JPH08245737A - Hydrophilic fluorine-containing siloxane monomer and ophthalmologic lens material comprising the composition - Google Patents

Abstract

PURPOSE: To obtain a hydrophilic fluorine-containing siloxane monomer which has (meth)acryl groups on both chain termini through urethane groups and is useful as a starting material for hydrophilic compositions sutable for an ophthalmologic lens material, excellent in water wettability, gas permeation, antistaining properties, flexibility, optical transparency and strength. CONSTITUTION: This monomer is represented by formula I X is formula II [R5 is H, methyl; Z1 is NHCOO, the formula: OOCNH-R6 NHCOO (R6 is a 4-13C hydrocarbon group); (m) is 0-10; (n) is 1-20; (p) is 0 when m=0, or 1 when m>=1; (q) is 0-20; R1 -R4 are each a 1-12C hydrocarbon group, trimethylsiloxy; Y is a unit (A1 ) of formula III (R7 , R8 are each R1 ), a unit (A2 ) of formula IV [R9 , R10 are R1 , a 1-12C F-substituted hydrocarbon group (FR) and at least either one is the FR] and a unit of formula (V) (R11 , R12 are each R1 , a hydrophilic group and at least either one is the hydrophilic group), where A1 /(A2 +A3 )=1/10 to 100/1, A2 /A3 =1/10 to 10/1 and A1 +A2 +A3 =10 to 100}.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an ophthalmic lens material comprising a novel siloxane monomer and its composition. More specifically, a hydrophilic composition excellent in water wettability, gas permeability, stain resistance, flexibility, optical transparency, and strength, which is useful as an ophthalmic soft lens, and a novel hydrophilic fluorine-containing composition which is a raw material thereof It relates to a siloxane monomer.

[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).

Contact lenses are roughly classified into hard lenses and soft lenses. Hard contact lenses are hard and have a bad feeling to wear, but recent improvements in oxygen permeability are remarkable, and products capable of continuous wear have also appeared. . On the other hand, soft contact lenses are soft and have a good wearing feeling, but there are various problems. A detailed look at soft contact lenses can be divided into hydrous soft contact lenses and non-hydrous soft contact lenses. The hydrous soft contact lens is composed of a copolymer obtained by polymerizing a hydrophilic monomer such as hydroxyethyl methacrylate or N-vinylpyrrolidone as a main component, and a lens is prepared by cutting or casting method and swelled in physiological saline. It is a lens having a water content of about 40 to 70%.

As the 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 a molding method is used. Between a soft contact lens and a hard contact lens consisting of a polymer mainly composed of polyperfluoroether with a silicone rubber lens obtained by a method of heating and curing at a both end and a polymerizable group such as methacryloxy group Flexible lenses having an elastic modulus are known (JP 54-81363 A, JP 58-127914 A). Also (meta)
A lens is prepared by cutting from a hard substrate made by copolymerizing acrylic acid and (meth) acrylic acid ester, and the lens is esterified and / or transesterified to give a good wearing feeling Contact lenses are also manufactured (Japanese Patent Application Laid-Open No. 48-75047).

Hydrous contact lenses are liable to break and have poor durability, and are easily contaminated by components in tear fluid, which may cause bacterial growth. Often inconvenient. Further, although the high water content soft lens is somewhat improved, the oxygen permeability is not sufficient, and it is not satisfactory for long-time wear. On the other hand, non-hydrous contact lenses also have the following problems. Silicone lens
Oxygen permeability was extremely high, and there were great expectations at the beginning, but the wettability of tear fluid is poor due to the hydrophobicity of the lens surface, and plasma treatment and surface hydrophilic treatment such as grafting of hydrophilic monomer have been performed. , Hydrophilicity and durability are not sufficient. In addition, it is easily contaminated with proteins and lipids in tear fluid, which causes a problem of sticking during wearing. Therefore, attempts have been made to introduce a hydrophilic substituent into the polysiloxane itself (for example, Japanese Patent Publication No. 62-29776 and Japanese Patent Laid-Open Publication No. 5 (1994) -1971).
0-108881). Alternatively, attempts have been made to introduce a fluorine substituent in order to improve the stain resistance of the siloxane compound, but this results in a decrease in wettability. Therefore,
From the viewpoint of the balance between hydrophilicity and stain resistance, satisfactory materials have not yet been found. On the other hand, a non-hydrous soft lens made of poly-fluoropolyether or acrylic ester copolymer, which is a material other than silicone, does not have the oxygen permeability of a silicone material and is not suitable for long-term wear.

[0006]

Therefore, an object of the present invention is to solve the above-mentioned drawbacks, that is, it has good wettability with water, and further has stain resistance, gas permeability, flexibility, strength, and optical transparency. It is an object of the present invention to provide a composition useful as a satisfactory ophthalmic lens material, and further to disclose a novel siloxane monomer that provides the composition.

[0007]

[Means for solving the problems] As a result of various studies,
It has been found that a polysiloxane compound having a hydrophilic substituent and a fluorine-containing substituent in the same molecule and further having a polymerizable group linked by a urethane bond is extremely useful for solving the above problems. Invented. That is, the present invention provides a hydrophilic fluorine-containing siloxane monomer represented by the following formula (1), a composition thereof, and an ophthalmic lens material comprising the composition.

[0008]

[Chemical 9]

[In the formula, X is a substituent having an unsaturated group represented by the formula (2).

[0010]

[Chemical 10]

(Wherein Z ₁ is a --NHCOO-- group or --O
OCNH-R ₆ -NHCOO- group (R ₆ is a carbon number 4 to 13
A hydrocarbon group), R ₅ is hydrogen or methyl, m is 0, n is an integer of 1 to 20, p is 0 when m is 0, when m is 1 or more 1 Is. q is 0 to 20
Is an integer. ) R ₁ , R ₂ , R ₃ , and R ₄ are each a group selected from a hydrocarbon group having 1 to 12 carbon atoms or a trimethylsiloxy group, and may be the same or different. Y consists of structural units [I], [II] and [III] represented by the following formula, and the ratio of structural units [I], [II] and [III] is [I] / ([II] + [[ III]) = 1/10 to 1
00/1, and [II] / [III] = 1 /
10 to 10/1, [I], [II] and [I
The total number of [II] is 10 to 1000.

[0012]

[Chemical 11]

(Here, each of R ₇ and R ₈ has 1 carbon atom.
To 12 hydrocarbon groups or trimethylsiloxy groups, which may be the same or different. R ₉ and R ₁₀ are each a hydrocarbon group having 1 to 12 carbon atoms, a trimethylsiloxy group or a fluorine-substituted hydrocarbon group having 1 to 12 carbon atoms, and at least one of R _{9 and} R ₁₀ is a fluorine-substituted hydrocarbon group. And each may be the same or different. R ₁₁
And R ₁₂ are each a hydrocarbon group having 1 to 12 carbon atoms, a trimethylsiloxy group or a hydrophilic substituent, and at least one of R _{11 and} R ₁₂ is a hydrophilic substituent, and each is the same. It can be different. The hydrophilic substituent referred to here is a chain or cyclic hydrocarbon group formed by bonding at least one substituent selected from a hydroxyl group, a carboxylic acid group, an amino group, an imino group, an amide group and an oxyalkylene group. Say. )]

In the present invention, the hydrophilic fluorine-containing siloxane monomer represented by the formula (1) has a hydrophilic substituent and a fluorine-containing substituent in the same molecule and is polymerizable unsaturated through a urethane bond. Has a structure linked to a group. The hydrophilic substituent has a high polarity and has at least one functional group selected from a nonionic functional group selected from a hydroxyl group, a carboxylic acid group, an amino group, an imino group, an amide group and an oxyalkylene group. A chain or cyclic hydrocarbon group. Furthermore, a functional group consisting of a hydroxyl group or an oxyalkylene group which is stable to an acid or a base is preferable, and a substituent represented by the following formula is particularly preferable. That is, in R13 substituent (here represented by -R ₁₃ (OH) a is a hydrocarbon group having 3 to 12 carbon atoms, an oxygen atom between carbon atoms, -CO -, - COO-,
May have across the group consisting -OOC-, OH groups are substituted only one is on the same carbon atom, a is a number greater than 1), or -R ₁₄ - (OR ₁₅₎ c- (OR ₁₆ ) d-
A group represented by OZ ₂ (wherein R ₁₄ is a hydrocarbon group having a carbon number of 3 to 12, and an oxygen atom, —CO—, —C between carbon and carbon).
The group consisting of OO- and -OOC- may be sandwiched, and R
₁₅ and R ₁₆ are hydrocarbons having 2 to 4 carbon atoms and may be the same or different. b and c are 0 to 20 respectively
0 and b + c is at least 1. Z ₂ is a hydrogen atom, a hydrocarbon having 1 to 12 carbon atoms, —R ₁₇ OH (R ₁₇ is a hydrocarbon group having 2 to 10 carbon atoms), or —COR ₁₈ (R ₁₈
Is a group selected from a hydrocarbon group having 1 to 12 carbon atoms). ). In addition, in the above formula, when R ₁₅ and R ₁₆ are hydrocarbon groups having different structures, the structural formulas in which the bonding forms of both are block-wise are shown, but here, they are randomly bonded. It also includes the structure.

To give examples of these hydrophilic substituents,
For example, -C₃H₆OH, -C₈H₁₆OH, -C ₃H₆OC₂H_FourO
H, -C₃H₆OCH₂CH (OH) CH₃, -C₂H_FourCOO
C₂H_FourOH, -C₂H_FourCOOCH₂CH (OH) C₂H_FiveWhat
Which monohydric alcohol group, -C₃H₆OCH₂CH (OH) C
H₂OH, -C₂H_FourCOOCH₂CH (OH) CH₂OH,
-C₃H₆OCH₂C (CH₂OH)₃Polyhydric alcohol such as
Group, -C₃H₆(OC₂H_Four) _FourOH, -C₃H₆(OC₂H_Four)
₃₀OH, -C₃H₆(OC₂H_Four)_TenOCH₃, -C₃H₆(O
C₂H_Four)_Ten-(0C₃H₆)_TenOC_FourH₉Such as polyoxy
There are alkylene groups and the like. On the other hand, fluorine-containing substituents are sparse
It is a group showing water oleophobicity and imparts stain resistance to the polymer,
Substitution in which a fluorine atom is bonded to a hydrocarbon having 1 to 12 carbon atoms
Any group can be used, for example, 3, 3,
3-trifluoropropyl group, 1,1,2,2-tetra
Hydroperfluorooctyl group, 1,1,2,2-teto
Lahydroperfluorodecyl group and the like, among which
A 3,3,3-trifluoropropyl group is preferred.

In addition to the hydrophilic substituent and the fluorine-containing substituent, the substituent bonded to the Si atom has 1 carbon atom.
To 12 hydrocarbon groups or trimethylsiloxy groups, which may be the same or different and preferably have 1 carbon atom.
Is an alkyl group of 3 to 3, particularly preferably a methyl group. A siloxane chain having a small substituent such as a methyl group is highly flexible and has good gas permeability.

A siloxane structural unit [II] having a fluorine-containing substituent bonded thereto, a siloxane structural unit [III] having a hydrophilic substituent bonded thereto, and a siloxane structural unit having both a fluorine-containing substituent and a hydrophilic substituent not bonded [ The ratio of I] is [I] / ([II] + [III]) 1/10 to 1
It is 00/1, preferably 1/5 to 50/1, more preferably 1/1 to 20/1. When the proportion of the siloxane structural unit [I] is low, the flexibility and gas permeability of the siloxane chain are reduced, while when the fluorine-containing substituent and the hydrophilic substituent are too small, stain resistance is reduced and hydrophilicity is reduced. Run short. [II] / [III] is 1/10
If it is out of this range, either the hydrophilicity or the stain resistance is deteriorated and the balance of performance is deteriorated. Further, the total number of siloxane structural units [I] and [II] and [III] is preferably 10 to 1000, more preferably 20 to 500. If the siloxane chain is short, the flexibility and gas permeability of the polymer will decrease. On the other hand, if the siloxane chain is too long, the viscosity of the monomer itself is significantly increased, which makes the production and handling of the monomer difficult and lowers the polymerization rate, which is not preferable.

The polymerizable unsaturated group is bonded to the terminal of the siloxane chain, and the structure of the unsaturated group is preferably an acrylate group or a methacrylate group from the viewpoint of polymerizability. A hydrocarbon group containing a urethane bond is preferable as a connecting group with the Si atom, and may be via an oxyethylene group. The urethane bond has high polarity and increases the hydrophilicity of the polymer as well as the strength. Furthermore, the compatibility with other monomers is enhanced and the optical transparency of the polymer is improved. A structure in which two urethane linking groups are bonded is introduced by a reaction with a diisocyanate compound, and there are hydrocarbons having 4 to 13 carbon atoms between the urethane linking groups, which are chain, cyclic or aromatized hydrocarbons. May be. An aliphatic hydrocarbon having good light resistance is more preferable. Examples of diisocyanates that can be used include trimethylene diisocyanate, hexamethylene diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4-tolylene diisocyanate and the like.

Various methods of synthesizing the hydrophilic fluorine-containing siloxane monomer disclosed in the present invention are conceivable. That is, hydrosilane (Si
-H) -containing cyclic siloxane, a fluorine-substituted hydrocarbon group-containing cyclic siloxane, a hydrocarbon group-containing cyclic siloxane, and a hydroxysiloxane-containing disiloxane at both ends are treated with sulfuric acid, trifluoromethanesulfonic acid, acid clay or the like. Ring-opening polymerization is carried out using an acidic catalyst to obtain a hydrosilane-containing fluorine-containing siloxane compound having hydroxyl groups at both ends. At that time, by changing the charging ratios of the respective cyclic siloxanes and disiloxane compounds, siloxane compounds having different polymerization degrees and introduction ratios of fluorine substituents and hydrosilane groups can be obtained. Next, an isocyanate-substituted acrylate or an isocyanate-substituted methacrylate is reacted with a hydroxyl group at the siloxane terminal to obtain a hydrosilane-containing fluorine-containing siloxane compound having a polymerizable unsaturated group at both terminals. Here, the isocyanate-substituted methacrylate compound includes, for example, methacryloyloxyethyl isocyanate, methacryloyl isocyanate, and the like, and is obtained by reacting a hydroxy group-containing acrylate such as hydroxyethyl methacrylate or hydroxybutyl acrylate or a hydroxy group-containing methacrylate with various diisocyanate compounds. An acrylate group- or methacrylate group-containing isocyanate compound can also be used. Next, a hydrophilic fluorine-containing siloxane monomer can be obtained by utilizing a so-called hydrosilylation reaction in which a hydrophilic compound having an unsaturated hydrocarbon group is subjected to an addition reaction with hydrosilane using a transition metal catalyst such as chloroplatinic acid. it can.

During the hydrosilylation reaction, a hydroxyl group,
It is known that when an active hydrogen compound such as carboxylic acid is present, a dehydrogenation reaction occurs as a side reaction. Therefore,
When these active hydrogens are present in the hydrophilic compound to be introduced, the active hydrogens are protected in advance with a methylsilyl group, an acetyl group, an acetal group, an acetonide group, or a buffer agent is added to suppress the side reaction. The reaction must be suppressed. (For example, US Pat. No. 390785.
No. 1, JP-A-62-195389). As another synthetic route, after synthesis of a hydrosilane-containing fluorine-containing siloxane compound having hydroxyl groups at both ends, a hydrophilic compound is first introduced by hydrosilylation, and finally an isocyanate-substituted methacrylate is reacted to polymerize the siloxane end. There is also a method of introducing a sexual group. Also in this case, when active hydrogen capable of reacting with isocyanate is present in the hydrophilic compound, a protecting group must be introduced to prevent the reaction with isocyanate. Further, instead of the cyclic siloxane, a silicic acid ester derivative such as a dimethoxysilane compound or a diethoxysilane compound can be used as a starting material.

The ophthalmic lens material of the present invention comprises one kind or two or more kinds of the hydrophilic fluorine-containing siloxane monomer represented by the formula (1), or copolymerized with the hydrophilic fluorine-containing siloxane monomer alone. A hydrophilic composition containing a crosslinkable polymer obtained by copolymerizing one or more possible monomers. The term "hydrophilic composition" as used herein refers to a composition that has good water wettability as a surface property and does not repel water, while it has a large water content of 1% or more in terms of bulk property. Means In the present invention, either of them is defined as a “hydrophilic composition”. The ratio of the hydrophilic composition and the hydrophilic fluorine-containing siloxane monomer in the composition is preferably 10 to 100% by weight, more preferably 30 to
When the content of the hydrophilic fluorine-containing siloxane structure is too small in the composition, oxygen permeability and flexibility are insufficient. The structure of a good hydrophilic fluorine-containing siloxane monomer depends on the target performance of the ophthalmic lens material, such as oxygen permeability, softness, stain resistance, strength, and water content (1). In the formula, the type and number of bonds of the constitutional unit constituting Y and the residue constituting X are selected. The composition comprising the hydrophilic fluorine-containing monomer disclosed in the present invention is applied not only to a composition containing substantially no water having a water content of 1% or less, but also to a water-containing composition having a water content of more than 1%. It That is, the contact lens material can be used as a non-water-containing soft lens material or a water-containing soft lens material. Further, it is also useful as an intraocular lens and a corneal lens which are other ophthalmic lens materials.

The hydrophilic polymer of the present invention can be obtained by cross-linking and polymerizing one of the above monomers or a monomer copolymerizable with the above monomer. Here, the copolymerizable monomer will be described below. In the present invention, any monomer can be used as long as it can be copolymerized,
Above all, hydrophilic monomers are useful. That is,
This is because it has good compatibility with the hydrophilic fluorine-containing monomer of the present invention and can be used as a monomer for further improving the surface wettability of the polymer or changing the water content. For example, hydroxyl group-containing monomers such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, glycerol methacrylate, and 3- (1,1,2,2-tetrafluoroethoxy) -2-hydroxypropyl methacrylate. Hydroxyl group-containing monomer having a fluorine-containing substituent, carboxylic acid group-containing monomer such as methacrylic acid, acrylic acid and itaconic acid, alkyl-substituted amino group-containing monomer such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate, N, N'-dimethylacrylamide , N, N'-diethyl acrylamide, N-methyl acrylamide, methylene bis acrylamide, diacetone acrylamide, N vinyl N methyl acetamide,
Examples thereof include amide group- or imide group-containing monomers such as N-vinylpyrrolidone, and oxyalkylene group-containing monomers such as methoxypolyethylene glycol monomethacrylate and polypropylene glycol monoacrylate. Here, the number of repeating units of the oxyalkylene group is selected according to the target performance and the compatibility with the hydrophilic fluorine-containing monomer.

In addition, examples of other usable monomers include fluorine-containing monomers such as acrylic acid fluoroalkyl ester and methacrylic acid fluoroalkyl ester, for example, trifluoroethyl acrylate, tetrafluoroethyl acrylate, tetrafluoropropyl acrylate, Examples include pentafluoropropyl acrylate, hexafluorobutyl acrylate, hexafluoroisopropyl acrylate, and methacrylates of these acrylates, which can be selected according to the required compatibility, hydrophilicity, water content, and stain resistance. Further, an acrylic acid alkyl ester monomer and a methacrylic acid alkyl ester monomer can be used if necessary. Examples include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, tert-butyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate,
Examples include n-stearyl acrylate and methacrylates corresponding to these acrylates.

If desired, the following monomers may be copolymerized in order to further improve the mechanical properties and dimensional stability. Examples of the monomer for improving mechanical properties include aromatic vinyl compounds such as styrene, tert-butylstyrene, and α-methylstyrene. Examples of the monomer for improving dimensional stability include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, and bisphenol A dimethacrylate. , Vinyl methacrylate, acrylic methacrylate, acrylates corresponding to these methacrylates, divinylbenzene, triallyl isocyanurate, and the like. These monomers may be used alone or in combination of two or more.

Optical properties of hydrophilic materials, oxygen permeability, mechanical strength, deformation recovery, stain adhesion when worn on the eye,
In order to improve the dimensional stability in tear fluid and the property balance such as its change with time, a mixed monomer in which these copolymerizable monomers are combined can be used. Further, if necessary, various additives may be added before or after the polymerization. As the additive, for example, various coloring agents,
There are UV absorbers and antioxidants.

The crosslinkable polymer used as the ophthalmic lens material of the present invention is a cast obtained by, for example, filling a mold with a mixture of a hydrophilic fluorine-containing siloxane monomer and a copolymerizable monomer and radically polymerizing the mixture by a known method. A contact lens or the like can be molded by a polymerization method, a method of charging a monomer mixture in a rotating half-face mold and polymerizing it, or a method of freezing and cutting the copolymer at low temperature. Depending on the case, the lens surface may be further subjected to plasma treatment, ozone treatment, graft polymerization or the like for surface modification.

The copolymerization method is preferably a method in which a photopolymerization initiator is present in the monomer mixture and irradiation is performed with ultraviolet rays to perform polymerization, or a radical polymerization method in which polymerization is performed using an azo compound or an organic peroxide. . As one example of the photopolymerization initiator used, benzoin ethyl ether, benzyl dimethyl ketal, α, α′-diethoxyacetophenone, and the like, benzoyl peroxide as an organic peroxide,
As azo compounds such as t-butyl peroxide, azobisisobutyronitrile, azobisdimethylvaleronitrile and the like are used. The above-mentioned crosslinkable polymer can be identified by nuclear magnetic resonance analysis (NMR) or chemical decomposition method.

[0028]

The present invention will be described in detail below with reference to Examples.
The invention is in no way limited to these examples. For confirmation of the structure of the synthetic product, infrared absorption spectroscopy (IR) and nuclear magnetic resonance spectroscopy ( ¹ H-NM
R). IR is PE-1 manufactured by Perkin Elmer
It was measured on a KBr plate using a Model 640. ¹ H-NMR was measured as a heavy chloroform solution using AC-200P type manufactured by Bruker. Each evaluation item was determined as follows. (1) Optical transparency Visual inspection. A sample with no cloudiness and good transparency was evaluated as O, a sample with cloudiness and translucency as Δ, and a sample with cloudiness and no opacity as X. (2) Water wettability The wettability with purified water was visually evaluated. After immersing the sample piece in purified water for 24 hours, it was pulled up vertically and the water film was retained for 5 seconds or longer.
When it was 2 seconds or less, it was marked with x. (3) Water content The weight of the sample piece dried under vacuum at 80 ° C. for 24 hours was taken as the dry weight, and the weight after storage in purified water for 1 week or more was taken as the water content weight.

(4) 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. The unit in Table 1 is (ml · cm / cm ² · sec · mmHg) × 1
^0-11 . (5) Tensile Strength A tensile tester AGS-50B manufactured by Shimadzu Corporation was used. The measurement is in a constant temperature room at 25 ° C., and the test piece is 5 mm wide, 20 mm long, and 0.1 mm.
A 3 mm thickness was used. The unit in Table 1 is (g / mm ² ). (6) Stain Adhesion The stain adhesion was evaluated as the amount of protein attached. Lysozyme (0.2%) in a Tris-HCl buffer solution (PH = 7.4)
%) And the test piece is immersed in this solution (37 ° C.
3 Hr), immersed in purified water and dried. The surface infrared spectroscopic analysis was measured before and after the contamination treatment, and the absorption amount of the amide group derived from the protein was calculated from the difference spectrum. The larger the value, the greater the amount of dirt attached. The values shown in Table 1 are values obtained by multiplying the actual values by 1000.

[0030]

Example 1 [Synthesis of hydrosilane-containing siloxane diol (A1)] Octamethylcyclotetrasiloxane 150 g,
2,3,5-trimethyltrifluoropropylcyclotrisiloxane 22.6 g, 1,3,5,7-tetramethylcyclotetrasiloxane 17.4 g, 1,3-bis (4-hydroxypropyl) tetramethyldisiloxane 7 0.2 g, chloroform 200 g, and trifluoromethanesulfonic acid 1.5 g are stirred in a flask at 25 ° C. for 24 hours, and then repeatedly washed with purified water until the pH becomes neutral. After separating water, chloroform was distilled off under reduced pressure. The residual liquid was dissolved in isopropanol, reprecipitated with methanol, and the separated liquid was subjected to removal of volatile components under vacuum to obtain a transparent viscous liquid. 98 g of siloxane diol (A1) having hydrosilane represented by the following formula (7) was obtained. In addition,
Although the structural formula of the skeleton Y is shown as if it is a block of each siloxane, it actually contains a random structure, and only the proportion of each siloxane is shown here. The same applies to the following examples and comparative examples.

[0031]

[Chemical 12]

[Synthesis of Hydrosilane-Containing Siloxane Dimethacrylate (B1)] The above siloxane diol (A
1) 50 g, methacryloyloxyethyl isocyanate 3.9 g, dry acetone 100 g, and dibutyltin dilaurate 0.02 g were added to a brown flask and stirred under a nitrogen atmosphere at 25 ° C. for 24 hours, and then purified water 1.4 was added.
g and stir for a further 3 hours. Acetone was distilled off under reduced pressure, the residual liquid was washed with methanol, and then the volatile matter was removed again under vacuum, whereby a transparent viscous liquid was obtained. 48.7 g of siloxane dimethacrylate (B1) having hydrosilane represented by the following formula (8) was obtained.

[0033]

[Chemical 13]

[Synthesis of alcohol group-containing siloxane dimethacrylate (C1)] 48 g of the above siloxane dimethacrylate (B1), 11.6 g of allyl alcohol, 96 g of isopropyl alcohol, 0.04 g of potassium acetate,
Chloroplatinic acid 10 mg, di-t-butylcresol 10 m
g was placed in a flask equipped with a reflux condenser and heated and stirred at 50 ° C. for 3 hours under a nitrogen atmosphere. After separating the reaction solution by filtration, the isopropanol was distilled off under reduced pressure, and the residue was washed with 5% water-containing methanol. Further, when the volatile matter was removed under vacuum, a transparent viscous liquid was obtained. Alcohol group-containing siloxane dimethacrylate represented by the following formula (9) (C
It was 1). IR and ¹ H-NMR spectra are shown in (FIG. 1) and (FIG. 2), respectively.

[0035]

Embedded image

[0036]

Example 2 50 g of siloxane dimethacrylate (B1) synthesized in Example 1, 20 g of 2- (trimethylsiloxy) ethyl acrylate, 100 g of toluene, 10 mg of chloroplatinic acid, 10 mg of di-t-butylcresol were added to a flask equipped with a reflux condenser. And heated under reflux in a nitrogen atmosphere for 5 hours. After cooling, after distilling off toluene under reduced pressure,
300 g of acetic acid and 50 g of purified water were added and heated at 50 ° C. for 8 hours to remove the protective group. Next, when the volatile components were removed under vacuum, 52 g of a transparent and viscous liquid was obtained. As a result of the analysis, the skeleton Y in the formula (9) in Example 1 was an alcohol group-containing siloxane dimethacrylate (C2) represented by the following formula (10).

[0037]

[Chemical 15]

[0038]

Example 3 In the same manner as in Example 2, except that vinyl acetic acid trimethylsilyl ester was used in place of 2- (trimethylsiloxy) ethyl acrylate, the same reaction and purification were carried out. In, a carboxylic acid group-containing siloxane dimethacrylate (C3) having a skeleton Y represented by the following formula (11) was obtained.

[0039]

Embedded image

[0040]

Example 4 40 g of siloxane dimethacrylate (B1) synthesized in Example 1, 15 g of N, N-dimethylacrylamide, 100 g of toluene, 10 mg of chloroplatinic acid and 10 mg of di-t-butylcresol were charged in a flask equipped with a reflux condenser. The mixture was heated under reflux in a nitrogen atmosphere for 5 hours. After cooling, the toluene was distilled off under reduced pressure, the residue was washed with 10% methanol containing water, and then volatile components were removed under vacuum to obtain 41 g of a transparent viscous liquid. As a result of the analysis, the skeleton Y in the formula (9) of Example 1 was an alcohol group-containing siloxane dimethacrylate (C4) represented by the following formula (12).

[0041]

[Chemical 17]

[0042]

Example 5 To 35 g of the hydrosilane-containing siloxane dimethacrylate (B1) described in Example 1, 15 g of 3-allyloxy-1,2-propanediol, 80 g of isopropyl alcohol, 0.03 g of potassium acetate, and 6 chloroplatinic acid.
mg and di-t-butylcresol 7 mg were placed in a flask equipped with a reflux condenser, and the reaction and purification were carried out in the same manner as in the synthesis of (C1) in Example 1 to obtain 33 g of a transparent viscous liquid. In the formula (9) of Example 1, the skeleton Y is represented by the following formula (1
It was an alcohol group-containing siloxane dimethacrylate (C5) represented by 3).

[0043]

Embedded image

[0044]

Example 6 3-allyloxy-1,2 in Example 5
-Reaction and purification were carried out in the same manner as in Example 5 using 7 g of allylamine instead of propanediol. As a result, in the formula (9) of Example 1, the skeleton Y has the amino group-containing siloxane dimethacrylate (C6) 3 represented by the formula (14).
5 g was obtained.

[0045]

[Chemical 19]

[0046]

Example 7 [Synthesis of hydrosilane-containing siloxane diol (A2)] Octamethylcyclotetrasiloxane 190 g,
100 g of 1,3,5-trimethyltrifluoropropylcyclotrisiloxane, 7.7 g of 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-bis (2-
Hydroxyethyloxypropyl) tetramethyldisiloxane (14.4 g), chloroform (300 g) and trifluoromethanesulfonic acid (2.3 g) were placed in a flask and synthesized and purified in the same manner as the siloxane diol (A1) of Example 1. 110 g of liquid was obtained. As a result of the analysis, it was a siloxane diol (A2) having a hydrosilane represented by the following formula (15).

[0047]

Embedded image

[Synthesis of polyoxyethylene group-containing siloxane diol (D1)] 35 g of the above-mentioned hydrosilane-containing siloxane diol (A2), 14 g of polyoxyethylene allyl methyl ether (molecular weight about 400), 100 g of isopropyl alcohol, 0.03 g of potassium acetate, 6 mg of chloroplatinic acid was placed in a flask equipped with a reflux condenser and heated under reflux for 3 hours under a nitrogen atmosphere. After separating the reaction solution by filtration,
After isopropanol was distilled off under reduced pressure, it was washed with methanol containing 5% water. Further, the volatile matter was removed under vacuum to obtain 42 g of a transparent viscous liquid. As a result of the analysis, the following formula (1
It was a polyoxyethylene group-containing siloxane diol (D1) represented by 6).

[0049]

[Chemical 21]

[Synthesis of Polyoxyethylene Group-Containing Siloxane Dimethacrylate (C5)] 40 g of the obtained polyoxyethylene group-containing siloxane diol (D1) and 85 g of dry acetone were added to a brown flask and dissolved.
2.0 g of methacryloyl isocyanate was added, and the mixture was stirred at 25 ° C. for 3 hours under a nitrogen atmosphere. Purified water (1.4 g) was added and the mixture was further stirred for 2 hours, and then acetone was distilled off under reduced pressure. The residual liquid was washed with methanol containing 5% water, and then the volatile matter was removed again under vacuum to obtain 48.7 g of a transparent viscous liquid. As a result of the analysis, it was a siloxane dimethacrylate (C5) having a polyoxyethylene group represented by the following formula (17).

[0051]

[Chemical formula 22]

[0052]

Comparative Example 1 In the synthesis of the hydrosilane-containing siloxane diol (A1) of Example 1, 1,3,5,7-tetramethylcyclotetrasiloxane was not added, and the reaction was carried out in the same manner to obtain the siloxane diol (A3). Obtained. Then, a reaction similar to the synthesis of the hydrosilane-containing siloxane dimethacrylate (B1) of Example 1 was performed, and the following formula (1
A siloxane dimethacrylate (R1) having no hydrophilic group of 8) was obtained.

[0053]

[Chemical formula 23]

[0054]

Comparative Example 2 In the synthesis of the hydrosilane-containing siloxane diol (A1) described in Example 1, 1,3-bis (4
-Hydroxypropyl) tetramethyldisiloxane, 11.3 g of 1,3-bis (3-methacryloxypropyl) tetramethyldisiloxane was added and reacted and purified in the same manner to obtain siloxane dimethacrylate (B2).
I got Then, (B2) was used in place of the siloxane dimethacrylate (B1) in the synthesis of the alcohol group-containing siloxane dimethacrylate (C1) described in Example 1, and the reaction was carried out. The siloxane dimethacrylate (R2) containing alcohol group shown in was obtained. The connection between the polymerizable group and the siloxane chain is not via a urethane group but via an ester group.

[0055]

[Chemical formula 24]

[0056]

Comparative Example 3 In the synthesis of the hydrosilane-containing siloxane diol (A1) of Example 1, 1,3,5-trimethyltrifluoropropylcyclotrisiloxane was not added, and the reaction was performed in exactly the same manner. Then, according to the method described in Example 1, a hydrosilane-containing siloxane dimethacrylate (B3) and then an alcohol group-containing siloxane dimethacrylate (R3) having no fluorine substituent were synthesized. The structure is shown in the following formula (20).

[0057]

[Chemical 25]

[0058]

Example 8 80 parts by weight of the alcohol group-containing siloxane dimethacrylate (C1) described in Example 1, 20 parts by weight of 2-hydroxypropyl methacrylate (hereinafter referred to as HP), and 2,4,6-trimethylbenzoyldiphenylphosphine. 0.5 part by weight of oxide was added, and the mixture was stirred in a nitrogen atmosphere with a magnetic stirrer for about 1 hour.
Dissolved and mixed. Then, in a nitrogen atmosphere, the mixed liquid solution was injected into a cell assembled by two glass plates (thickness 10 mm, width 60 mm, length 90 mm) with a silicone rubber gasket interposed therebetween, 40 to 50
When ultraviolet rays were irradiated for 2 hours at a temperature of ° C, a transparent and flexible sheet-like polymer was obtained. This copolymer was evaluated for water wettability, water content, oxygen permeability coefficient, tensile strength and stain adhesion. The results are shown in Table 1.

[0059]

Examples 9 to 14 The hydrophilic fluorine-containing siloxane monomers described in Examples 2 to 7 were polymerized under the same composition and conditions as in Example 8 to obtain copolymers. The results of physical property evaluation are shown in Table 1.

[0060]

Comparative Examples 4 to 6 The siloxane monomers described in Comparative Examples 1 to 3 were polymerized under the same composition and conditions as in Example 8 to obtain copolymers. The results of physical property evaluation are shown in Table 1. As is clear from Table 1, the polymerization composition using the hydrophilic fluorine-containing siloxane monomer of the present invention has transparency, tensile strength,
Good balance of dirt adhesion and good oxygen permeability.

[0061]

Example 15 In Example 8, 80 parts by weight of alcohol group-containing siloxane dimethacrylate (C1), 3, 3,
3-trifluoroethyl methacrylate (hereinafter referred to as 3FM) 10 parts by weight, n-butyl methacrylate (hereinafter referred to as n)
5 parts by weight of BA, 3 parts by weight of methacrylic acid (hereinafter referred to as MAA), 2 parts of 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA), 0.5 parts by weight of ethylene glycol dimethacrylate (hereinafter referred to as ED), and Two
0.5 parts by weight of 4,6-trimethylbenzoyldiphenylphosphine oxide was added and photopolymerized in the same manner.
As a result, a flexible and transparent sheet was obtained. This sheet had a water content of 0.5% and was a substantially non-water-containing material, but had good water wettability. Furthermore, oxygen permeability coefficient 23
5 × 10 ⁻¹¹ ml · cm / cm ² · sec · mmHg and a tensile strength of 295 g / mm ² showed sufficient performance as a contact lens.

[0062]

Example 16 In Example 15, 60 parts by weight of the siloxane dimethacrylate (C1) containing an alcohol group, 20 parts by weight of HP, 15 parts by weight of nBA and 0.5 parts by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Part was added and photopolymerized in the same manner. A flexible and transparent sheet was obtained. This sheet had a water content of 2% and had good water wettability. The oxygen permeability coefficient is 114 × 10 ^-11.
ml · cm / cm ² · sec · mmHg, tensile strength 2
It showed 35 g / mm ² and sufficient performance as a contact lens.

[0063]

Example 17 In Example 8, instead of HP,
When N, N-dimethylacrylamide was used, a highly hydrated sheet having good transparency and a water content of 55% was obtained. The oxygen permeability coefficient was measured to be 85 × 10
^{It has a} high oxygen permeability of ^-11 (ml · cm / cm ² · sec · mmHg) and is useful for highly water-containing materials such as ophthalmic water-containing lenses.

[0064]

Example 18 Next, the hydrophilic fluorine-containing siloxane monomer described in Example 8 and HP were placed in a polypropylene concave-convex mold (lens diameter 13.7 mm) prepared by injection molding.
The mixture solution was injected and filled, and ultraviolet rays were irradiated for 2 hours for polymerization. The lens taken out from the mold after polymerization is transparent and flexible and has good wettability with water. In addition, the resolving power as a lens was good and it was useful as a lens material.

[0065]

[Table 1]

[0066]

The hydrophilic fluorine-containing siloxane monomer of the present invention is a novel compound, and by homopolymerization or copolymerization, optical transparency, water wettability, stain resistance, gas permeability,
It gives a hydrophilic composition having good flexibility and is useful as an ophthalmic lens material such as a contact lens.

[Brief description of drawings]

1 is an infrared absorption spectrum (I) of the alcohol group-containing siloxane dimethacrylate (C1) obtained in Example 1.
R) FIG.

2 is a nuclear magnetic resonance spectrum of the alcohol group-containing siloxane dimethacrylate (C1) obtained in Example 1 (
^{It is a} < ¹ > H-NMR) figure.

Claims (11)

[Claims] 1. A hydrophilic fluorine-containing siloxane monomer represented by the following formula (1). Embedded image [In the formula, X is a substituent having an unsaturated group represented by the formula (2). Embedded image R ₁ , R ₂ , R ₃ , and R ₄ are each a group selected from a hydrocarbon group having 1 to 12 carbon atoms or a trimethylsiloxy group. Y is composed of structural units [I], [II] and [III] represented by the following formula, and structural units [I], [II],
The ratio of [III] is [I] / ([II] + [III])
= 1/10 to 100/1, and further [II]
/ [III] = 1/10 to 10/1,
The total number of [I], [II] and [III] is 10 to 10.
00. (Here, Z ₁ is a —NHCOO— group or —O
OCNH-R ₆ -NHCOO- group (R ₆ is a carbon number 4 to 13
A hydrocarbon group), R ₅ is hydrogen or methyl, m is 0, n is an integer of 1 to 20, p is 0 when m is 0, when m is 1 or more 1 Is. q is 0 to 20
Is an integer. ) [Chemical 3] (Here, R ₇ and R ₈ are respectively a hydrocarbon group having 1 to 12 carbon atoms or a trimethylsiloxy group and may be the same or different, and R ₉ and R ₁₀ are each a hydrocarbon group having 1 to 12 carbon atoms, Trimethylsiloxy group or C1-C1
2, wherein at least one of R _{9 and} R ₁₀ is a fluorine-substituted hydrocarbon group. R ₁₁ and R ₁₂ are each a hydrocarbon group having 1 to 12 carbon atoms, a group consisting of a trimethylsiloxy group or a hydrophilic substituent,
At least one of R _{11 and} R ₁₂ is a hydrophilic substituent. The hydrophilic substituent referred to here is a chain or cyclic hydrocarbon group formed by bonding at least one substituent selected from a hydroxyl group, a carboxylic acid group, an amino group, an imino group, an amide group and an oxyalkylene group. Say. )] 2. The hydrophilic fluorine-containing siloxane monomer according to claim 1, wherein the hydrophilic substituent is a group represented by formula (3) or formula (4). [Chemical 4] (Here, R ₁₃ is a hydrocarbon of hydrocarbons 3 to 12, and is an oxygen atom between carbon and carbon, —CO—, —COO—, —OOC.
The group consisting of-may be sandwiched, and only one OH group is substituted on the same carbon atom, and a is a number larger than 1. ) [Chemical 5] (Here, R ₁₄ is a hydrocarbon having 3 to 12 hydrocarbons, and an oxygen atom, —CO—, —COO—, —OOC between carbon and carbon.
The group consisting of − may be sandwiched. R ₁₅ and R ₁₆ are hydrocarbons having 2 to 4 carbon atoms. b and c are 0 to
200 and b + c is at least 1. Z ₂ is a hydrogen atom, a hydrocarbon having 1 to 12 carbon atoms, R ₁₇ OH (R ₁₇ is a hydrocarbon having 1 to 12 carbon atoms) or —OCOR ₁₈ (R ₁₈
Represents a group selected from hydrocarbons having 1 to 12 carbon atoms). ) 3. A structural unit whose structure Y is represented by the following formula:
The hydrophilic fluorine-containing siloxane monomer according to claim 2, which comprises [I ′], [II ′] and [III ′]. [Chemical 6] (R ₁₉ is a hydrophilic group and is a group represented by the following formula (5) or (6). (Here, R ₁₃ is a hydrocarbon having 3 to 12 carbon atoms, and an oxygen atom, —CO—, —COO—, —OOC— is present between the carbon atoms.
The OH group is substituted on the same carbon atom only once, and a is a number larger than 1. ) [Chemical 8] (Here, R ₁₄ is a hydrocarbon having 3 to 12 hydrocarbons, and an oxygen atom, —CO—, —COO—, —OOC between carbon and carbon.
The group consisting of − may be sandwiched. R ₁₅ and R ₁₆ are hydrocarbons having 2 to 4 carbon atoms. b and c are 0 to
200 and b + c is at least 1. Z ₂ is a hydrogen atom, a hydrocarbon having 1 to 12 carbon atoms, R ₁₇ OH (R ₁₇ is a hydrocarbon having 1 to 12 carbon atoms) or —OCOR ₁₈ (R ₁₈
Represents a group selected from hydrocarbons having 1 to 12 carbon atoms). ) 4. A hydrophilic fluorine-containing siloxane monomer according to claim 1, wherein one or more hydrophilic fluorine-containing siloxane monomer is used alone or a copolymerizable monomer is used. A hydrophilic composition comprising a crosslinkable polymer obtained by copolymerizing two or more kinds. 5. The hydrophilic fluorine-containing siloxane monomer according to claim 2 is used alone or in combination with one or more hydrophilic fluorine-containing siloxane monomer alone or as a copolymerizable monomer. A hydrophilic composition comprising a crosslinkable polymer obtained by copolymerizing two or more kinds. 6. A hydrophilic fluorine-containing siloxane monomer according to claim 3, wherein at least one hydrophilic fluorine-containing siloxane monomer is used alone or a copolymerizable monomer is used. A hydrophilic composition comprising a crosslinkable polymer obtained by copolymerizing two or more kinds. 7. A chain-like or cyclic hydrocarbon in which the copolymerizable monomer has at least one substituent selected from a hydroxyl group, a carboxylic acid group, an amino group, an imino group, an amide group, and an oxyalkylene group bonded thereto. The hydrophilic composition according to claim 6, which is a polymerizable unsaturated compound having a group. 8. An ophthalmic lens material comprising the hydrophilic composition according to claim 4. 9. An ophthalmic lens material comprising the hydrophilic composition according to claim 5. 10. An ophthalmic lens material comprising the hydrophilic composition according to claim 6. 11. An ophthalmic lens material comprising the hydrophilic composition according to claim 7.