JP2852374B2 - Contact lens comprising (meth) acrylate copolymer containing silicon substituent - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a contact lens having excellent oxygen permeability, comprising a novel alicyclic (meth) acrylate copolymer containing a silicon substituent.

2. Description of the Related Art Since the cornea of the eye is a tissue without blood vessels, oxygen required for its respiratory metabolism is obtained by diffusion from the eyelid conjunctiva and aqueous humor when the eyelid is closed, and in the atmosphere when the eyelid is opened. We adopt from. Therefore, wearing a contact lens on the eyeball leads to impaired oxygen metabolism in the cornea,
When worn over an extended period of time, hyperemia, edema, and other corneal disorders often occur. Therefore, it is essential that the material for a contact lens has excellent oxygen permeability in addition to excellent optical properties, chemical properties, physical properties and the like. Furthermore, it is important that the material for contact lenses has excellent resistance to stains, such as proteins, lipids, and mucins, which are tear components, resistance to bacteria and fungi, feeling of wearing, and biocompatibility. is there.

Conventionally, polymethyl methacrylate and various methacrylate copolymers have been widely used as materials for such contact lenses. These materials are satisfactory with regard to optical properties, but have insufficient oxygen permeability, and contact lenses made of them cannot withstand prolonged wearing.

Therefore, in order to improve the oxygen permeability of the methacrylate polymer, for example, Japanese Patent Publication No. 52-33502,
Silicone methacrylate-based polymers in which siloxane bonds are introduced into methacrylate molecules have been proposed, and are disclosed in JP-A-57-51705 and JP-A-61-111308.
Japanese Patent Laid-Open Publication No. H11-15064 proposes a contact lens using an oxygen-permeable polymer mainly composed of cellulose acetate butyrate or a fluorine-containing methacrylate polymer.

However, such a polymer is somewhat improved in oxygen permeability as compared with the above-mentioned polymethyl methacrylate and methacrylate ester-based polymers, but is still
It is not enough, and there is still room for improvement in stain resistance and wearability.

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems in a conventional contact lens, and is based on a novel silicon-substituted alicyclic (meth) acrylate copolymer. It is an object of the present invention to provide a contact lens having excellent oxygen permeability.

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems in a conventional contact lens, and is based on a novel silicon-substituted alicyclic (meth) acrylate copolymer. It is an object of the present invention to provide a contact lens having excellent oxygen permeability.

Means for Solving the Problems The contact lens according to the present invention has the general formula (I) (Wherein, R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrocarbon group having 0 to 3 carbon atoms, and Cy is a carbon atom having 3 to 20 carbon atoms.
Alicyclic hydrocarbon group, R ⁴ , R ⁵ and R ⁶ are each independently a hydrocarbon group having 1 to 6 carbon atoms, a fluoroalkyl group, an alkoxy group or (Wherein, R ⁷ independently represents an alkyl group having 1 to 3 carbon atoms, a fluoroalkyl group or an alkoxy group, and n represents an integer of 1 to 10). ) Containing a silicon substituent containing a structural unit represented by (meta)
It is characterized by comprising an acrylate copolymer.

The contact lens according to the present invention preferably comprises (a) a silicon-substituted alicyclic (meth) acrylate unit represented by the general formula (I), and (b) a general formula (In the formula, R ¹ is the same as described above, and R represents a hydrogen, an alkyl group, an alkyl group having a hydroxyl group, a cycloalkyl group or an alkyl group having fluorine.) It is characterized by comprising a silicon-substituent-containing alicyclic (meth) acrylate copolymer containing (meth) acrylate units.

The silicon substituent-containing alicyclic (meth) acrylate copolymer constituting the contact lens according to the present invention comprises:
It contains the structural unit represented by the general formula (I). In this structural unit (I), Cy represents an alicyclic hydrocarbon group having 3 to 20 carbon atoms. And the like.

In the structural unit represented by the general formula (I), R ¹ represents a hydrogen atom or a methyl group. R ² and R ³ are
Each independently represents a hydrocarbon group having 0 to 3 carbon atoms, which may be the same or different. When the number of carbon atoms is 0, it is a carbon-carbon bond. Examples of the hydrocarbon group having 1 to 3 carbon atoms include lower alkylene groups such as a methylene group, an ethylene group, and a propylene group.

R ⁴ , R ⁵ and R ⁶ are each independently a hydrocarbon group having 1 to 6 carbon atoms, a fluoroalkyl group, an alkoxy group or (Wherein, R ⁷ independently represents an alkyl group having 1 to 3 carbon atoms, a fluoroalkyl group or an alkoxy group, and n represents an integer of 1 to 10). R ⁴ , R ⁵ and R ⁶ may be the same as or different from each other, and preferred specific examples thereof include, for example,
Examples thereof include a methyl group, an ethyl group, a propyl group, a trifluoropropyl group, a phenyl group, a methoxy group, and a phenoxy group, and a methyl group is particularly preferable. Also,
R ⁷ may be the same as or different from each other, and preferred specific examples thereof include a methyl group, an ethyl group, a propyl group, a trifluoropropyl group, a methoxy group, a phenoxy group and the like. Particularly, a methyl group is preferable.

Such a silicon substituent-containing (meth) acrylate copolymer is represented by the general formula (I ′): (Wherein, R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrocarbon group having 0 to 3 carbon atoms, and Cy is a carbon atom having 3 to 20 carbon atoms.
Alicyclic hydrocarbon group, R ⁴ , R ⁵ and R ⁶ are each independently a hydrocarbon group having 1 to 6 carbon atoms, a fluoroalkyl group, an alkoxy group or (Wherein, R ⁷ independently represents an alkyl group having 1 to 3 carbon atoms, a fluoroalkyl group or an alkoxy group, and n represents an integer of 1 to 10). ) Can be obtained by copolymerizing a silicon-substituent-containing alicyclic (meth) acrylate represented by the formula (1) with a second monomer having copolymerizability therewith. In the copolymer according to the present invention, the silicon-substituted alicyclic (meth) acrylate component is used in an amount of 10 to 95% by weight, preferably 30 to 90% by weight.

Here, the second monomer is a silicon-substituent-containing alicyclic (meth) represented by the general formula (I ′).
If it has copolymerizability with acrylic acid ester,
Although not particularly limited, for example, acrylic acid,
Methacrylic acid, methyl acrylate, ethyl acrylate,
In addition to methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, and 2-ethylhexyl methacrylate, the following (meth) acrylate monomers can be exemplified.

And (meth) acrylic acid esters, And the like.

These (meth) acrylate monomers are used alone or as a mixture of two or more.

These (meth) acrylate monomer components are
In the silicon substituent-containing (meth) acrylate copolymer, it is used in an amount of 1 to 60% by weight, preferably 3 to 45% by weight.

Particularly preferably, in the present invention, the second comonomer is represented by the general formula (II ′) (Wherein, R ¹ is the same as described above, and R represents hydrogen, an alkyl group, an alkyl group having a hydroxyl group, a cycloalkyl group, or an alkyl group having fluorine.) (Meth) acrylic acid esters are preferably used.

In the structural unit represented by the general formula (II ′),
R ¹ is the same as described above, and R is hydrogen, an alkyl group, an alkyl group having a hydroxyl group, a cycloalkyl group, or an alkyl group having fluorine. In particular, R is, for example, a lower alkyl group such as a methyl group, an ethyl group, and a propyl group;
Preferred specific examples include an alkyl group having a hydroxyl group such as -hydroxypropyl group, a cycloalkyl group such as a cyclohexyl group, and an alkyl group having fluorine such as a trifluoropropyl group.

Therefore, preferred specific examples of the structural unit (II ′) include
Examples thereof include a methyl methacrylate unit, a 2-hydroxyethyl methacrylate unit, a cyclohexyl methacrylate unit, and a trifluoroethyl methacrylate unit.

Accordingly, the silicon-substituted (meth) acrylate copolymer preferably has the general formula (II) (Wherein, R ¹ is the same as described above, and R represents hydrogen, an alkyl group, an alkyl group having a hydroxyl group, a cycloalkyl group or an alkyl group having fluorine.) Contains (meth) acrylate units.

In the silicon substituent-containing (meth) acrylate copolymer used in the present invention, such (meth)
The acrylic acid unit or (meth) acrylic ester unit will be apparent from the correspondence with the above (meth) acrylic acid or (meth) acrylic ester.

Since the alicyclic (meth) acrylate containing a silicon substituent represented by the general formula (I ′) is a novel compound, its production will be described first.

In the silicon substituent-containing alicyclic (meth) acrylate represented by the general formula (I ′), R ¹ , R ²
And R ³ , Cy, R ⁴ , R ⁵ and R ⁶ are the same as above,
Preferred specific examples of the silicon-substituted alicyclic (meth) acrylate include, for example, And the like.

Accordingly, from the preferred alicyclic (meth) acrylic ester containing a silicon substituent (I ′), the preferred alicyclic (meth) acrylic acid ester unit containing a silicon substituent (I) in the copolymer according to the present invention is also changed. It will be obvious.

The silicon substituent-containing alicyclic (meth) acrylate (I ′) as described above has the general formula (III) (Wherein, R ² , R ³ , Cy, R ⁴ , R ⁵ and R ⁶ are the same as described above). (Meth) acrylic acid or (meth) acrylic halide Can be obtained by reacting

In the silicon substituent-containing alicyclic alcohol represented by the general formula (III), Cy, R ² , R ³ , R ⁴ , R ⁵ and R
⁶ is the same as described above. Accordingly, preferred specific examples of the silicon-substituted alicyclic alcohol include, for example, 4-tris (trimethylsiloxy) siloxycyclohexanol, 3-tris (trimethylsiloxy) siloxycyclohexanol, 4-bis (trimethylsiloxy) methyl Silyloxycyclohexanol, trimethylsiloxycyclohexanol, trifluoropropyldimethylsiloxycyclohexanol, 5-tris (trimethylsiloxy) siloxy-1-decanol, 4
-Bis (trimethylsiloxy) methylsiloxycyclohexane-1-methanol, And the like.

Here, silicon-substituted group containing an alicyclic alcohol represented by the general formula (III) also, shall apply in the new compounds of general formula ^{(IV) HO-R 2 -Cy} -R 3 -OH (IV) ( wherein , R ² , R ³ and Cy are the same as described above.) The alicyclic polyhydric alcohol represented by the general formula (V) (Wherein, R ⁴ , R ⁵ and R ⁶ are the same as above, and X represents hydrogen or a halogen atom).

In the alicyclic polyhydric alcohol represented by the above general formula (IV), R ² , R ³ and Cy are the same as described above, and thus, for example, cyclohexane-1,4-
Diol, cyclohexane-1,3-diol, cyclohexane-1,2-diol, cyclopentane-1,3-diol, cyclopentane-1,2-diol, cyclooctane-1,4-diol, cyclooctane-1, 3-diol, cyclohexane-1,4-dimethanol, decalin-1,5-diol, And the like.

In the silicon compound represented by the general formula (V), R ⁴ , R ⁵ and R ⁶ are the same as described above, and X represents a hydrogen atom or a halogen atom, preferably a chlorine atom. Accordingly, as such a silicon compound, for example,
Tris (trimethylsiloxy) silyl chloride, trimethylsilyl chloride, bis (trimethylsiloxy)
Examples thereof include methylsilyl chloride, 3,3,3-trifluoropropylsilyl chloride, trimethylsiloxydimethylsilyl chloride, triphenylsilyl chloride, and dimethoxymethylsilyl chloride.

In the reaction between the alicyclic polyhydric alcohol (IV) and the silicon compound (V), the alicyclic polyhydric alcohol (I
V) is used in a molar amount of 1 to 50 times, preferably 2 to 10 times the molar amount of the silicon compound (V). The reaction is carried out in the presence or absence of a solvent, preferably in the presence of a basic compound, under an inert atmosphere, at -10 to 300 ° C, preferably
The reaction is usually performed at a temperature in the range of 0 to 200 ° C for 0.2 to 20 hours.

As the reaction solvent, hydrocarbons, ketones, ethers and the like are preferably used, and for example, hexane, pentane, benzene, toluene, cyclohexane, acetone, methyl isobutyl ketone, diethyl ether, diisopropyl ether, tetrahydrofuran and the like are used.

As the basic compound, any of inorganic and organic bases can be used. Examples of the inorganic base include sodium hydroxide, alkali metal hydroxides such as potassium hydroxide, sodium carbonate, potassium carbonate, and carbonate. Alkali metal carbonates and hydrogen carbonates such as sodium hydrogen and potassium hydrogen carbonate are used. Further, as the organic base, an amine compound is preferable, for example, triethylamine, methyldiethylamine, triisopropylamine,
Pyridine or the like is used.

These basic compounds are the same as those of the silicon compound (V).
An 8 to 10 times molar amount, preferably 1 to 3 times molar amount is used. In particular, a 1.1- to 1.2-fold molar amount is preferred.

After completion of the reaction, the solvent is separated and removed from the obtained reaction mixture under reduced pressure, extracted with a suitable hydrocarbon, for example, hexane, and the obtained hexane layer is distilled under reduced pressure to obtain the compound represented by the general formula (III). Can be obtained.

Further, as described above, by reacting (meth) acrylic acid or (meth) acrylic halide with such a silicon-substituted alicyclic alcohol (III), the compound represented by the general formula (I ′) can be obtained. The silicon-substituted alicyclic (meth) acrylate represented by the following formula can be obtained.

As the above (meth) acrylic halide, (meth)
Acrylic acid chloride is preferably used. Such a (meth) acrylic halide is used in an amount of 0.8 to 10 times, preferably 1 to 3 times the molar amount of the alicyclic alcohol having a silicon substituent.

The reaction between the silicon-substituted alicyclic alcohol (III) and (meth) acrylic acid or (meth) acrylic halide is also preferably carried out in the same manner as described above, in the presence of the same basic compound as described above. The reaction is carried out in the presence or absence of a solvent.

In the reaction of the silicon-substituted alicyclic alcohol (III) with (meth) acrylic acid or (meth) acrylic halide, the basic compound is 0.8 to 10 times the molar amount of (meth) acrylic halide. , Preferably 1 to
Three times the molar amount is used. The reaction is usually performed at 0 to 150 ° C,
Preferably, it is carried out at a temperature of 0 to 80 ° C. The reaction time is
Usually, it is about 0.2 to 50 hours.

After completion of the reaction, excess or unreacted (meth) acrylic acid halide remaining in the reaction mixture is decomposed, if necessary, using an alcohol such as methanol, a solid substance is filtered, the filtrate is concentrated, and the solvent is removed. The basic compound of the reaction and the (meth) acrylic acid ester by-produced in the above decomposition operation are removed, for example, by distillation to obtain a silicon-substituted alicyclic (meth) acrylic acid represented by the general formula (II). An acid ester can be obtained.

In the present invention, the silicon-substituted alicyclic (meth) acrylic acid ester copolymer constituting the contact lens is the same as the silicon-substituted alicyclic (meth) acrylic acid ester (I ') described above. Can be obtained by copolymerizing the above-mentioned second monomer having copolymerizability with a general radical copolymerization method using a polymerization initiator. If necessary, before or after the polymerization, various stabilizers, pigments, thickeners and the like can be added to the reaction mixture.

In the present invention, in the production of a silicon-substituted alicyclic (meth) acrylate copolymer constituting a contact lens, if necessary, a small amount of a bifunctional or more polyfunctional compound may be used as a comonomer component. Poly (meth) acrylate, which is a reactive monomer, can be used. As such poly (meth) acrylate, for example, as a specific example, And the like.

Of these, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and the like are particularly preferably used.

Such a polyfunctional monomer is used in an amount of 40% by weight or less, preferably 20% by weight or less, if necessary, in the silicon-substituted (meth) acrylate copolymer.

In the production of the silicon substituent-containing (meth) acrylate copolymer constituting the contact lens according to the present invention, any of a thermal polymerization initiator and a photopolymerization initiator can be used as the polymerization initiator. Examples of the thermal polymerization initiator include azobisisobutyronitrile, azobiscyclohexanecarbonitrile, phenylazobisbutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, di-t-butyl peroxide, and t-butyl peroxide.
Butyl hydroperoxide and the like can be mentioned. Further, as the photopolymerization initiator, for example, a general formula (Wherein, R ⁸ represents an alkyl group), benzophenones such as benzophenone and benzoate, xanthones such as xanthone and thioxanthone, and p-hydroxyisobutyrylisopropylbenzene. Can be mentioned.

The reaction temperature of the thermal polymerization is usually 40 to 200 ° C, preferably 4 to 200 ° C.
5 to 120 ° C., and the radical initiator is usually present in an amount of 0.005 to 10% by weight, preferably 0.0
It is used in the range of 1 to 5% by weight. The time required for the polymerization is usually 0.5 to 5000 minutes, preferably 30 to 2000 minutes.

On the other hand, in the case of photopolymerization, the polymerization time, the type and amount of the monomer and the photopolymerization initiator to be used, and further, ultraviolet rays, infrared rays, γ rays, etc., differ depending on the type of light source used, for example, When the above-mentioned p-hydroxyisobutyrylisopropylbenzene is used as the photopolymerization initiator, practically, it is exposed to ultraviolet rays for a time ranging from several seconds to several minutes.
A copolymer having sufficient strength can be obtained. Also, a polymer can be obtained by a solution polymerization method.

The contact lens according to the present invention is obtained by injecting the above-mentioned monomer component and polymerization initiator together with other additives as necessary into a predetermined mold and polymerizing the same to obtain a copolymer. It can be obtained by cutting into a required shape and cutting and polishing. Further, it can also be obtained by a method such as polymerization molding using a contact lens mold having a predetermined shape.

The contact lens according to the present invention thus obtained is not only excellent in oxygen permeability, but also excellent in feeling of wearing and stain resistance to tear components as compared with conventional ones,
Since it is excellent in biocompatibility, it can be worn for a long time.

Effect of the Invention As described above, the contact lens according to the present invention contains a silicon-substituted alicyclic (meth) acrylate as an essential monomer component, and preferably, as a second monomer component, It is made of a copolymer containing methyl methacrylate component, and has excellent optical properties and oxygen permeability.
It is excellent in contamination resistance to bacteria, fungi, etc. as well as tear components such as lipids and mucins.

Effect of the Invention The silicon-substituted alicyclic (meth) acrylate copolymer according to the present invention, in particular, a copolymer containing at least a methyl methacrylate unit as the second comonomer component is improved in transparency. It is excellent and has high oxygen permeability, and is useful as a polymer constituting a medical oxygen permeable material, particularly, an oxygen permeable material such as a contact lens.

Examples Hereinafter, Examples of the present invention will be described together with Reference Examples showing the production of monomers for producing a silicon-substituted alicyclic (meth) acrylic acid ester copolymer. It is not limited at all by the examples.

Reference Example 1 (Production of 4-tris (trimethylsiloxy) siloxycyclohexanol) 300 ml of tetrahydrofuran as solvent and cyclohexane-1,4-
80 g (689 mmol) of diol and 25 ml of triethylamine (17
8 mmol), 57 g (171 mmol) of tris (trimethylsiloxy) silyl chloride was slowly added dropwise thereto at a temperature of 40 ° C. while stirring under a nitrogen stream in 5 hours, and then reacted for 2 hours. I let it.

A part of the obtained reaction mixture was sampled and analyzed by gas chromatography. As a result, no peak based on tris (trimethylsiloxy) silyl chloride was observed, and monoadduct and diadduct of silicon substituent were newly added. And a peak based on this ratio appeared at a ratio of 95/5.

After the reaction mixture was concentrated under reduced pressure to remove the solvent, excess hexane was added, and the mixture was washed repeatedly with a separating funnel, and the water tank was separated and removed.

After concentrating the obtained hexane layer, distillation under reduced pressure
-62 g of tris (trimethylsiloxy) siloxycyclohexanol were obtained as a colorless transparent liquid having a boiling point of 125-126 ° C / 0.1-0.2 mmHg. Gas chromatographic purity was 98.8%. FIG. 1 shows the infrared absorption spectrum.

Elemental analysis (C ₁₅ H ₃₈ O ₅ as Si ₄₎ C H Si theory 43.85 9.32 27.35 Found 43.78 9.29 27.19 Infrared absorption spectrum ^{νO-H 3320cm -1 νC-Si} 1250cm -1 νSi-O and νC-O 1160- 1000 cm ^-1 . Mass spectrometry M ⁺ 411 (Production of 4-tris (trimethylsiloxy) siloxycyclohexanyl methacrylate) Then, the inside of a 500-capacity four-necked flask equipped with a thermometer was purged with nitrogen, and the flask was placed under a nitrogen stream. 62 g (151 mmol) of 4-tris (trimethylsiloxy) siloxycyclohexanol
At the same time, 125 g (212 mmol) of tetrahydrofuran 125 and 23 g of methacrylic acid chloride were charged, and 25 g (250 mmol) of triethylamine was slowly added dropwise thereto over 4 hours while stirring in an ice bath. Thereafter, the mixture was stirred in an ice bath for 2 hours, and further reacted at room temperature for 3 hours.

Then, the reaction mixture was cooled again in an ice bath, and 7 ml of methanol was slowly added thereto over 1 hour to terminate the reaction.

The obtained reaction mixture was filtered, the solvent was distilled off under reduced pressure, then excess hexane was added, and the mixture was filtered.After that, hexane was again distilled off, concentrated, and further heated under reduced pressure. Then, volatiles are distilled off, and 4-tris (trimethylsiloxy) siloxycyclohexanitrile methacrylate 58
g was obtained. Gas chromatographic purity was 97.8%. FIG. 2 shows the infrared absorption spectrum.

Elemental analysis (as C ₁₉ H ₄₂ O ₆ Si ₄ ) CH Si theoretical 47.65 8.84 23.46 found 47.52 8.77 23.32 mass spectrometry M ⁺ 479 proton NMR spectrum (90 MHz, solvent CDCl ₃ , δ (pp
m)) Reference Example 2 (Production of 5-tris (trimethylsiloxy) siloxy-1-decalol) In Example 1, 250 g of tetrahydrofuran, 30 g of 1,5-decalindiol, 7.9 g of triethylamine and 20 g of tris (trimethylsiloxy) silyl chloride were used. Except for the above, in the same manner as in Example 1, 18 g of 5-tris (trimethylsiloxy) siloxy-1-decalol was obtained as a colorless liquid.

Boiling point 153~154 ℃ / 0.1~0.2mmHg Elemental analysis (C ₁₉ H ₄₄ O as ₅ Si ₄₎ C H Si theory 49.30 9.54 24.17 Found 49.21 9.48 24.08 Infrared absorption spectrum ^{νO-H 3250cm -1 νC-Si} 1250cm - ¹ νSi-O and νC-O 1160-1000cm ^-1 . Mass spectrometry M ⁺ 465 (Production of 5-tris (trimethylsiloxy) siloxy- ¹ -decanol methacrylate) Then, the above-mentioned 5-tris (trimethylsiloxy) siloxy-1 -14.6 g of 5-tris (trimethylsiloxy) siloxy-1-decalol methacrylate was used as a transparent liquid in the same manner as in Example 1 except that 15 g of decalol, 125 g of tetrahydrofuran, 5.4 g of methacrylic acid chloride and 7.0 g of triethylamine were used. Obtained. Gas chromatographic purity was 97.2%.

Elemental analysis (as C ₂₃ H ₄₈ O ₆ Si ₄ ) CH Si theoretical 51.83 9.08 21.08 actual 51.75 9.04 21.02 infrared absorption spectrum νC-O 1720 cm ^-1 νC = C 1640 cm ^-1 mass spectrometry M ⁺ 533 proton NMR spectrum ( 90 MHz, solvent CDCl ₃ , δ (pp
m)) Reference Example 3 (Production of 4-bis (trimethylsiloxy) methylsiloxycyclohexane-1-methanol) In Example 1, tetrahydrofuran 200, 25 g of 1,4-cyclohexanedimethanol, 12 g of triethylamine, and bis (trimethylsiloxy) silylmethyl chloride were used.
Except for using 16 g, 21 g of 4-bis (trimethylsiloxy) methylsiloxycyclohexane-1-methanol was obtained as a colorless liquid in the same manner as in Example 1.

Boiling point 126~130 ℃ / 1.0~2.0mmHg Elemental analysis (C ₁₉ H ₄₄ O as ₅ Si ₄₎ C H Si theory 49.40 9.95 23.11 Found 49.27 9.83 23.02 Infrared absorption spectrum ^{νO-H 3400cm -1 νC-Si} 1260cm - ¹ νSi-O and νC-O 1150-1000cm ^-1 . Mass spectrometry M ⁺ 365 (Production of 4-bis (trimethylsiloxy) methylsiloxycyclohexane-1-methanol methacrylate) Then, the above-mentioned 4-bis (trimethylsiloxy) methyl Except that 18 g of siloxycyclohexane-1-methanol, 150 g of tetrahydrofuran, 8 g of methacrylic chloride and 9 g of triethylamine were used,
17 g of 4-bis (trimethylsiloxy) methylsiloxycyclohexane-1-methanol methacrylate was obtained as a transparent liquid. Gas chromatographic purity was 98.4%.

Elemental analysis (as C ₁₉ H ₄₀ O ₅ Si ₃ ) CH Si theoretical 52.73 9.32 19.47 actual 52.66 9.19 19.33 infrared absorption spectrum νC-O 1720 cm ^-1 νC = C 1640 cm ^-1 mass spectrometry M ⁺ 433 proton NMR spectrum ( 90 MHz, solvent CDCl ₃ , δ (pp
m)) Reference Example 4 (Production of 4- (3,3,3-trifluoropropyl) dimethylsiloxycyclohexanol) In Example 1, tetrahydrofuran 30 was used as a solvent.
The reaction was carried out in the same manner as in Example 1 except that 0 ml, 50 g of 1,4-cyclohexanediol, 20 ml of triethylamine and 25 g of 3,3,3-trifluoropropyldimethylchlorosilane were used, and 4- (3,3, 26 g of 3-trifluoropropyl) dimethylsiloxycyclohexanol with a boiling point of 111 to 113
° C / 0.1-0.2 mmHg, obtained as a colorless transparent liquid.

Elemental analysis (C ₁₁ H ₂₁ SiF ₃ as O ₂₎ C H Si F theory 48.86 7.84 10.39 21.08 Found 48.89 7.87 10.32 21.04 IR spectrum ^{νO-H 3100-3600cm -1 νC-H} 2930,2880,2850cm -1 δC-H 1440 cm ^-1 νC-Si 1250 cm ^-1 νCF 1200 cm ^-1 . Mass spectrometry M ⁺ 270 proton NMR spectrum (90 MHz, solvent CDCl ₃ , δ (pp
m)) (Production of 4- (3,3,3-trifluoropropyl) dimethylsiloxycyclohexanyl methacrylate) Next, 25 g of the above 4- (3,3,3-trifluoropropyl) dimethylsiloxycyclohexanol and isopropyl as a solvent 125 ml of ether, methacrylic chloride 1
An esterification reaction was carried out in the same manner as in Example 1 except that 4.5 g and 15.0 g of triethylamine were used.

Hexane was added to the obtained reaction mixture, and water washing was repeatedly performed to separate an aqueous layer. Next, the organic layer was concentrated under reduced pressure, further heated under reduced pressure, and volatile components were distilled off to obtain 19 g of 4- (3,3,3-trifluoropropyl) dimethylsiloxycyclohexanyl methacrylate. Was. Gas chromatographic purity was 98.5%.

Elemental analysis (C ₁₅ H ₂₅ as _{OSiF 3 O 3) C H Si} F theory 53.22 7.46 8.30 16.84 Found 53.28 7.53 8.26 16.89 IR spectrum ^{νC-H 2950,2880,2850cm -1 δC-H} 1450cm -1 νC = O 1720 cm ^-1 νC-Si 1260 cm ^-1 . ΝC-F 1210 cm ^-1 . ΝC = C 1640 cm ^-1 Mass spectrometry M ⁺ 338 Proton NMR spectrum (90 MHz, solvent CDCl ₃ , δ (pp
m)) Reference Example 5 (Production of 4-bis (trimethylsiloxy) methylsiloxycyclohexanol) In Example 1, tetrahydrofuran 16 was used as a solvent.
The reaction was carried out in the same manner as in Example 1 except that 0 ml, 40 g of 1,4-cyclohexanediol, 11.5 g of triethylamine and 26.4 g of bis (trimethylsiloxy) methylsilyl chloride were used to obtain 4-bis (trimethylsiloxy) methyl. 27.2 g of siloxycyclohexanol with a boiling point of 141 ° C / 24 mmH
g, obtained as a colorless transparent liquid.

Elemental analysis (C ₁₃ H ₃₂ Si ₃ as O ₄₎ C H Si theory 46.37 9.60 25.03 Found 46.39 9.62 25.01 Infrared absorption spectrum ^{νO-H 3150-3550cm -1 νC-H} 2960,2910,2875cm -1 δC-H 1450,1380 cm ^-1 νC-Si 1255 cm ^-1 νSi-O 1100-1130 cm ^-1 . Mass spectrometry M ⁺ 337 proton NMR spectrum (90 MHz, solvent CDCl ₃ , δ (pp
m)) (Production of 4-bis (trimethylsiloxy) methylsiloxycyclohexanyl methacrylate) Next, 26 g of the above 4-bis (trimethylsiloxy) methylsiloxycyclohexanol, 60 ml of tetrahydrofuran as a solvent, 12.4 g of methacrylic acid chloride and 19 ml of triethylamine were used. An esterification reaction was carried out in the same manner as in Example 1 except for the above, to obtain 23 g of 4-bis (trimethylsiloxy) methylsiloxycyclohexanyl methacrylate as a transparent liquid.

Elemental analysis (C ₁₇ H ₃₆ Si ₃ as O ₅₎ C H Si theory 50.44 8.98 20.82 Found 50.46 8.96 20.84 Infrared absorption spectrum ^{νC-H 2960,2900,2875cm -1 δC-H} 1450,1380cm -1 νC = O 1720 cm ^-1 νC-Si 1255 cm ^-1 νC = C 1640 cm ^-1 νSi-O 1020-1125 cm ^-1 . Mass spectrometry M ⁺ 405 Proton NMR spectrum (90 MHz, solvent CDCl ₃ , δ (pp
m)) Example 1 4-Tris (trimethylsiloxy) obtained in Reference Example 1
As shown in Table 1, 73 parts by weight of siloxycyclohexanyl methacrylate were mixed with 20 parts by weight of methyl methacrylate, 1.0 part by weight of ethylene glycol dimethacrylate, and 6 parts by weight of methacrylic acid. 0.3 parts by weight of lonitrile was mixed and stirred to make it uniform.

The mixture was poured into a glass test tube, the inside of which was thoroughly purged with nitrogen, sealed, immersed in a thermostat, and heated at 40 ° C for 24 hours.
The polymerization was carried out at 65 ° C. for 48 hours, then at 90 ° C. for 24 hours. After cooling, the obtained round bar-shaped molded product is cut, cut,
Polishing was performed to obtain a contact lens having a diameter of 10 to 14 mm and a thickness of 0.2 mm as a test piece.

The oxygen permeability coefficient (DKg value (× 10 ⁻¹¹⁾
ml · cm / cm ² · sec · mmHg) was measured using a KAKENHI film oxygen permeability meter. The Vitzkars hardness was also measured with a Vickers hardness tester manufactured by Taiyo Tester Co., Ltd. Table 1 shows the measurement results together with the appearance and properties.

Comparative Examples 1 and 2 93 parts by weight of methyl methacrylate, 1 part by weight of ethylene glycol dimethacrylate and 6 parts by weight of methacrylic acid were copolymerized in the same manner as in Example 1, and the obtained methyl methacrylate copolymer was processed. Thus, a hard contact lens that has been widely used was obtained.

Table 1 shows the oxygen transmission coefficient and Vickers hardness of these hard contact lenses, as well as their appearance and properties.

Examples 2-5 As shown in Table 2, together with 4-tris (trimethylsiloxy) siloxycyclohexanyl methacrylate,
A contact lens was obtained in the same manner as in Example 1 except that various comonomers were used.

Table 2 shows the oxygen permeability coefficient and Vickers hardness of these test pieces together with their appearance and properties.

Examples 6 to 9 As shown in Table 3, various copolymers were obtained using the silicon-substituted (meth) acrylic acid ester obtained in Reference Examples 2 to 5, to obtain Examples 1 and 2. A contact lens was obtained in the same manner as in Example 1.

Table 3 shows the oxygen permeability coefficient and Vickers hardness of these test pieces together with their appearance and properties.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of an example of a silicon-substituent-containing alicyclic alcohol which is a raw material for producing a (meth) acrylate copolymer according to the present invention, and FIG. 3 shows an infrared absorption spectrum of an example of a contained alicyclic (meth) acrylic acid ester.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Hideo Mitsuyama 2-248 Mitsuhashi, Omiya City, Saitama Prefecture (56) References JP-A-56-51714 (JP, A) JP-A-62-215231 (JP, A) ( 58) Surveyed field (Int.Cl. ⁶ , DB name) G02C 7/04

Claims (4)

(57) [Claims] 1. The compound of the general formula (I) (Wherein, R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrocarbon group having 0 to 3 carbon atoms, and Cy is a carbon atom having 3 to 20 carbon atoms.
Alicyclic hydrocarbon group, R ⁴ , R ⁵ and R ⁶ are each independently a hydrocarbon group having 1 to 6 carbon atoms, a fluoroalkyl group, an alkoxy group or (Wherein, R ⁷ independently represents an alkyl group having 1 to 3 carbon atoms, a fluoroalkyl group or an alkoxy group, and n represents an integer of 1 to 10). A contact lens comprising a silicon-substituted alicyclic (meth) acrylate copolymer containing a structural unit represented by the following formula: (A) General formula (I) (Wherein, R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrocarbon group having 0 to 3 carbon atoms, and Cy is a carbon atom having 3 to 20 carbon atoms.
Alicyclic hydrocarbon group, R ⁴ , R ⁵ and R ⁶ are each independently a hydrocarbon group having 1 to 6 carbon atoms, a fluoroalkyl group, an alkoxy group or (Wherein, R ⁷ independently represents an alkyl group having 1 to 3 carbon atoms, a fluoroalkyl group or an alkoxy group, and n represents an integer of 1 to 10). A) alicyclic (meth) acrylate units containing a silicon substituent represented by the formula: and (b) a general formula (In the formula, R ¹ is the same as described above, and R represents a hydrogen, an alkyl group, an alkyl group having a hydroxyl group, a cycloalkyl group or an alkyl group having fluorine.) A contact lens comprising a silicon-substituted alicyclic (meth) acrylate copolymer containing a (meth) acrylate unit. 3. The contact lens according to claim 2, wherein the (meth) acrylate unit is a methyl methacrylate unit. 4. The contact lens according to claim 1, wherein the silicon-substituted alicyclic (meth) acrylate copolymer contains bifunctional or higher poly (meth) acrylate units. .