocarbon group. R ₁₀ and R
₁₁ is a hydrocarbon group having 1 to 12 carbon atoms or a vinyl group, a styryl group, and an allyl group, and at least one of them is a vinyl group, a styryl group, and an allyl group. ] 2. One type or two or more types of the polyfunctional organosiloxane macromer represented by the above chemical formula 7 or one type or two types of monomers copolymerizable only with the polyfunctional organosiloxane macromer.
A three-dimensional crosslinked polymer obtained by polymerizing together with one or more species.

3. Obtained by polymerizing one or more polyfunctional organosiloxane macromers represented by the above chemical formula 7 together with one or more monomers copolymerizable with only the polyfunctional organosiloxane macromers. Soft material for ophthalmology. 4. One or two or more kinds of polyfunctional organosiloxane macromers represented by the following chemical formula 9 or one or two kinds of monomers copolymerizable with only the polyfunctional organosiloxane macromers.
A soft ophthalmic material obtained by polymerizing with more than one kind.

[0014]

[Chemical 9]

[Wherein R₁Is hydrogen or a methyl group, Y is below
Comprising the structural units (I ′) to (III ′) shown in Formula 4
, (I ') / (II') = 1/10 to 10/1,
[(I ') + (II')] / (III) = 100 / 1-
100/20, (I ') + (II') = 7-3
00. m and n are the same or different 1-2
An integer of 0, p is an integer of 0 to 20, l is 0 when m is 0
And is 1 when m is 1 or more. X is -NHCOO
-Group or -OOCHN-R_Ten-NHCOO- group (R_TenIs
A hydrocarbon group having 4 to 13 carbon atoms). ]

[0016]

[Chemical 10]

5. One or more polyfunctional organosiloxane macromers represented by the following chemical formula 11 and one or more selected from acrylic acid fluoroalkyl ester, methacrylic acid fluoroalkyl ester, acrylic acid alkyl ester and methacrylic acid alkyl ester. A soft ophthalmic medical material consisting of a copolymer containing two or more main components.

[0018]

[Chemical 11]

[Wherein R₁Is hydrogen or a methyl group, Y is below
Comprising the structural units (I ′) to (III ′) shown in Formula 4
, (I ') / (II') = 1/10 to 10/1,
[(I ') + (II')] / (III) = 100 / 1-
100/20, (I ') + (II') = 7-3
00. m and n are the same or different 1-2
An integer of 0, p is an integer of 0 to 20, l is 0 when m is 0
And is 1 when m is 1 or more. X is -NHCOO
-Group or -OOCHN-R_Ten-NHCOO- group (R_TenIs
A hydrocarbon group having 4 to 13 carbon atoms). ]

[0020]

[Chemical 12]

The present invention will be described in detail below. When the molecular weight of the polyfunctional organosiloxane macromer represented by the formula (1) increases, if the number of functional groups in the side chain is the same, the interchain functional group of the main chain becomes long, so that the oxygen permeability is high. Improve,
Further, since the cohesive energy is lowered and the glass transition point is lowered, the soft contact lens has a great effect on the physical properties shown by softness and rubber elasticity. In the formula (1), R1 is hydrogen or a methyl group,
R ₂ , R ₃ , R ₄ and R ₅ are each a hydrocarbon group having 1 to 12 carbon atoms or a trimethylsiloxy group, and may be the same or different. A hydrocarbon group having 1 to 3 carbon atoms or a trimethylsiloxy group is preferable from the viewpoint of softness, elasticity, strength and stain adhesion of the contact lens. m and n are integers of 1 to 20 and P is 0.
It is an integer of 20, and if it exceeds 20 and becomes large, the compatibility with other monomers deteriorates and white turbidity easily occurs, which is not preferable.

The structure of Y in the formula (1), which is the siloxanyl unit of the macromer for determining the molecular weight, is represented by (I), (II) and (III) in the above chemical formula 8. The structural units (I), (II) and (III) each have the following characteristics. The structural unit (I) has the effect of increasing oxygen permeability as the number in the molecule increases,
Further, since it also has an effect of lowering the glass transition point, it is a structure essential for physical properties such as the returning property when the lens is used (the property of returning to the original position when the lens is deformed). However, when the structural unit (I) is continuously present in the molecule, the hydrophobic property causes adsorption of proteins and the like in tear fluid, which easily causes contamination.

Next, in the structural unit (II), at least one of the side chains of the siloxanyl group is a fluorine-substituted hydrocarbon group, and the side chain has a fluorine-substituted hydrocarbon group, which results from the fluorine atom. A decrease in critical surface tension occurs. From this, the contact lens material of the present invention has water-repellent and oil-repellent properties, which has the effect of suppressing the contact lens surface from being contaminated by proteins and lipids in the tear fluid, inorganic components, and the like. It has the property of easily peeling off even if contaminants adhere. However, the structural unit (II) does not tend to increase oxygen permeability as much as the structural unit (I) does, and if too much is present in the molecule, it becomes difficult to obtain the desired oxygen permeability. Structural unit (II
In I), at least one of the side chains of the siloxanyl group is a polymerizable group such as a vinyl group, an allyl group, and a styryl group, and the presence of the polymerizable group in the side chain increases the crosslinking efficiency in the molecule and maintains the shape retention. It leads to improvement of physical properties such as strength and strength.

However, the large amount of the structural unit (III) present in the molecule causes a decrease in oxygen permeability and an increase in hardness. As described above, when the number of structural units (I), (II) and (III) present in the molecule is too large, the macromer becomes cloudy and is obtained, or the compatibility with a copolymerizable monomer is increased. Deteriorates, phase separation occurs, and white turbidity occurs during polymerization. Also, if the number is small, not only the oxygen permeability decreases, but also the softness and flexibility,
This causes poor shape retention and the like. For the above reasons, the abundance ratio and the number of the structural units (I) and (II) contained in the molecule are such that the ratio of structural unit (I): structural unit (II) is 1: 1.
0 to 10: 1 is preferably 1: 8 to 8: 1, and the total number of structural units (I) and (II) is 7 to 300, preferably 20 to 220.

The structural unit (III) contained in the molecule is represented by the ratio with the total number of structural units (I) and (II), and the ratio of structural unit (I) + (II): structural unit (III). Is 10
0: 1 to 100: 20, preferably 100: 2 to 100: 10. The side chains of the siloxanyl group of the structural unit (I) are each a hydrocarbon group having 1 to 12 carbon atoms, and preferably a methyl group. At least one side chain of the siloxanyl group of the structural unit (II) needs to be a fluorine-substituted hydrocarbon group, for example, 3,
3,3-trifluoropropyl group, 1,1,2,2-tetrahydroperfluorooctyl group, 1,1,2,2-
Examples thereof include a tetrahydroperfluorodecyl group, and among them, a trifluoropropyl group is preferable. Structural unit (I
It is necessary that at least one of the side chains of the siloxanyl group of II) contains a polymerizable group, and a vinyl group, an allyl group, a styryl group and the like can be mentioned, and a vinyl group is preferable.

Next, X in the formula (1) represents a residue of a monofunctional isocyanate or a bifunctional isocyanate, each of which is --NHCOO-- or --OOCNH--R8 --NHCO.
An O-group (R8 is a divalent hydrocarbon group having 4 to 13 carbon atoms, which is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group). By including these urethane bonds in the molecular structure, strength and water wettability can be improved. As the residue of the bifunctional isocyanate, for example, hexamethylene diisocyanate, tetramethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, 3-isocyanate methyl-
There are residues such as 3,5,5-trimethylcyclohexyl isocyanate, disidicyclohexylmethane-4,4'-diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, and isophorone diisocyanate, and among them, hexamethylene diisocyanate and isophorone diisocyanate. Is preferred.

The polyfunctional organosiloxane macromer represented by the formula (1) is, for example, 1,3-bis- (4-hydroxyalkyl) tetramethyldisiloxane, octamethylcyclotetrasiloxane and 1,3,5-. A diol having a polysiloxane structure obtained by a ring-opening insertion reaction of trimethyltrifluoropropylcyclotrisiloxane and tetravinyltetramethylcyclotetrasiloxane is reacted with, for example, an equivalent amount of isocyanate ethyl methacrylate or twice equivalent amount of diisocyanate. Obtained by The structure of the obtained polyfunctional organosiloxane macromer can be analyzed from NMR (nuclear magnetic resonance spectrum) and IR absorption spectrum.

Further, the structural unit (I) contained in the molecule,
The abundance ratio and number of (II) and (III) are determined by NMR
It can be determined by measuring (nuclear magnetic resonance spectrum). For example, when the structural unit (I) is dimethylsiloxane, the structural unit (II) is methyl-trifluoropropylsiloxane, and the structural unit (III) is vinylmethylsiloxane, a methyl group, a trifluoropropyl group, which appears on the NMR spectrum, It can be obtained by measuring the integral value of the proton absorption for the vinyl group and further measuring the integral value of the proton absorption for the methylene group contained in the same molecule.

The medical soft material of the present invention comprises one polyfunctional organosiloxane macromer represented by the formula (1) or two or more polyfunctional organosiloxane macromers alone or as a copolymerizable monomer. It consists of a cross-linked polymer obtained by polymerizing with one or more kinds. Depending on the target performance of the medical soft material, such as the required oxygen permeability, softness, stain resistance, strength, etc., the type and number of bonds of the constituent unit that constitutes Y in the formula (1) , And the residues that make up X are selected.

The copolymerizable monomer will be described below.
Acrylic acid fluoroalkyl ester and methacrylic acid fluoroalkyl ester used as a copolymerizable monomer in the present invention have water-repellent and oil-repellent properties due to a reduction in critical surface tension due to a fluorine atom.
This has the effect of suppressing the surface of the contact lens from being contaminated by components such as proteins and lipids in tear fluid.

Specific examples of these acrylic acid fluoroalkyl ester and methacrylic acid fluoroalkyl ester include trifluoroethyl acrylate, tetrafluoroethyl acrylate, tetrafluoropropyl acrylate, pentafluoropropyl acrylate, hexafluorobutyl acrylate and hexafluoroisopropyl acrylate. , Heptafluorobutyl acrylate, octafluoropentyl acrylate, nonafluoropentyl acrylate, dodecafluoropentyl acrylate, dodecafluorooctyl acrylate, tridecafluorooctyl acrylate, tridecafluoroheptyl acrylate, and methacrylates of these acrylates. Preferably trifluoroethyl meta Relate, hexafluoroisopropyl methacrylate, octafluoropentyl methacrylate, trifluoroethyl acrylate, tetrafluoroethyl acrylate, dodecamethylene perfluorooctyl acrylate is used. These monomers may be used alone or in combination of two or more.

The acrylic acid alkyl ester monomer and methacrylic acid alkyl ester monomer used as the copolymerizable monomer in the present invention improve the compatibility between the polyfunctional organosiloxane macromer and the (meth) acrylic acid fluoroalkyl ester. It is effective and plays a role in broadening its range of use. Specific examples of these acrylic acid alkyl esters and methacrylic acid alkyl esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, n-octyl acrylate, n. -Heptyl acrylate, n-nonyl acrylate, n-decyl acrylate, isodecyl acrylate, n-lauryl acrylate, tridecyl acrylate, n-dodecyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, n-stearyl acrylate and their acrylates Methacrylates and the like can be mentioned, preferably n-
Butyl acrylate, n-octyl acrylate, n-
Lauryl methacrylate, n-stearyl methacrylate, etc. are used. These monomers may be used alone or in combination of two or more.

Further, in order to improve mechanical properties, surface wettability, dimensional stability, etc., the following monomers can be copolymerized, if desired. Examples of the monomer for improving mechanical properties include styrene and t
Examples thereof include aromatic vinyl compounds such as ert-butyl styrene and α-methyl styrene. Examples of the monomer for improving surface wettability include methacrylic acid, acrylic acid, itaconic acid, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, glycerol methacrylate,
Polyethylene glycol methacrylate, N, N'-dimethylacrylamide, N, N'-diethylacrylamide, N-methylacrylamide, dimethylaminoethylmethacrylate, methylenebisacrylamide, diacetoneacrylamide, N-vinylpyrrolidone, N-vinylN-methylacetamide, etc. Can be mentioned.

Examples of the monomer for improving the dimensional stability 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. These monomers may be used alone or in combination of two or more. To improve the balance of properties such as optical characteristics of soft materials, oxygen permeability, mechanical strength, deformation recovery, dirt adhesion when worn on the eye, dimensional stability in tear fluid and its change over time. It is possible to use a mixed monomer in which these copolymerizable monomers are combined.

Examples of mixed monomers copolymerizable with the polyfunctional organosiloxane macromer of the present invention include trifluoroethyl methacrylate, n-butyl acrylate,
There are combinations of methacrylic acid, hydroxyethyl methacrylate, ethylene glycol dimethacrylate, and the like. The copolymer used as the medical soft material of the present invention is, for example, a cast polymerization method in which a monomer mixture is filled in a mold and radically polymerized by a known method, and the monomer mixture is charged in a rotating half-face mold. A contact lens or the like can be molded by a method of polymerizing, or a method of freezing and cutting the copolymer at a low temperature.

The copolymerization method is preferably a method of allowing a photopolymerization initiator to be present in the monomer mixture and irradiating it with ultraviolet rays for polymerization, or a method of using an azo compound or an organic peroxide.

[0037]

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, each physical property and molecular weight were calculated as follows. (1) Oxygen permeability coefficient Gas permeability measuring device K-315 manufactured by Rika Seiki Co., Ltd.
-N was used. The sample piece has a diameter of 30 mm and a thickness of 0.3 mm
The disk-shaped product of was used for the measurement. The measurement was carried out at a constant temperature room of 25 ° C. and a sample piece setting place of 35 ° C. (2) Mechanical Strength Tensile strength, elongation, and elastic modulus from initial stress were measured using a tensile tester AGS-50B manufactured by Shimadzu Corporation. The measurement is a constant temperature room at 25 ° C, and the test piece is 5 mm wide, 20 mm long and 0.3
mm thickness was used.

(3) Stain Adhesion Protein stains are Tris-HCl buffer solution (PH = 7.4)
Lysozyme (0.3%), albumin (0.4
%), Globulin (0.3%) dissolved, the test piece is dipped in this mixed solution (37 ° C., 3 Hr), dipped in purified water and dried, and surface infrared spectroscopic analysis is performed to measure the absorption amount of amide. did. The greater the absorption, the greater the amount of dirt attached. For stains caused by lipid, the swelling rate was measured by immersing the test piece in oleic acid.

(4) Compressive deformation return test A soft contact lens prepared by using a mold is dipped in pure water, a glass plate is placed on top of the soft contact lens, and a sample bottle having a weight of 50 g is placed on the soft contact lens. Deform by compression at room temperature for an hour. After 3 hours, remove the sample bottle and glass plate and measure the lens size 1 minute later (S
2) Do. With the initial size as (S1), the amount of deformation after 1 minute is calculated by the following equation. S2-S1 = ΔSt1 (mm) The deformation return amount is compared by this ΔSt1. (5) The molecular weight was determined by NMR and GPC.

[0040]

Example 1 (Synthesis of Macromer A) 10.7 g of 1,3-bis- (4-hydroxypropyl) tetramethyldisiloxane, 190 g of octamethylcyclotetrasiloxane, 1,3,5-trimethyltrifluoropropylcyclotri Siloxane 100g, 1,3
5,7-Tetravinyl 1,3,5,7-tetramethylcyclotetrasiloxane 11.05 g, toluene 174
g, 2,6-di-ter-butyl-P-cresol 30
Then, 100 mg of cesium hydroxide and 100 mg of cesium hydroxide were charged into a flask and reacted at reflux temperature for 12 hours.

After that, the solution was neutralized with acetic acid and then dissolved and washed with isopropyl alcohol. Then, methanol was added and the mixture was extracted with a separating funnel. By repeating the treatment, 119 g of an organosiloxane diol having hydroxyl groups at both ends was obtained. As a result of NMR (nuclear magnetic resonance spectrum) analysis of the obtained macromer, it was confirmed that the macromer had the structure shown in Chemical formula 13 below.

[0042]

[Chemical 13]

50 g of this organosiloxane diol, 100 g of acetone, 4.7 g of 2-isocyanatoethyl methacrylate, and 5 parts of dibutyltin dilaurylate were placed in a brown round bottom flask and reacted for 2 hours at the reflux temperature while stirring in a N ₂ atmosphere. After the reaction, 1.5 g of purified water was added and stirring was continued. After cooling, methanol was added, and washing and separation were repeated to obtain 46 g of a urethane bond-containing organosiloxane macromer. NMR of the obtained macromer
As a result of (nuclear magnetic resonance spectrum) analysis and IR analysis, it was confirmed to be a polyfunctional organosiloxane macromer containing a urethane bond shown in the following Chemical Formula 14 (Macromer A). An NMR spectrum diagram is attached to FIG. 1, and an IR spectrum diagram is attached to FIG.

[0044]

Embedded image

(Preparation of Polymer) 55 parts by weight of a polyfunctional organic siloxane macromer containing a urethane bond shown in Chemical Formula 14 (Macromer A), 45 parts by weight of trifluoroethyl acrylate (hereinafter referred to as 3FA), and methacrylic acid ( MAA) 4 parts by weight, ethylene glycol dimethacrylate (hereinafter ED) 1 part by weight, and benzyl dimethyl ketal (manufactured by Ciba-Geigy, trade name I-65).
1) 0.5 part by weight was added, and the mixture was dissolved and mixed by stirring in a nitrogen atmosphere with a magnetic stirrer for about 1 hour.

Then, in a nitrogen atmosphere, two glass plates (thickness: 10) with a silicone rubber gasket interposed therebetween.
mm, width 60 mm, length 90 mm), the reaction solution was injected into the cell and the cell was irradiated with ultraviolet rays at a temperature of 40 to 50 ° C. for 2 hours to obtain a transparent copolymer. The oxygen permeability coefficient, tensile strength, and stain adhesion of the thus obtained copolymer were measured. The results are shown in Table 1.

[0047]

Comparative Example 1 The urethane represented by the following chemical formula 16 (Macromer B) was prepared by reacting the organosiloxane diol represented by the following chemical formula 15 with 2-isocyanate ethyl methacrylate in the same manner as in Example 1 and purifying. An organosiloxane macromer containing bonds was obtained.

[0048]

[Chemical 15]

[0049]

Embedded image

55 parts by weight of the organosiloxane macromer containing a urethane bond shown in Chemical Formula 16 (Macromer B), 45 parts by weight of 3FA, 4 parts by weight of MAA, 1 part by weight of ED and 0.5 part by weight of benzyl dimethyl ketal were added,
Polymerization was carried out in the same manner as in Example 1 to obtain a transparent copolymer. The results of measuring the physical properties of the copolymer are shown in Table 1.
Shown in

[0051]

Example 2 and Comparative Example 2 Trifluoroethyl methacrylate (hereinafter 3FM) 10 was added to 80 parts by weight of each of the organosiloxane macromers containing the urethane bond shown in Chemical Formula 14 (Macromer A) and Chemical Formula 16 (Macromer B).
Parts by weight, n-butyl acrylate (hereinafter n-BA) 5 parts by weight, MAA 3 parts by weight, hydroxyethyl methacrylate (hereinafter HEMA) 2 parts by weight, ED 0.5 parts by weight, and 2,4,6-trimethylbenzoyldiphenylphosphine. 0.5 parts by weight of oxide was added and the mixture was polymerized in the same manner as in Example 1 to obtain a transparent copolymer. The results of measuring the physical properties of the copolymer are shown in Table 1. Next, each of the monomer mixture solutions was injected and filled into a polypropylene concave-convex mold (lens diameter: 13.7 mm) prepared by injection molding, and was irradiated with ultraviolet rays for 2 hours for polymerization. The lens taken out from the mold after the polymerization was transparent and flexible, and the strength was good first. With respect to each of the taken out lenses, the compressive deformation return property was measured. The results are shown in Table 1.

[0052]

COMPARATIVE EXAMPLE 3 55 parts by weight of macromer represented by the following chemical formula 17 (Macromer C) was added to 25 parts by weight of 3FA and n-BA2.
0 parts by weight, 6 parts by weight of MAA, 4 parts by weight of ED and 0.5 part by weight of benzyl dimethyl ketal were added and polymerized in the same manner as in Example 1 to obtain a transparent copolymer. The results of measuring the physical properties of the copolymer are shown in Table 1.

[0053]

[Chemical 17]

[0054]

[Table 1]

[0055]

The soft material for ophthalmology prepared by using the novel polyfunctional organosiloxane macromer of the present invention is
It is a material that is excellent in stain resistance of proteins and the like and has an excellent balance of physical properties such as oxygen permeability, mechanical strength, and deformation return property, and is suitable for contact lenses, intraocular lenses, and artificial corneas.

[Brief description of drawings]

1 is an NMR spectrum diagram of a polyfunctional organosiloxane macromer (Macromer A) obtained in Example 1. FIG.

FIG. 2 is an IR spectrum diagram of the polyfunctional organosiloxane macromer (Macromer A) obtained in Example 1.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08G 65/32 NQJ C08G 65/32 NQJ 77/08 NUG 77/08 NUG C08L 83/04 LRM C08L 83 / 04 LRM G02C 7/04 G02C 7/04

Claims (5)

[Claims] 1. A multivalued structure represented by the following chemical formula 1.
Functional organosiloxane macromer. [Chemical 1][In the formula, R₁Is hydrogen or a methyl group, R₂~ R_FiveAre each carbon
A hydrocarbon group of formula 1 to 12 or a trimethylsiloxy group
It Y is structural unit (I) to (III) shown in the following chemical formula 2
, (I) / (II) = 1/10 to 10/1,
[(I) + (II)] / (III) = 100/1 to 10
0/20 and (I) + (II) = 7 to 300
It m and n are the same or different 1 to 20 integers, respectively.
Number, p is an integer from 0 to 20, l is 0 when m is 0,
It is 1 when m is 1 or more. X is a -NHCOO- group or
Is -OOCHN-R_Ten-NHCOO- group (R_TenIs the carbon number
4 to 13 hydrocarbon groups). ] [Chemical 2][R₆And R₇Are each a hydrocarbon group having 1 to 12 carbon atoms, R₈
And R₉Are 1 to 12 hydrocarbon groups or fluorine groups, respectively.
A substituted hydrocarbon group, at least one of which is a fluorine group.
It is a hydrocarbon group that has been substituted. R_TenAnd R₁₁Each is charcoal
A hydrocarbon group having a prime number of 1 to 12, a vinyl group, a styryl group,
An allyl group, at least one of which is a vinyl group,
A tyryl group and an allyl group. ] 2. One or two or more kinds of the polyfunctional organosiloxane macromers represented by claim 1, or one or two or more kinds of monomers copolymerizable only with the polyfunctional organosiloxane macromers. A three-dimensional cross-linked polymer obtained by polymerization with. 3. One or two or more kinds of the polyfunctional organic siloxane macromers represented by claim 1, or one or more kinds of monomers copolymerizable with only the polyfunctional organic siloxane macromers. A soft material for ophthalmology that is obtained by polymerizing with. 4. A polyfunctional organosiloxane macromer
The soft ophthalmic medical material according to claim 3, which is represented by the following chemical formula 3.
Fee. [Chemical 3][In the formula, R₁Is hydrogen or a methyl group, and Y is shown in the following chemical formula 4.
Structural units (I ′) to (III ′), and (I ′) /
(II ') = 1/10 to 10/1, [(I') + (I
I ′)] / (III) = 100/1 to 100/20
Thus, (I ') + (II') = 7-300. m and
And n are the same or different integers of 1 to 20, and p is 0.
An integer from 20 to 20, l is 0 when m is 0 and m is 1 or more
Is 1 when. X is a -NHCOO- group or -OOC
HN-R_Ten-NHCOO- group (R_TenHas 4 to 13 carbon atoms
A hydrocarbon group). ] [Chemical 4] 5. A polyfunctional organic white represented by the following chemical formula 6.
One or more xanthomamers and acrylic acid
Fluoroalkyl ester, fluoroal methacrylate
Killester, alkyl acrylate and methacryc
1 type or 2 or more types selected from phosphoric acid alkyl ester
Soft material for ophthalmology consisting of copolymer containing
Fee. [Chemical 5][In the formula, R₁Is hydrogen or a methyl group, and Y is shown in the following chemical formula 6.
Structural units (I ′) to (III ′), and (I ′) /
(II ') = 1/10 to 10/1, [(I') + (I
I ′)] / (III) = 100/1 to 100/20
Thus, (I ') + (II') = 7-300. m and
And n are the same or different integers of 1 to 20, and p is 0.
An integer from 20 to 20, l is 0 when m is 0 and m is 1 or more
Is 1 when. X is a -NHCOO- group or -OOC
HN-R_Ten-NHCOO- group (R_TenHas 4 to 13 carbon atoms
A hydrocarbon group). ] [Chemical 6]