JP2901359B2 - Ophthalmic lens materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This invention relates to ophthalmic lens materials. More specifically, the present invention relates to an ophthalmic lens material having high oxygen permeability and high strength and suitable for use as, for example, a contact lens, an intraocular lens, an artificial cornea, and the like.

[0002]

2. Description of the Related Art Conventionally, polymethyl methacrylate has been used as a material for hard contact lenses because of its excellent optical characteristics. However, the material itself has almost no oxygen permeability and is required for metabolism of the cornea. It was difficult to supply oxygen.

[0003] Therefore, as a contact lens capable of solving such a drawback, a lens made of a copolymer such as siloxanyl methacrylate or fluoroalkyl methacrylate having excellent oxygen permeability has been widely used today.

However, when a contact lens is made of a material composed of such a silicone-based monomer or a fluorine-based monomer, the strength tends to decrease, and the contact lens may be damaged when the contact lens is washed. there were.

[0005] In addition to soft contact lenses, soft contact lenses are known as contact lenses, and soft contact lenses have the advantages of being soft and easy to fit into the cornea, and providing an excellent feeling of wearing. Generally, most of soft contact lenses absorb water and become soft, but such a water-containing soft contact lens has not so high oxygen permeability and may hinder corneal metabolism. In recent years, attempts have been made to increase the water content and improve the oxygen permeability, but there is a problem that the strength decreases as the water content increases, and that bacteria and the like easily propagate in the material.

Therefore, in order to solve such a problem,
A soft contact lens made of a soft material containing almost no water has been proposed, but such a non-hydrous soft contact lens still has insufficient mechanical strength.

As materials having relatively high oxygen permeability and mechanical strength, in addition to those described above, an ethylenic polymerizable group is introduced into both ends of a organosiloxane or at the end of a branched chain via a urethane bond or the like. Made of a copolymer of a mixture of a silicone macromonomer and a water-insoluble monomer and / or a water-soluble monomer (JP-A-59-102914, JP-A-63-297411), Silicone macromonomer having a polymerizable group introduced through a urethane bond (JP-A-59-229524)
It has been known.

Generally, a urethane bond gives high hardness to a material containing the urethane bond due to a hydrogen bond or the like.

However, the conventional silicone macromonomer has no urethane bond in the middle of the silicone chain, so that the content of the urethane bond per molecule is small, and sufficient strength cannot be imparted to the material. There are drawbacks. Therefore, in order to improve the strength,
If an attempt is made to increase the amount of urethane bonds, the amount of such a silicone macromonomer will inevitably increase, and it will be difficult to dissolve the silicone macromonomer in other copolymer components, and the resulting material will become cloudy. There is a problem.

[0010]

SUMMARY OF THE INVENTION In view of the above-mentioned prior art, the inventors of the present invention have developed an ophthalmic preparation which is excellent not only in transparency but also simultaneously in both oxygen permeability and mechanical strength. As a result of intensive studies on lens materials, a copolymer of a specific polysiloxane macromonomer and a monomer having an unsaturated double bond copolymerizable with the specific polysiloxane macromonomer has all of the above physical properties at the same time. And completed the present invention.

[0011]

That SUMMARY OF THE INVENTION The present invention has the general formula ^{(I): A 1 - U} 1 - (-S 1 - U 2 -) n - S 2 - U 3 - A 2 (I) ( wherein in, A ¹ is the general formula ^{(II): Y 21 -R 31} - (II) ( wherein, Y ²¹ is acryloyloxy group, methacryloyloxy group, a vinyl group or an allyl group, R ³¹ is 2 carbon atoms
6 straight or branched chain represents an alkylene group having) a group represented by; A ² of the general formula ^{(III): Y 22 -R 34} - (III) ( wherein, Y ²² is acryloyloxy group, methacryloyloxy Group, vinyl group or allyl group, R ³⁴ has 2 to 2 carbon atoms.
Groups represented by an alkylene group) having 6 linear or branched; U ¹ is the general formula ^{(IV): - X 21 -E} 21 -X 25 -R 32 - (IV) ( wherein, X ²¹ Is a covalent bond, an oxygen atom or an alkylene glycol group, and E ²¹ is a -NHCO- group (in this case,
X ²¹ is a covalent bond, E ²¹ forms a urethane bond with X ²⁵ ) or a divalent group derived from a diisocyanate selected from the group consisting of a saturated aliphatic system, an alicyclic system and an aromatic system ( Provided that X ²¹ is an oxygen atom or an alkylene glycol group, E ²¹ forms a urethane bond between X ²¹ and X ²⁵ ); X ²⁵ is an oxygen atom or an alkylene glycol group; R ³² Represents a linear or branched alkylene group having 1 to 6 carbon atoms); S ¹ and S ² each independently represent a general formula (VII):

[0012]

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(Wherein R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are each independently an alkyl or phenyl group having 1 to 3 carbon atoms, K is an integer of 1 to 1500; Is 0-1500
And K + L is an integer from 1 to 1500); U ²
The general formula ^{(V): - R 37 -X} 27 -E 24 -X 28 -R 38 - (V) ( wherein, R ³⁷ and R ³⁸ are 1 to carbon atoms independently
X ²⁷ and X ²⁸ each independently represent an oxygen atom or an alkylene glycol group; E ²⁴ is selected from the group consisting of a saturated aliphatic system, an alicyclic system and an aromatic system A divalent group derived from diisocyanate (where E ²⁴ forms a urethane bond between X ²⁷ and X ²⁸ ); U ³ has the general formula (VI): -R ³³ -X ^{26 -E 22 -X 22 - (VI} ) ( wherein, R ³³ is an alkylene group having a straight chain or branched chain of 1 to 6 carbon atoms, X ²² is a covalent bond, an oxygen atom or an alkylene glycol group, X ²⁶ is An oxygen atom or an alkylene glycol group, E ²² is an —NHCO— group (where X ²² is a covalent bond and E ²² forms a urethane bond with X ²⁶ ), or a saturated aliphatic group, 2 derived from a diisocyanate selected from the group consisting of a cyclic system and an aromatic system A group represented by a valent group (where X ²² is an oxygen atom or an alkylene glycol group, and E ²² forms a urethane bond between X ²² and X ²⁶ ),
n is an integer of 1 or more), and a polysiloxane macromonomer having a polymerizable group bonded to the siloxane main chain through one or two urethane bonds; The present invention relates to an ophthalmic lens material comprising a copolymer with a monomer having a heavy bond.

[0014]

Operation and Examples As described above, the ophthalmic lens of the present invention has the general formula (I): A ¹ -U ¹ -(-S ¹ -U ^2- ) _n -S ² -U ³ -A ² (I) (wherein, A ¹ is the general formula ^{(II): Y 21 -R 31} - (II) ( wherein, Y ²¹ is acryloyloxy group, methacryloyloxy group, a vinyl group or an allyl group, R ³¹ is a carbon Number 2
6 straight or branched chain represents an alkylene group having) a group represented by; A ² of the general formula ^{(III): Y 22 -R 34} - (III) ( wherein, Y ²² is acryloyloxy group, methacryloyloxy Group, vinyl group or allyl group, R ³⁴ has 2 to 2 carbon atoms.
Groups represented by an alkylene group) having 6 linear or branched; U ¹ is the general formula ^{(IV): - X 21 -E} 21 -X 25 -R 32 - (IV) ( wherein, X ²¹ Is a covalent bond, an oxygen atom or an alkylene glycol group, and E ²¹ is a -NHCO- group (in this case,
X ²¹ is a covalent bond, E ²¹ forms a urethane bond with X ²⁵ ) or a divalent group derived from a diisocyanate selected from the group consisting of a saturated aliphatic system, an alicyclic system and an aromatic system ( Provided that X ²¹ is an oxygen atom or an alkylene glycol group, E ²¹ forms a urethane bond between X ²¹ and X ²⁵ ); X ²⁵ is an oxygen atom or an alkylene glycol group; R ³² Represents a linear or branched alkylene group having 1 to 6 carbon atoms); S ¹ and S ² each independently represent a general formula (VII):

[0015]

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(Wherein R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are each independently an alkyl or phenyl group having 1 to 3 carbon atoms, K is an integer of 1 to 1500; Is 0-1500
And K + L is an integer from 1 to 1500); U ²
The general formula ^{(V): - R 37 -X} 27 -E 24 -X 28 -R 38 (V) ( wherein, R ³⁷ and R ³⁸ are 1 to carbon atoms independently
X ²⁷ and X ²⁸ each independently represent an oxygen atom or an alkylene glycol group; E ²⁴ is selected from the group consisting of a saturated aliphatic system, an alicyclic system and an aromatic system A divalent group derived from diisocyanate (where E ²⁴ forms a urethane bond between X ²⁷ and X ²⁸ ); U ³ has the general formula (VI): -R ³³ -X ^{26 -E 22 -X 22 - (VI} ) ( wherein, R ³³ is an alkylene group having a straight chain or branched chain of 1 to 6 carbon atoms, X ²² is a covalent bond, an oxygen atom or an alkylene glycol group, X ²⁶ is An oxygen atom or an alkylene glycol group, E ²² is an —NHCO— group (where X ²² is a covalent bond and E ²² forms a urethane bond with X ²⁶ ), or a saturated aliphatic group, 2 derived from a diisocyanate selected from the group consisting of a cyclic system and an aromatic system A group represented by a valent group (where X ²² is an oxygen atom or an alkylene glycol group, and E ²² forms a urethane bond between X ²² and X ²⁶ ),
n is an integer of 1 or more), and a polysiloxane macromonomer having a polymerizable group bonded to the siloxane main chain through one or two urethane bonds; It comprises a copolymer with a monomer having a heavy bond.

The polysiloxane macromonomer has an elastic bond called a urethane bond, reinforces the siloxane portion without impairing the flexibility and oxygen permeability of the material, and imparts elastic resilience to the brittleness. It is a component that imparts the property of improving mechanical strength. In addition, since the polysiloxane macromonomer has a silicone chain in the molecular chain, it imparts high oxygen permeability.

The polysiloxane macromonomer has polymerizable groups at both ends of the molecule, and copolymerizes other copolymerized components via such polymerizable groups. Not only physical reinforcement effect,
It has an excellent property of providing a reinforcing effect by chemical bonding.

The polysiloxane macromonomer is a compound represented by the general formula (I).

[0020] In the general formula (I), A ¹ is the general formula ^{(II): Y 21 -R 31} - (II) ( wherein, Y ²¹ and R ³¹ are as defined above) is a group represented by and a ² is the formula ^{(III): Y 22 -R 34} - (III) ( wherein, Y ²² and R ³⁴ are as defined above) is a group represented by. Y ²¹ and Y ²² are both polymerizable groups, but are acryloyloxy, methacryloyloxy and vinyl in that they can be easily copolymerized with a monomer having a copolymerizable unsaturated double bond. Groups are particularly preferred. R ³¹ and R ³⁴ are both linear or branched alkylene groups having 2 to 6 carbon atoms.

U ¹ , U ² and U ³ each represent a group containing a urethane bond in the molecular chain of the polysiloxane macromonomer.

In U ¹ and U ³ , E ²¹ and E ²²
, As described above, are each -NHCO- group or a saturated aliphatic, alicyclic and divalent groups of the diisocyanate-derived selected from the group of aromatic, in U ^2, E
²⁴ represents a divalent group derived from diisocyanate selected from the group consisting of a saturated aliphatic system, an alicyclic system and an aromatic system. Here, the divalent group derived from diisocyanate selected from the group consisting of saturated aliphatic, alicyclic and aromatic is, for example, a saturated aliphatic group such as ethylene diisocyanate, 1,3-diisocyanate propane and hexamethylene diisocyanate. Aromatic diisocyanate; 1,2-diisocyanatocyclohexane, bis (4-isocyanatocyclohexyl)
Alicyclic diisocyanates such as methane and isophorone diisocyanate; aromatic diisocyanates such as toluene diisocyanate and 1,5-diisocyanate naphthalene; and unsaturated aliphatic diisocyanates such as 2,2'-diisocyanate diethyl fumarate. Of these, hexamethylene diisocyanate, tolylene diisocyanate and isophorone diisocyanate are preferred because they are relatively easily available and easy to impart strength.

In U ¹ , when E ²¹ is a —NHCO— group, X ²¹ is a covalent bond, and E ²¹ is represented by X ²⁵ and a formula: —NH—
Form a urethane bond represented by COO-. When E ²¹ is a divalent group derived from the diisocyanate, X ²¹ is an oxygen atom or an alkylene glycol group, and E ²¹ forms a urethane bond between X ²¹ and X ²⁵ . X ²⁵ is an oxygen atom or an alkylene glycol group, and R ³² is a linear or branched alkylene group having 1 to 6 carbon atoms.

In U ² , R ³⁷ and R ³⁸ are each a linear or branched alkylene group having 1 to 6 carbon atoms. X ²⁷ and X ²⁸ are an oxygen atom or an alkylene glycol group, respectively. E ²⁴ is a divalent group derived from the diisocyanate, and a urethane bond is formed between X ²⁷ and X ²⁸ .

In U ³ , R ³³ is a linear or branched alkylene group having 1 to 6 carbon atoms. X ²⁶ is an oxygen atom or an alkylene glycol group. E ²² is, -N
When it is an HCO- group, it forms a urethane bond with X ²⁶ . Further, when E ²² is a divalent group derived from the diisocyanate, E ²² forms a urethane bond between the X ²² and X ^26. X ²² is an oxygen atom or an alkylene glycol group.

Here, X ²¹ , X ²⁵ , X ²⁷ , X ²⁸ , X
^{As the} alkylene glycol at ²² and X ²⁶ ,
For example the general formula _{(XII): -O- (C x} H 2x -O) y - (XII) ( wherein, x is an integer from 2 to 4, y is an integer of 1 to 5)
And the like. The general formula
In the formula (XII), when y is an integer of 6 or more, the oxygen permeability or mechanical strength tends to decrease. In the present invention, y is an integer of 1 to 5, particularly 1 to 5.
It is preferably an integer of 3.

S ¹ and S ² are each independently a group represented by the above general formula (VII). In the general formula (VII), K is an integer of 1 to 1500, L is an integer of 0 to 1500, and K + L is an integer of 1 to 1500. When K + L is larger than 1500, the molecular weight of the polysiloxane macromonomer becomes too large, and the compatibility with the monomer having a copolymerizable unsaturated double bond becomes poor. The polymer does not dissolve in water or becomes cloudy at the time of polymerization, making it difficult to obtain a uniform and transparent ophthalmic lens material. When the value is 0, the oxygen permeability of the obtained ophthalmic lens material becomes low. In addition, flexibility tends to decrease. K + L is preferably an integer of 2 to 500, more preferably 5 to 100. K is preferably 1
~ 250, more preferably an integer of 2 ~ 50, L is
It is preferably an integer of 1 to 250, more preferably 3 to 50.

In the general formula (I),-(-S ^1-
The number n of units represented by U ² -)-is an integer of 1 or more. When n is 0, there is no urethane bond in the middle of the siloxane molecular chain, and sufficient strength cannot be given as an ophthalmic lens material. When n is larger than 10, the minimum number of silicone chains necessary for securing oxygen permeability is inevitably increased in the molecule, and the compatibility with other copolymer components is reduced. The resulting ophthalmic lens material becomes cloudy.

The amount of the polysiloxane macromonomer is 100 parts by weight (parts by weight,
The same applies hereinafter), 3 to 70 parts, preferably 5 to 50 parts, more preferably 10 to 40 parts. When the amount of the polysiloxane macromonomer is less than the above range, the resulting ophthalmic lens material has insufficient oxygen permeability and mechanical strength. It becomes difficult to dissolve the copolymer component,
The resulting material becomes cloudy.

The monomer having an unsaturated double bond copolymerizable with the polysiloxane macromonomer (hereinafter, referred to as another copolymer component) is used to further impart oxygen permeability to the obtained ophthalmic lens material. To impart hardness or softness, impart hydrophilicity, further impart anti-lipid contamination, etc., cross-link to provide improved strength and durability, and to absorb ultraviolet light And a component that imparts color.

For example, in the case where the hardness is adjusted so as to impart hardness or softness or flexibility, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
Isopropyl (meth) acrylate, n-propyl (meth) acrylate, isobutyl (meth) acrylate,
n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate,
n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, tert-pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, Nonyl (meth) acrylate,
Stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxypropyl ( Meth) acrylate, ethylthioethyl (meth) acrylate,
Linear, such as methylthioethyl (meth) acrylate,
Branched or cyclic alkyl (meth) acrylate,
Alkoxyalkyl (meth) acrylate, alkylthioalkyl (meth) acrylate; styrene; α-methylstyrene; alkylstyrene such as methylstyrene, ethylstyrene, propylstyrene, butylstyrene, t-butylstyrene, isobutylstyrene, pentylstyrene; methyl -α-methylstyrene, ethyl-α-methylstyrene, propyl-α-methylstyrene, butyl-
α-methylstyrene, t-butyl-α-methylstyrene,
One or more alkyl-α-methylstyrenes such as isobutyl-α-methylstyrene and pentyl-α-methylstyrene are selected and used. In addition, "-(meth) acrylate" in this specification means "-acrylate and / or methacrylate", and the same applies to other (meth) acrylate derivatives. For example, when obtaining a soft contact lens or the like, these other copolymer components have a glass transition point (hereinafter, referred to as Tg) when formed into a homopolymer.
Those having a temperature of 40 ° C. or lower are preferably used. For example, when a hard contact lens or the like is to be obtained, a polymer having a Tg higher than 40 ° C. is preferably used when a homopolymer is used. The amount of these other copolymer components used is 100% of the total amount of the monomers used for the polymerization.
The amount is 5 to 60 parts, preferably 10 to 50 parts, particularly preferably 20 to 40 parts per part. When the amount is less than the lower limit, the obtained ophthalmic lens material tends to be brittle, and when the amount is more than the upper limit, the relative amount of the polysiloxane macromonomer is relatively large. Oxygen permeability and mechanical strength tend to decrease due to a decrease in the amount used.

When oxygen permeability is additionally provided to the obtained ophthalmic lens material, for example, pentamethyldisiloxanylmethyl (meth) acrylate, trimethylsiloxydimethylsilylpropyl (meth) acrylate, Methyl bis (trimethylsiloxy)
Silylpropyl (meth) acrylate, tris (trimethylsiloxy) silylpropyl (meth) acrylate,
Mono (methylbis (trimethylsiloxy) siloxy) bis (trimethylsiloxy) silylpropyl (meth) acrylate, tris [methylbis (trimethylsiloxy)
[Siloxy] silylpropyl (meth) acrylate, methyl [bis (trimethylsiloxy)] silylpropylglyceryl (meth) acrylate, tris (trimethylsiloxy) silylpropylglyceryl (meth) acrylate, mono [methylbis (trimethylsiloxy) siloxy] bis (trimethyl) Siloxy) silylpropyl glyceryl (meth) acrylate, trimethylsilylethyltetramethyldisiloxanylpropyl glyceryl (meth)
Acrylate, trimethylsilylmethyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, trimethylsilylpropylglyceryl (meth) acrylate, pentamethyldisiloxanylpropylglyceryl (meth) acrylate, methylbis (trimethylsiloxy) silylethyltetramethyldisiloxanyl Methyl (meth) acrylate, tetramethyltriisopropylcyclotetrasiloxanylpropyl (meth) acrylate, tetramethyltriisopropylcyclotetrasiloxybis (trimethylsiloxy) silylpropyl (meth) acrylate, trimethylsiloxydimethylsilylpropyl (meth) acrylate, etc. Organopolysiloxane-containing alkyl (meth) acrylates such as trimethylvinylsilane Le Kill vinylsilane; formula (VII
I):

[0033]

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(Wherein p is an integer of 1 to 15, q is 0 or 1, and r is an integer of 1 to 15). In the organopolysiloxane-containing styrene derivative represented by the general formula (VIII), when p or r is an integer of 16 or more, its purification and synthesis become difficult, and further, the hardness of the obtained ophthalmic lens material decreases. When q is an integer of 2 or more, the synthesis of the organopolysiloxane-containing styrene derivative tends to be difficult. Representative examples of the compound represented by the general formula (VIII) include, for example, tris (trimethylsiloxy) silylstyrene, bis (trimethylsiloxy) methylsilylstyrene, (trimethylsiloxy) dimethylsilylstyrene, trimethylsilylstyrene, tris (trimethylsiloxy) Siloxanyldimethylsilylstyrene, [bis (trimethylsiloxy) methylsiloxanyl] dimethylsilylstyrene, pentamethyldisiloxanylstyrene, heptamethyltrisiloxanylstyrene, nonamethyltetrasiloxanylstyrene, pentadecamethylhepta Siloxanyl styrene, heneicosamethyl decasiloxanyl styrene, heptacosa methyl tridecasiloxanyl styrene, hentria contamethyl pentadecasiloxanyl styrene, trimethyl Siloxypentamethyldisiloxymethylsilylstyrene, tris (pentamethyldisiloxy) silylstyrene, (tristrimethylsiloxy) siloxanylbis (trimethylsiloxy) silylstyrene, bis (heptamethyltrisiloxy) methylsilylstyrene, tris (methylbistrimethylsiloxysiloxy) ) Silylstyrene, trimethylsiloxybis (tristrimethylsiloxysiloxy) silylstyrene, heptakis (trimethylsiloxy) trisiloxanylstyrene, nonamethyltetrasiloxyundecylmethylpentasiloxymethylsilylstyrene, tris (tristrimethylsiloxysiloxy) silylstyrene, (Tristrimethylsiloxyhexamethyl) tetrasiloxy (tristrimethylsiloxy) siloxytrimethyl B silyl styrene, Nonakisu (trimethylsiloxy)
Tetrasiloxanylstyrene, bis (tridecamethylhexasiloxy) methylsilylstyrene, heptamethylcyclotetrasiloxanylstyrene, heptamethylcyclotetrasiloxybis (trimethylsiloxy) silylstyrene, tripropyltetramethylcyclotetrasiloxanylstyrene And so on. The amount of these other copolymerization components to be used is 2 to 50 parts, preferably 5 to 40 parts, particularly preferably 10 to 30 parts, based on 100 parts of the total amount of the monomers to be subjected to the polymerization. When the amount is less than the lower limit, the effect of improving the oxygen permeability by adding the other copolymer component is not so expected, and when the amount is larger than the upper limit, The use amount of the polysiloxane macromonomer is relatively small, and the mechanical strength tends to decrease.

In order to impart hydrophilicity to the obtained ophthalmic lens material, a hydroxyalkyl (eg, 2-hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate) (Meth) acrylate; (alkyl) aminoalkyl (meth) acrylate such as 2-dimethylaminoethyl (meth) acrylate and 2-butylaminoethyl (meth) acrylate; alkyl (meth) acrylamide such as N, N-dimethylacrylamide; propylene Polyglycol mono (meth) acrylates such as glycol mono (meth) acrylate; vinylpyrrolidone; (meth) acrylic acid; maleic anhydride; maleic acid; fumaric acid; fumaric acid derivatives; aminostyrene; Alternatively, two or more kinds are used in combination. The amount of these other copolymer components to be used is 2 to 50 parts, preferably 3 to 30 parts, more preferably 5 to 20 parts, based on 100 parts of the total amount of monomers to be subjected to polymerization. When the amount is smaller than the lower limit, the effect of improving the hydrophilicity by adding the other copolymer component is not so much expected, and when the amount is larger than the upper limit, the relative amount is relatively small. Therefore, the amount of the polysiloxane macromonomer used tends to be small, so that high oxygen permeability and high mechanical strength tend not to be expected.

In order to impart anti-lipid contamination to the obtained ophthalmic lens material, for example, the general formula (IX): CH ₂ = CR ₇ COOC _s H _{(2s-t-u + 1)} F _t (OH) _u (IX) (wherein, R ₇ is a hydrogen atom or CH ₃ , s is an integer of 1 to 15, t is an integer of 1 to (2s + 1), and u is an integer of 0 to 2) For example, a fluorine-containing monomer represented by Specific examples of the monomer represented by the general formula (IX) include, for example, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2 , 3,3-Tetrafluoro-t-pentyl (meth) acrylate, 2,2,3,4,4,4-hexafluorobutyl (meth) acrylate, 2,2,3,4,4,4-hexafluoro -t
-Hexyl (meth) acrylate, 2,3,4,5,5,5-hexafluoro-2,4-bis (trifluoromethyl) pentyl (meth) acrylate, 2,2,3,3,4,4- Hexafluorobutyl (meth) acrylate, 2,2,2,2 ', 2', 2'-hexafluoroisopropyl (meth) acrylate, 2,2,3,
3,4,4,4-heptafluorobutyl (meth) acrylate,
2,2,3,3,4,4,5,5-octafluoropentyl (meth) acrylate, 2,2,3,3,4,4,5,5,5-nonafluoropentyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl (meth) acrylate, 3,3,4,4,5,
5,6,6,7,7,8,8-dodecafluorooctyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-trideca Fluorooctyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6,
7,7,7-tridecafluoroheptyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-hexadecafluoro Decyl (meth) acrylate, 3,3,4,4,5,5,6,6,
7,7,8,8,9,9,10,10,10-Heptadecafluorodecyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8,8 , 9,9,10,1
0,11,11-octadecafluoroundecyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11, 11,11
-Nonadecafluoroundecyl (meth) acrylate,
3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12-eicosafluorododecyl (meth) acrylate, 2 -Hydroxy-4,4,5,5,6,7,7,7-octafluoro-6-trifluoromethylheptyl (meth) acrylate, 2-hydroxy
-4,4,5,5,6,6,7,7,8,9,9,9-dodecafluoro-8-trifluoromethylnonyl (meth) acrylate, 2-hydroxy-4,4,5,5 , 6,6,7,7,8,8,9,9,10,11,11,11-hexadecafluoro-10-trifluoromethylundecyl (meth) acrylate.

The amount of the fluorine-containing monomer to be used is 5 to 80 parts, preferably 10 to 60 parts, more preferably 30 to 50 parts, based on 100 parts of the total amount of the monomers to be subjected to the polymerization.
If the amount is less than the lower limit,
If the obtained ophthalmic lens material is not sufficiently imparted with anti-lipid contaminating properties, and if it is more than the above upper limit, the amount of the polysiloxane macromonomer used is relatively small, resulting in high oxygen permeability and high oxygen permeability. There is a tendency that high mechanical strength cannot be expected.

In order to impart further enhanced mechanical strength and durability to the obtained ophthalmic lens material, other copolymer components such as ethylene glycol di (meth) acrylate and diethylene glycol di (meth) Acrylate, triethylene glycol di (meth)
Acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, methacryloyl oxydiethyl acrylate, divinylbenzene, diallyl phthalate , Diallyl adipate, triallyl isocyanurate, α-methylene-N-
Vinylpyrrolidone, 4-vinylbenzyl (meth) acrylate, 3-vinylbenzyl (meth) acrylate, 2,2-bis (p- (meth) acryloyloxyphenyl) hexafluoropropane, 2,2-bis (m- (meta ) Acryloyloxyphenyl) hexafluoropropane, 2,2-bis (o-
(Meth) acryloyloxyphenyl) hexafluoropropane, 2,2-bis (p- (meth) acryloyloxyphenyl) propane, 2,2-bis (m- (meth) acryloyloxyphenyl) propane, 2,2-bis (O- (meth) acryloyloxyphenyl) propane, 1,4-bis (2- (meth) acryloyloxyhexafluoroisopropyl)
Benzene, 1,3-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene, 1,2-bis (2-
(Meth) acryloyloxyhexafluoroisopropyl) benzene, 1,4-bis (2- (meth) acryloyloxyisopropyl) benzene, 1,3-bis (2- (meth) acryloyloxyisopropyl) benzene, 1,2-bis (2-
Crosslinking agents such as (meth) acryloyloxyisopropyl) benzene are used, and these crosslinking agents are used alone or in combination of two or more. The compounding amount of the crosslinking agent is 0.01 to 10 with respect to 100 parts of all monomers subjected to polymerization.
Parts, preferably 0.05 to 8 parts, more preferably 0.1 to 5 parts.
Department. If the amount of the crosslinking agent is less than the lower limit, the effect of adding the crosslinking agent is not sufficiently exhibited, and if the amount exceeds the upper limit, the material tends to become brittle.

Further, in order to absorb or color ultraviolet rays in the obtained ophthalmic lens material, other copolymerizable components such as a polymerizable ultraviolet absorber, a polymerizable dye, and a polymerizable ultraviolet absorbing dye are used. May be used.

Specific examples of the polymerizable ultraviolet absorber include, for example, 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- (meth) acryloyloxy-5-tert-butylbenzophenone, Hydroxy-4- (meth) acryloyloxy-2 ', 4'-dichlorobenzophenone, 2-hydroxy-4- (2'-hydroxy
Benzophenone-based polymerizable ultraviolet absorbers such as -3 '-(meth) acryloyloxypropoxy) benzophenone;
2- (2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2'
-Hydroxy-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (
2'-hydroxy-5 '-(meth) acryloyloxypropylphenyl) -2H-benzotriazole, 2- (2'-
Hydroxy-5 '-(meth) acryloyloxypropyl
Benzotriazole polymerizable ultraviolet absorbers such as -3'-tert-butylphenyl) -5-chloro-2H-benzotriazole; salicylic acid derivative polymerizable ultraviolet absorbers such as phenyl 2-hydroxy-4-methacryloyloxymethylbenzoate Agents; other polymerizable ultraviolet absorbers such as 2-cyano-3-phenyl-3- (3 '-(meth) acryloyloxyphenyl) propenyl acid methyl ester;
These polymerizable ultraviolet absorbers are used alone or in combination of two or more.

Specific examples of the polymerizable dye include, for example, 1-phenylazo-4- (meth) acryloyloxynaphthalene, 1-phenylazo-2-hydroxy-3- (meth) acryloyloxynaphthalene, 1-naphthylazo-2- Hydroxy-3- (meth) acryloyloxynaphthalene, 1-
(Α-anthrylazo) -2-hydroxy-3- (meth) acryloyloxynaphthalene, 1-((4 ′-(phenylazo) -phenyl) azo) -2-hydroxy-3- (meth) acryloyloxynaphthalene, 1- (2 ', 4'-xylylazo) -2- (meth) acryloyloxynaphthalene, 1-
(O-tolylazo) -2- (meth) acryloyloxynaphthalene, 2- (m- (meth) acryloylamide-anilino) -4,6-bis (1 '-(o-tolylazo) -2'-naphthylamino) -1,3,5-triazine, 2- (m-vinylanilino) -4
-(4'-nitrophenylazo) -anilino) -6-chloro
-1,3,5-triazine, 2- (1 '-(o-tolylazo) -2'-naphthyloxy) -4- (m-vinylanilino) -6-chloro-
1,3,5-triazine, 2- (p-vinylanilino) -4- (1'-
(o-tolylazo) -2'naphthylamino) -6-chloro-1,3,
5-triazine, N- (1 '-(o-tolylazo) -2'-naphthyl) -3-vinylphthalic acid monoamide, N- (1'-(o-tolylazo) -2'-naphthyl) -6-vinylphthalic acid Monoamide, 3-vinylphthalic acid-(4 '-(p-sulfophenylazo) -1'-naphthyl) monoester, 6-vinylphthalic acid
-(4 '-(p-Sulfophenylazo) -1'-naphthyl) monoester, 3- (meth) acryloylamide-4-phenylazophenol, 3- (meth) acryloylamide-4-
(8'-Hydroxy-3 ', 6'-disulfo-1'-naphthylazo) -phenol, 3- (meth) acryloylamide-4-
(1'-phenylazo-2'-naphthylazo) -phenol, 3- (meth) acryloylamide-4- (p-tolylazo) phenol, 2-amino-4- (m- (2'-hydroxy-
1'-naphthylazo) anilino) -6-isopropenyl-1,
3,5-triazine, 2-amino-4- (N-methyl-p- (2'-hydroxy-1'-naphthylazo) anilino) -6-isopropenyl-1,3,5-triazine, 2-amino- 4- (m- (4'-hydroxy-1'-phenylazo) anilino) -6-isopropenyl-1,3,5-triazine, 2-amino-4- (N-methyl-p
-(4'-hydroxyphenylazo) anilino) -6-isopropenyl-1,3,5-triazine, 2-amino-4- (m- (3'-
Methyl-1'-phenyl-5'-hydroxy-4'-pyrazolylazo) anilino) -6-isopropenyl-1,3,5-triazine, 2-amino-4- (N-methyl-p- (3 ' -Methyl-1 '
-Phenyl-5'-hydroxy-4'-pyrazolylazo) anilino) -6-isopropenyl-1,3,5-triazine, 2-amino-4- (p-phenylazoanilino) -6-isopropenyl- Azo-based polymerizable dyes such as 1,3,5-triazine and 4-phenylazo-7- (meth) acryloylamide-1-naphthol; 1,5-bis ((meth) acryloylamino) -9,10-anthraquinone; 1- (4'-vinylbenzoylamide) -9,1
0-anthraquinone, 4-amino-1- (4'-vinylbenzoylamide) -9,10-anthraquinone, 5-amino-1- (4'-
Vinylbenzoylamide) -9,10-anthraquinone, 8-amino-1- (4'-vinylbenzoylamide) -9,10-anthraquinone, 4-nitro-1- (4'-vinylbenzoylamide) -9,10 -Anthraquinone, 4-hydroxy-1- (4'-vinylbenzoylamide) -9,10-anthraquinone, 1- (3 '
-Vinylbenzoylamide) -9,10-anthraquinone, 1-
(2'-vinylbenzoylamide) -9,10-anthraquinone, 1- (4'-isopropenylbenzoylamide) -9,10-
Anthraquinone, 1- (3'-isopropenylbenzoylamide) -9,10-anthraquinone, 1- (2'-isopropenylbenzoylamide) -9,10-anthraquinone, 1-4-bis
(4'-vinylbenzoylamide) -9,10-anthraquinone, 1-4-bis- (4'-isopropenylbenzoylamide) -9,10-anthraquinone, 1-5'-bis- (4'-vinylbenzoyl Amide) -9,10-anthraquinone, 1,5-bis
-(4'-isopropenylbenzoylamide) -9,10-anthraquinone, 1-methylamino-4- (3'-vinylbenzoylamide) -9,10-anthraquinone, 1-methylamino-4-
(4'-vinylbenzoyloxyethylamino) -9,10-anthraquinone, 1-amino-4- (3'-vinylphenylamino) -9,10-anthraquinone-2-sulfonic acid, 1-amino-4
-(4'-vinylphenylamino) -9,10-anthraquinone
2-sulfonic acid, 1-amino-4- (2'-vinylbenzylamino) -9,10-anthraquinone-2-sulfonic acid, 1-amino
-4- (3 '-(meth) acryloylaminophenylamino) -9,10-anthraquinone-2-sulfonic acid, 1-amino-4
-(3'- (meth) acryloylaminobenzylamino)
-9,10-anthraquinone-2-sulfonic acid, 1- (β-ethoxycarbonylallylamino) -9,10-anthraquinone, 1-
(Β-carboxyallylamino) -9,10-anthraquinone, 1,5-di- (β-carboxyallylamino) -9,10-anthraquinone, 1- (β-isopropoxycarbonylallylamino) -5-benzoylamide -9,10-anthraquinone, 2- (3 '-(meth) acryloylamide-anilino)
-4- (3'- (3 "-sulfo-4" -aminoanthraquinone-
1 ″ -yl) -amino-anilino) -6-chloro-1,3,5-
Triazine, 2- (3 '-(meth) acryloylamide-anilino) -4- (3'-(3 "-sulfo-4" -aminoanthraquinone-1 "-yl) -amino-anilino) -6-hydrazino- 1,3,5-triazine, 2,4-bis-((4 "-methoxyanthraquinone-1" -yl) -amino) -6- (3'-vinylanilino) -1,3,5-triazine, 2- (2'-vinylphenoxy) -4- (4 '-(3 "-sulfo-4" -aminoanthraquinone-1 "-yl-amino) -anilino) -6-chloro-1,3,5
-Anthraquinone-based polymerizable dyes such as triazine; nitro-based polymerizable dyes such as 0-nitroanilinomethyl (meth) acrylate; (meth) acryloylated tetraamino copper phthalocyanine, (meth) acryloylated (dodecanoylated tetraamino copper phthalocyanine) And the like. These polymerizable dyes may be used alone or in combination of two or more.

Specific examples of the polymerizable ultraviolet absorbing dye include, for example, 2,4-dihydroxy-3 (p-styrenoazo) benzophenone, 2,4-dihydroxy-5- (p-styrenoazo) benzophenone, 2,4-dihydroxy -3- (p- (meth) acryloyloxymethylphenylazo) benzophenone, 2,4-dihydroxy-5- (p- (meth) acryloyloxymethylphenylazo) benzophenone, 2,4-dihydroxy-3- (p- (Meth) acryloyloxyethylphenylazo) benzophenone, 2,4-dihydroxy-5-
(P- (meth) acryloyloxyethylphenylazo)
Benzophenone, 2,4-dihydroxy-3- (p- (meth) acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy-5- (p- (meth) acryloyloxypropylphenylazo) benzophenone, 2,4- Dihydroxy-3- (o- (meth) acryloyloxymethylphenylazo) benzophenone, 2,4-dihydroxy-5-
(O- (meth) acryloyloxymethylphenylazo)
Benzophenone, 2,4-dihydroxy-3- (o- (meth) acryloyloxyethylphenylazo) benzophenone, 2,4-dihydroxy-5- (o- (meth) acryloyloxyethylphenylazo) benzophenone, 2,4- Dihydroxy-3- (o- (meth) acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy-5-
(O- (meth) acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy-3- (p- (N, N-
Di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-5- (p- (N,
N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-3- (o-
(N, N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-5-
(O- (N, N-di (meth) acryloylethylamino) phenylazo) benzophenone, 2,4-dihydroxy-3- (p-
(N-ethyl-N- (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy
-5- (p- (N-ethyl-N- (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-3- (o- (N-ethyl-N- (meth) acryloyloxyethylamino ) Phenylazo) benzophenone,
2,4-dihydroxy-5- (o- (N-ethyl-N- (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-3- (p- (N-ethyl-N- (meta ) Acryloylamino) phenylazo) benzophenone, 2,4-dihydroxy-5- (p- (N-ethyl-N- (meth)
Acryloylamino) phenylazo) benzophenone,
2,4-dihydroxy-3- (o- (N-ethyl-N- (meth) acryloylamino) phenylazo) benzophenone, 2,4-
Benzophenone-based polymerizable ultraviolet absorbing dyes such as dihydroxy-5- (o- (N-ethyl-N- (meth) acryloylamino) phenylazo) benzophenone;
Benzoic acid-based polymerizable ultraviolet-absorbing dyes such as phenyl 4- (p-styrenoazo) benzoate, and the like. These polymerizable ultraviolet-absorbing dyes are used alone or in combination of two or more.

The amount of the polymerizable ultraviolet absorbent, the polymerizable dye and the polymerizable ultraviolet absorbing dye is greatly affected by the thickness of the lens. Parts or less, more preferably 0.1 to 2 parts. If the amount is more than 3 parts, the physical properties of the lens, such as mechanical strength, tend to decrease. Also, considering the toxicity of ultraviolet absorbers and dyes, contact lenses and biological It tends to be unsuitable as a material for an ophthalmic lens such as an intraocular lens to be embedded therein. In addition, especially in the case of pigments, if the amount is too large, the color of the lens becomes too deep, the transparency is reduced, and the lens tends to be hard to transmit visible light.

In order to further impart oxygen permeability to the obtained ophthalmic lens material as the other copolymer component, for example, a compound represented by the following general formula (X):

[0045]

Embedded image

Wherein Y ¹¹ and Y ¹² are each independently an acryloyl, methacryloyl, vinyl or allyl group; X ¹¹ and X ¹² are each independently a covalent bond, an oxygen atom or an alkylene glycol group; ¹¹ and R ¹² are each independently a linear or branched alkylene group having 1 to 6 carbon atoms; R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ ,
R ¹⁷ and R ¹⁸ are each independently an alkyl group or phenyl group having 1 to 3 carbon atoms, i is an integer of 1 to 1500, and j is 0
To ( 1500-i ) , a polysiloxane macromonomer having a polymerizable group at both terminals (hereinafter referred to as macromonomer (B)) or the like may be used. The macromonomer (B) imparts excellent oxygen permeability to the ophthalmic lens material and, at the same time, has a polymerizable group at both ends of the molecule, so that the macromonomer (B) also polymerizes with other copolymerization components and obtains the obtained ophthalmic lens. It is not likely to elute from the lens material for use. In the general formula (X), Y ¹¹ and Y ¹² each independently represent an acryloyl group, a methacryloyl group, a vinyl group or an allyl group, as described above. X ¹¹ and X
¹² each independently a covalent bond, an oxygen atom or an alkylene glycol group, as such alkylene glycol group, for example the general formula (XI): - O - ( C g H 2g - O) h (XI) ( wherein , G is an integer of 2 to 4, h is an integer of 1 to 5)
And the like. The general formula
In (XI), when h is an integer of 6 or more, since oxygen permeability or mechanical strength tends to decrease, in the present invention, h is an integer of 1 to 5, particularly 1 to 5. 3
Is preferably an integer. R ¹¹ and R ¹² are each independently a linear or branched alkylene group having 1 to 6 carbon atoms. When the alkylene group has 7 or more carbon atoms, oxygen permeability decreases. The number of carbon atoms of the alkylene group which tends to be particularly preferred is 1 to 3. R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent an alkyl group having 1 to 3 carbon atoms or a phenyl group. i is an integer of 1 to 1500 and j is an integer of 0 to ( 1500-i ) . When i + j is larger than 1500, the molecular weight of the macromonomer (B) becomes too large, and other copolymer components With i.e., there is a tendency that the compound does not dissolve sufficiently at the time of compounding, becomes cloudy at the time of polymerization, and a uniform and transparent material cannot be obtained, and when i + j is 0, the oxygen permeation of the obtained material In addition to the reduced properties, the resulting material tends to be brittle, so that i + j is 1-1500,
It is preferably from 3 to 500, particularly preferably from 5 to 100.

The amount of the macromonomer (B) is 3 to 45 parts per 100 parts of the total amount of the monomers to be subjected to polymerization.
Preferably it is in the range of 5 to 35 parts, more preferably 5 to 25 parts, particularly preferably 10 to 15 parts. If the amount of the macromonomer (B) is less than the lower limit, the effect of using the macromonomer (B) will not be sufficiently exerted.If the amount is more than the upper limit, other essential components will be used. There is a tendency that compatibility with the polymerization component becomes poor, and it is difficult to obtain a uniform and transparent material.

In the present invention, one or more of the other copolymer components are selected as macromonomers, and these are used as one of the lens components other than the essential polymer components. You may further mix | blend with a copolymerization component.

The other copolymer components such as the polysiloxane macromonomer are subjected to copolymerization after being appropriately adjusted according to the intended use of an ophthalmic lens such as a contact lens or an intraocular lens. .

In the present invention, a desired amount of the polysiloxane macromonomer and the other copolymerization component is adjusted within the above-mentioned range, and a radical polymerization initiator is added thereto to polymerize in a usual manner. Thereby, a copolymer can be obtained.

The above-mentioned ordinary method means that, for example, after mixing a radical polymerization initiator, the mixture is gradually heated in a temperature range from room temperature to about 130 ° C.
This method is performed by irradiating an electromagnetic wave such as a line. In the case of heat polymerization, the temperature may be raised stepwise. The polymerization may be performed by a bulk polymerization method, a solution polymerization method using a solvent or the like, or may be performed by another method.

Specific examples of the radical polymerization initiator include, for example, azobisisobutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, te
Examples thereof include rt-butyl hydroperoxide and cumene hydroperoxide. These radical polymerization initiators may be used alone or in combination of two or more. When the polymerization is carried out by using a light beam or the like, it is preferable to further add a photopolymerization initiator or a sensitizer. The amount of the polymerization initiator or sensitizer to be added depends on the amount of the lens component used for polymerization.
Suitably it is about 0.001-2 parts, preferably 0.01-1 part, per 100 parts.

When molding as an ophthalmic lens such as a contact lens or an intraocular lens, a molding method commonly used by those skilled in the art is employed. Examples of such a molding method include a cutting method and a mold method. In the cutting method, polymerization is performed in an appropriate mold or container, and a rod-shaped, block-shaped, or plate-shaped material (polymer) is obtained, and then processed into a desired shape by mechanical processing such as cutting or polishing. Is the way. The mold method is a method of preparing a mold corresponding to the shape of a desired ophthalmic lens, polymerizing the lens components in the mold to obtain a molded product, and mechanically finishing the product as necessary. It is.

When the ophthalmic lens material used in the present invention can be obtained as a soft material at a temperature near room temperature, a molding method using a mold method is generally suitable for molding the ophthalmic lens. As a casting method, a spin casting method, a static casting method, and the like are known.

Further, apart from these methods, for example, a soft material is impregnated with a monomer which gives a hard polymer, and then the monomer is polymerized to harden the whole material.
A method of obtaining a molded article made of a soft material by removing a hard polymer from a molded article which has been subjected to a cutting process and processed into a desired shape (Japanese Patent Application Laid-Open Nos. 62-2780241 and 1-11854), and the like. It can be preferably applied to the invention.

Further, when the intraocular lens is obtained, the supporting portion of the lens may be manufactured separately from the lens and attached to the lens later, or may be molded simultaneously (integrally) with the lens. .

Next, the ophthalmic lens material of the present invention will be described in detail with reference to Examples, but the present invention is not limited to only these Examples.

Production Example 1 1 equipped with a stirrer, a thermometer, a cooling pipe and a dripping funnel
33.3 g (0.15 mol) of isophorone diisocyanate, 270 g of butyl acetate and 0.6 g of dibutyltin dilaurate were charged into a liter four-necked flask and mixed and stirred.
The mixture in the flask is heated to 70 ° C. and the formula is added using a dropping funnel:

[0059]

Embedded image

241 g (0.10 mol) of polydimethylsiloxane having one hydroxyl group at each end represented by
The mixture was added dropwise over 2 hours while maintaining the temperature, and then stirring was continued at 80 ° C. for 3 hours.

Next, 0.3 g of 2,6-di-t-butyl-p-cresol (hereinafter referred to as BHT) was added, and 11.6 g of hydroxyethyl acrylate (0.
10 mol) and 11.6 g of butyl acetate were added dropwise over 30 minutes. After stirring at 80 ° C. for 3 hours, the reaction solution was sampled, a predetermined amount of di-n-butylamine was added, mixed, and the reaction rate was determined by potentiometric titration using hydrochloric acid. Was 100%.

After adding 20 g of commercially available ethanol to the obtained reaction solution and stirring at 70 ° C. for 1 hour, the solvent and low-boiling substances were removed at 80 ° C. under reduced pressure to produce a pale yellow transparent viscous reaction. 260.7g of product was obtained. IR and ¹ H-NMR of the reaction product
As a result of measuring and analyzing

[0063]

Embedded image

It was confirmed that the compound represented by the formula (hereinafter referred to as macromonomer A) was obtained.

Production Example 2 In Production Example 1, the amount of isophorone diisocyanate used was 49.8 g (0.22 mol), and the amount of butyl acetate was 300.
g, the amount of dibutyltin dilaurate used is 0.8 g, and a polydimethylsiloxane having one hydroxyl group at each end is represented by the following formula:

[0066]

Embedded image

The amount of use is represented by
The reaction was carried out in the same manner as in Production Example 1 except that 4.2 g (0.15 mol), the amount of BHT used was 0.3 g, the amount of hydroxyethyl acrylate used was 17.4 g (0.15 mol), and the amount of butyl acetate used was 17.4 g. The product was obtained.

The IR and ¹ H-NMR of the obtained reaction product were measured and analyzed.

[0069]

Embedded image

It was confirmed that the compound represented by the formula (hereinafter referred to as macromonomer B) was obtained.

Example 1 10 parts of macromonomer A, 50 parts of hexafluoroisopropyl acrylate, 40 parts of n-butyl acrylate, 0.5 part of ethylene glycol dimethacrylate and 2,2'-azobis (2,4-dimethylvaleronitrile as a polymerization initiator )
0.3 part (hereinafter referred to as V-65) was uniformly mixed to obtain a clear solution. This was injected into a mold in which a fluorine resin gasket was sandwiched between polyester films from both sides, and the outside thereof was further sandwiched between glass plates.

Next, the mold was moved into a circulation dryer,
After heating at 50 ° C for 18 hours, at a rate of 10 ° C per 2 hours
The polymerization was carried out by raising the temperature to 110 ° C. to obtain a film-like copolymer.

Even when the obtained copolymer was folded in two and released, the resilience was good, for example, the copolymer was immediately restored to its original state. Therefore, this copolymer is preferable as a soft ophthalmic lens material. It turned out to have flexibility. Also,
As a result of observing the test piece in water with the naked eye, the appearance was transparent and there was no problem at all.

Next, the obtained film-like copolymer was punched out to a diameter of about 14 mm with a punch, and these were used as test pieces.
Various physical properties were measured. The measurement of physical properties was performed according to the method described later. Table 1 shows the results. [Transparency] The test piece in water was visually observed. (Evaluation Criteria) 透明: Transparent ：: Slightly cloudy X: Significantly cloudy [Rebound] The test piece was folded in two, and it was examined whether or not the test piece quickly returned to the original state when the hand was released. (Evaluation criteria) ○: Quickly return to the original shape △: Return to the original shape after a short time ×: Almost no return to the original shape [Flexibility] The test piece was pulled from both sides and its elongation was examined. . (Evaluation criteria) ○: Expands well △: Does not expand much ×: Does not expand almost [Pull-out strength] (a) Pull-out load Pressing a 1/16 inch diameter to the center of the test piece using an Instron type compression tester. A needle was applied, and the load (g) at break of the test piece was measured. However, the values listed in the table are values obtained by converting the thickness of the test piece to 0.2 mm. (B) Elongation The elongation (%) at break of the test piece was measured at the time of measuring the above-mentioned punching load (g). (C) Strength index The strength of the material depends on both the elongation (%) and the punching load (g). Therefore, an intensity index was calculated by the following equation as a measure of relative intensity.

[0075]

(Equation 1)

[Average thickness] The average thickness (mm) of the test piece when the oxygen permeability coefficient was measured by the following method was measured. [Oxygen Permeability Coefficient] The oxygen permeability coefficient of the test piece was measured in physiological saline at 35 ° C. using a Kakenhi type film oxygen permeability meter manufactured by Rika Seiki Industry Co., Ltd. The unit of the oxygen permeability coefficient is ml (STP) · cm ² / (cm ³ · sec · mmHg), and the oxygen permeability coefficient in the table is a value obtained by multiplying the original oxygen permeability coefficient by 10 ^11. is there. [Oleic acid swelling coefficient] Oleic acid is one component of eye oil. The fact that the material swells in oleic acid means that it has a good affinity for oleic acid. Therefore, by measuring the swelling coefficient of the material in oleic acid, it can be used as a measure of whether or not the lipid easily adheres to the material.

The oleic acid swelling coefficient was obtained by dividing the size of a test piece in oleic acid at 35 ° C. by the size in physiological saline (no unit). [Water absorption] After the residual monomers and the like in the test piece were extracted by reflux extraction using hexane, the water absorption of the test piece was measured according to the following equation.

[0078]

(Equation 2)

Here, W represents the weight (g) of the test piece in an equilibrium hydrated state, and Wo represents the weight (g) of the test piece in a dry state. [Contact Angle] The contact angle was measured at room temperature by a droplet method using a contact angle measuring device CA-A (manufactured by Kyowa Interface Science Co., Ltd.). [Refractive index] Temperature 25 ° C, humidity using ATAGO refractometer 1T
It was measured under 50% conditions.

Example 2 Example 1 was repeated except that 20 parts of macromonomer A, 50 parts of hexafluoroisopropyl acrylate, 30 parts of n-butyl acrylate and 0.3 part of V-65 as a polymerization initiator were used.
Polymerization was carried out in the same manner as in the above to obtain a film-like copolymer.

This film was rich in resilience and elasticity, and had favorable flexibility as a non-water-containing soft ophthalmic lens material.

Next, various physical properties were measured in the same manner as in Example 1 using the obtained film-like copolymer. Table 1 shows the results.

Example 3 Example 1 was repeated except that 10 parts of macromonomer B, 50 parts of hexafluoroisopropyl acrylate, 40 parts of n-butyl acrylate and 0.3 part of V-65 as a polymerization initiator were used.
Polymerization was carried out in the same manner as in the above to obtain a film-like copolymer.

This film was rich in resilience and elasticity, and had favorable flexibility as a non-water-containing soft ophthalmic lens material.

Next, various physical properties were measured in the same manner as in Example 1 using the obtained film-like copolymer. Table 1 shows the results.

Comparative Example 1 In Example 1, instead of macromonomer A, the formula:

[0087]

[Formula 10]

Example 1 was repeated except that 10 parts of macromonomer C having a urethane bond only at both ends represented by
A film-like copolymer was obtained in the same manner as described above.

Although the obtained film-like copolymer had flexibility, the punch-out strength was lower and the water wettability was inferior to that of the film-like copolymer obtained in Example 1. Was something.

Next, various physical properties were measured in the same manner as in Example 1 using the obtained film-like copolymer. Table 1 shows the results.

Comparative Example 2 A film-like copolymer was obtained in the same manner as in Example 2 except that 20 parts of macromonomer C was used instead of macromonomer A.

Although the obtained film-like copolymer had flexibility, the punch-out strength was lower and the water wettability was inferior to that of the film-like copolymer obtained in Example 2. Was something.

Next, various physical properties were measured in the same manner as in Example 1 using the obtained film-like copolymer. Table 1 shows the results.

Comparative Example 3 In Example 3, instead of macromonomer B, the formula:

[0095]

[Formula 11]

Example 1 was repeated except that 10 parts of the macromonomer D having a urethane bond only at both ends was used.
A film-like copolymer was obtained in the same manner as described above.

Although the obtained film-like copolymer had flexibility, the punch-out strength was lower than that of the film-like copolymer obtained in Example 3, and it was inferior in water wettability. Was something.

Next, various physical properties were measured in the same manner as in Example 1 using the obtained film-like copolymer. Table 1 shows the results.

[0099]

[Table 1]

Examples 4 to 11 In the same manner as in Example 1, various components were blended and polymerized so as to have the composition shown in Table 2, to obtain a film-like copolymer, which was processed and tested. I got a piece. Various physical properties of the obtained test pieces were measured in the same manner as in Example 1. The results are also shown in Table 2.

The obtained copolymer was folded in two and released, and the copolymer was preferable as a soft ophthalmic lens material because of good repulsion such as immediate restoration to the original state. It turned out to have flexibility. Further, as a result of observing the test piece in water with the naked eye, the test piece was transparent, and there was no problem with the transparency at all.

Next, various physical properties were measured in the same manner as in Example 1 using the obtained film-like copolymer. Table 2 shows the results.

In Table 2, 6FPA means hexafluoroisopropyl acrylate, BuA means n-butyl acrylate, and EDMA means ethylene glycol dimethacrylate.

[0104]

[Table 2]

Example 12 40 parts of macromonomer A, 60 parts of trifluoroethyl methacrylate, 7 parts of methyl methacrylate, 2 parts of methacrylic acid, and 2 parts of ethylene glycol dimethacrylate
And 0.2 part of V-65 were mixed to make a homogeneous solution.
The mixture was poured into a 15 mm glass test tube, stoppered, and allowed to stand in a constant temperature water bath at 35 ° C. 40 hours at 35 ° C, 8 hours at 50 ° C, then
The temperature was raised to 120 ° C. to complete the polymerization. The obtained polymer was colorless, transparent and hard.

The obtained polymer could be sufficiently machined and polished.

As the physical properties of the obtained polymer, Rockwell hardness, Shore D hardness, impact strength and oxygen permeability coefficient were measured by the following methods, and the refractive index was measured in the same manner as in Example 1. Table 3 shows the results. [Rockwell hardness] Using a Rockwell superficial hardness tester manufactured by Akashi Seisakusho, load 30kg, indenter
The measurement was performed on a test piece 12.7 mm in diameter and 4.0 mm thick in a constant temperature and humidity of 25 ° C. and 50% RH at 1/4 inch (about 0.64 mm). [Shore D hardness] Diameter in constant temperature and humidity of 25 ° C and 50% RH using a durometer GS-702 manufactured by Teklock Co., Ltd.
The measurement was performed on a test piece having a thickness of 12.7 mm and a thickness of 4.0 mm. [Impact strength] Load of 6.75 g in a constant temperature and humidity environment of 25 ° C and 50% RH
Was dropped on a test piece having a thickness of 0.5 mm, and the height (mm) when the test piece was broken was indicated as impact resistance. [Oxygen Permeability Coefficient] Measurement was performed on a test piece having a diameter of 13 mm and a thickness of 0.5 mm using a gas permeability measuring device Model GTR-10 manufactured by Yanagimoto Seisakusho. Units ^{ml (STP) · cm 2 /} (cm 3 · se
c · mmHg).

Example 13 60 parts of macromonomer A, 40 parts of trifluoroethyl methacrylate, 7 parts of methyl methacrylate, 2 parts of methacrylic acid, and 2 parts of ethylene glycol dimethacrylate
And V-65 were mixed and polymerized in the same manner as in Example 12. The obtained polymer was colorless and transparent and had a hardness that could be machined.

The physical properties of the obtained polymer were examined in the same manner as in Example 12. Table 3 shows the results.

[0110]

[Table 3]

As is clear from the above results, the ophthalmic lens material of the present invention was obtained using a novel urethane bond-containing silicone macromonomer, and this macromonomer is different from the conventional macromonomer. In addition to having urethane bonds at both ends, urethane bonds are arbitrarily introduced in the middle of the silicone chain. Therefore, when compared with the same molecular weight, the number of urethane bonds is larger than that of the conventional silicone macromonomer, so that even with the same molecular weight and the same compounding amount, the material is further imparted with mechanical strength without impairing oxygen permeability. You can see that.

[0112]

The ophthalmic lens material of the present invention has the following effects. (A) Since the ophthalmic lens material of the present invention is substantially non-water-containing, there is no disadvantage that the mechanical strength is reduced due to the improvement of the water content, which is observed in conventional water-containing lenses. There is no loss of shape retention as a lens.
In addition, since bacteria and the like are difficult to propagate in the material, there is an effect that complicated treatment such as boiling disinfection is not required when a contact lens is used. (B) Since the ophthalmic lens material of the present invention is excellent in oxygen permeability, it has an effect of not impairing the metabolic function of the cornea when formed into a contact lens. (C) Since the ophthalmic lens material of the present invention is excellent in mechanical strength, it has an effect that the shape of the lens is stable and the lens is not damaged by various physical treatments. (D) Further, the ophthalmic lens material of the present invention has a good wearing feeling when formed into a soft lens, for example, a soft contact lens, and deforms through a small incision without damaging ocular tissue when formed into a soft intraocular lens. Can be inserted. In addition, when a hard lens is used, it has excellent mechanical strength, so that it has an effect of being hardly damaged by various impacts and the like. (E) Further, the ophthalmic lens material of the present invention comprises a hard lens,
For example, when a hard contact lens is used, since it has excellent mechanical strength as described above, it has an effect of extremely excellent impact resistance.

──────────────────────────────────────────────────の Continued on the front page (72) Inventor Hiroshi Yoshioka 2-3-1-1, Isobe, Annaka-shi, Gunma Shin-Etsu Chemical Co., Ltd. Silicone Electronics Materials Research Laboratory (72) Inventor Toshio Yamazaki Isobe, Annaka-shi, Gunma No. 2-13-1, Shin-Etsu Chemical Co., Ltd. Examiner at Silicone Electronic Materials Technology Laboratory Tsutomu Onodera (56) References JP-A-4-50814 (JP, A) JP-A-3-228014 (JP, A) JP-A-4-46311 (JP, A) JP-A-63-85719 (JP, A) JP-A-4-172419 (JP, A) JP-A-4-85314 (JP, A) JP-A-4-57814 (JP , A) JP-A-61-21121 (JP, A) Patent 2518984 (JP, B2) Patent 2716187 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 290/00-290 / 14 C08F 299/00-299/08 C08G 18 / 00-18/87 C08G 77/00-77/62 G02B 1/00-1/12 A61L 27/00

Claims (1)

(57) [Claims] 1. A general formula (I): A ¹ -U ¹ -(-S ¹ -U ^2- ) _n -S ² -U ³ -A ² (I) (where A ¹ is a group represented by the general formula (II) ^{): Y 21 -R 31 - (} II) ( wherein, Y ²¹ is acryloyloxy group, methacryloyloxy group, a vinyl group or an allyl group, R ³¹ is 2 carbon atoms
6 straight or branched chain represents an alkylene group having) a group represented by; A ² of the general formula ^{(III): Y 22 -R 34} - (III) ( wherein, Y ²² is acryloyloxy group, methacryloyloxy Group, vinyl group or allyl group, R ³⁴ has 2 to 2 carbon atoms.
Groups represented by an alkylene group) having 6 linear or branched; U ¹ is the general formula ^{(IV): - X 21 -E} 21 -X 25 -R 32 - (IV) ( wherein, X ²¹ Is a covalent bond, an oxygen atom or an alkylene glycol group, and E ²¹ is a -NHCO- group (in this case,
X ²¹ is a covalent bond, E ²¹ forms a urethane bond with X ²⁵ ) or a divalent group derived from a diisocyanate selected from the group consisting of a saturated aliphatic system, an alicyclic system and an aromatic system ( Provided that X ²¹ is an oxygen atom or an alkylene glycol group, E ²¹ forms a urethane bond between X ²¹ and X ²⁵ ); X ²⁵ is an oxygen atom or an alkylene glycol group; R ³² Represents a linear or branched alkylene group having 1 to 6 carbon atoms); S ¹ and S ² each independently represent a group represented by the general formula (VII): (Wherein R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are each independently an alkyl group or phenyl group having 1 to 3 carbon atoms, K is an integer of 1 to 1500, and L is 0 to 1500 is an integer from, K + L is an integer of 1 to 1500); U ² is the general formula
^{(V): - R 37 -X} 27 -E 24 -X 28 -R 38 - (V) ( wherein, R ³⁷ and R ³⁸ are 1 to carbon atoms independently
X ²⁷ and X ²⁸ each independently represent an oxygen atom or an alkylene glycol group; E ²⁴ is selected from the group consisting of a saturated aliphatic system, an alicyclic system and an aromatic system A divalent group derived from diisocyanate (where E ²⁴ forms a urethane bond between X ²⁷ and X ²⁸ ); U ³ has the general formula (VI): -R ³³ -X ^{26 -E 22 -X 22 - (VI} ) ( wherein, R ³³ is an alkylene group having a straight chain or branched chain of 1 to 6 carbon atoms, X ²² is a covalent bond, an oxygen atom or an alkylene glycol group, X ²⁶ is An oxygen atom or an alkylene glycol group, E ²² is an —NHCO— group (where X ²² is a covalent bond and E ²² forms a urethane bond with X ²⁶ ), or a saturated aliphatic group, 2 derived from a diisocyanate selected from the group consisting of a cyclic system and an aromatic system A group represented by a valent group (where X ²² is an oxygen atom or an alkylene glycol group, and E ²² forms a urethane bond between X ²² and X ²⁶ ),
n is an integer of 1 or more), and a polysiloxane macromonomer having a polymerizable group bonded to the siloxane main chain through one or two urethane bonds; An ophthalmic lens material comprising a copolymer with a monomer having a heavy bond.