JPWO2001071415A1 - Ophthalmic lens materials - Google Patents

Abstract

(57) [Abstract] An ophthalmic lens material comprising a copolymer obtained by heating and ultraviolet irradiation using a template method to polymerize polymerization components primarily consisting of polysiloxane macromonomer A, Si-containing alkyl methacrylate B, hydrophilic monomer C, which is NVP C-1 and another hydrophilic monomer C-2, another monomer D, and low-molecular-weight crosslinking monomer E, which is a crosslinking monomer E-1 containing an acryloyl, vinyl, or allyl group and a methacryloyl group, and two or more methacryloyl group-containing crosslinking monomers E-2, wherein the copolymer has an (A+B)/C (weight ratio) of 30/70 to 70/30, A/B of 25/75 to 75/25, C-1/C-2 of 50/50 to 100/0, and D of 0 to 20% by weight of the polymerization components, and exhibits high oxygen permeability, high mechanical strength, excellent surface water wettability, and low surface friction.

Description

The present invention relates to an ophthalmic lens material. More specifically, the present invention relates to an ophthalmic lens material that has high oxygen permeability and high mechanical strength, as well as excellent surface water wettability and low surface friction, and is suitable for use in contact lenses, intraocular lenses, artificial corneas, etc.

BACKGROUND ART Conventionally, soft materials have generally been suitable for contact lens materials that are comfortable to wear and for intraocular lens materials that can be deformed and inserted simply by making a small incision in the eyeball without damaging the ocular tissue.

The soft materials include water-absorbent materials that absorb water, swell, and become soft, and substantially water-free materials. The oxygen permeability of such water-absorbent materials depends on the water content, and their oxygen permeability coefficient never becomes greater than that of water.

As a material for obtaining a contact lens that is water-absorbent and has excellent oxygen permeability, for example, a hydrogel containing silicone (hereinafter referred to as silicone hydrogel) can be mentioned (see Japanese Patent Application Laid-Open No. 3-179422 and Japanese Patent Application Laid-Open No. 3-19617).
(See Japanese Patent Application Laid-Open No. 3-196118 and Japanese Patent Laid-Open No. 3-196118.) The reason why such silicone hydrogels have excellent oxygen permeability is that they have higher oxygen permeability than water.

Furthermore, because the silicone hydrogel contains a hydrophobic component, the water wettability of the surface of the material is poor, and when such a material is molded, the surface becomes highly tacky. Furthermore, if the amount of silicon-containing monomer is increased to further improve the oxygen permeability of the material, the resulting material becomes semi-hard, making it difficult to use such a material to produce contact lenses that are comfortable to wear or intraocular lenses that can be inserted by simply making a small incision in the eyeball. Furthermore, when such ophthalmic lenses are worn or attached, they suffer from poor comfort, and in addition, their high hydrophobicity leads to increased adhesion of lipids and other substances. However, if a large amount of hydrophilic components is used to improve the wearing comfort of the material, the oxygen permeability of the material naturally becomes dependent on the water content.

The optimal hydrogel material for ophthalmic lenses must have high oxygen permeability, ideal rigidity, high water wettability, and low friction. This is because high water wettability and low friction maintain the smoothness of the lens, allowing it to be worn comfortably on the eye. Therefore, the following methods have been proposed to improve the water wettability and reduce friction of the material.

U.S. Pat. No. 4,099,859 discloses a method in which the surface of a contact lens is coated with a hydrophilic monomer and then irradiated with ultraviolet light, thereby grafting a hydrophilic polymer onto the surface of a silicone rubber contact lens material.
Also, U.S. Patent No. 4,143,949 discloses a method for applying a hydrophilic coating to a hydrophobic contact lens by radiation polymerization, and U.S. Patent Nos. 4,311,573 and 4,589,964 disclose methods for hydrophilizing the surface of a hydrophobic polymer by ozone treatment followed by grafting of a vinyl monomer by decomposition of the resulting peroxy groups.
No. 64 discloses that a crosslinked siloxane-urethane polymer is obtained in the form of an interpenetrating network polymer (generally referred to as an IPN) with a hydrophilic vinyl polymer.

However, all of the above methods have various problems, such as complicated processes, difficulty in uniformly treating all lenses and checking the degree of treatment, and difficulty in producing the raw materials, making it difficult to easily obtain the desired hydrogel material that is optimal for ophthalmic lenses.

In addition to the above, the following various materials have been proposed:

For example, Japanese Patent Application Laid-Open No. 54-22487 discloses a water-insoluble hydrophilic gel consisting of a crosslinked copolymerization reaction product of 20 to 90% by weight of a water-soluble monomer and a water-insoluble monoolefinic monomer such as methyl methacrylate with 10 to 80% by weight of a hydrophobic siloxane macromer. Japanese Patent Application Laid-Open No. 55-500418 discloses a hydrophilic composition which is a copolymer of comonomers consisting of 15 to 65% by weight of an amide group-containing monomer, 10 to 75% by weight of an organosilicon compound, and 0.1 to 65% by weight of an ester of an alkanol and (meth)acrylic acid, and which has improved flexibility and oxygen permeability after hydration. Japanese Patent Application Laid-Open No. 4-46311 discloses a composition which is a copolymer of comonomers consisting of 15 to 65% by weight of an amide group-containing monomer, 10 to 75% by weight of an organosilicon compound, and 0.1 to 65% by weight of an ester of an alkanol and (meth)acrylic acid, and which has improved flexibility and oxygen permeability after hydration.
and then reacting with diisocyanate to obtain a macromer, which is then polymerized with other monomers.
826 discloses ophthalmic lens materials composed of copolymers containing polysiloxane macromonomer and alkyl(meth)acrylamide as main components, with the weight ratio of the two (polysiloxane macromonomer/alkyl(meth)acrylamide) being 5/95 to 90/10.

The various gels, compositions, contact lenses and materials described above are all obtained using silicon (particularly silicone)-containing components, and therefore, although they have excellent oxygen permeability, their surface water wettability is not so good and their friction is not sufficiently low. Therefore, they cannot be said to be materials that simultaneously satisfy high oxygen permeability, high surface water wettability and low friction.

The present invention has been made in view of the above-mentioned prior art, and an object of the present invention is to provide an ophthalmic lens material which has high oxygen permeability and high mechanical strength, as well as excellent surface water wettability and a low surface friction.

DISCLOSURE OF THE INVENTION The present invention relates to a compound of formula (A) (I):¹-U¹-(-S¹-U²−)_n-S²-U³-A² (I) [In the formula, A¹is represented by the general formula (II): Y²¹-Z²¹-R³¹- (II) (In the formula, Y²¹is an acryloyl group, a vinyl group or an allyl group, Z²¹is an oxygen atom
or a direct bond, R³¹is a direct bond or a straight chain, branched chain or
(represents an alkylene group having an aromatic ring); A²is represented by general formula (III): -R³⁴-Z²²-Y²² (III) (In the formula, Y²²is an acryloyl group, a vinyl group or an allyl group, Z²²is an oxygen atom
or a direct bond, R³⁴is a direct bond or a straight chain, branched chain or
or an alkylene group having an aromatic ring) (wherein Y in general formula (II)²¹and Y in general formula (III)²²are the same
may be the same or different); U¹is represented by general formula (IV): -X²¹-E²¹−X²⁵-R³²- (IV) (In the formula, X²¹and X²⁵are each independently a direct bond, an oxygen atom, and an arsenic atom.
E is selected from the group consisting of alkylene glycol groups;²¹is a —NHCO— group (wherein,
X²¹is a direct bond, and X²⁵is an oxygen atom or an alkylene glycol group
Ri, E²¹is X²⁵and forms a urethane bond), -CONH- group (where
, in this case, X²¹is an oxygen atom or an alkylene glycol group, and X²⁵teeth
is a direct bond, and E²¹is X²¹and urethane bonds) or saturated
or a diisocyanate selected from the group consisting of unsaturated aliphatic, alicyclic and aromatic diisocyanates.
A divalent group derived from a carboxylate (in this case, X²¹and X²⁵are independent of each other.
E is selected from an oxygen atom and an alkylene glycol group;²¹is X²¹and X
²⁵Two urethane bonds are formed between R³²is a group having 1 to 6 carbon atoms
A group represented by the formula (representing a linear or branched alkylene group); S¹and S²are each independently represented by general formula (V):(In the formula, R²³, R²⁴, R²⁵, R²⁶, R²⁷and R²⁸are independent
as an alkyl group having 1 to 6 carbon atoms, a fluorine-substituted alkyl group, or a phenyl group
, K is an integer of 1 to 1500, L is 0 or an integer of 1 to 1499, and K+L is
a group represented by (wherein U is an integer from 1 to 1500);²is represented by general formula (VI): -R³⁷−X²⁷-E²⁴−X²⁸-R³⁸- (VI) (In the formula, R³⁷and R³⁸each independently represents a linear or branched chain having 1 to 6 carbon atoms;
a branched alkylene group; X²⁷and X²⁸are each independently an oxygen atom or
or an alkylene glycol group; E²⁴is saturated or unsaturated aliphatic, alicyclic
and divalent groups derived from diisocyanates selected from the group consisting of aromatic groups (provided that
In the case of E²⁴is X²⁷and X²⁸Two urethane bonds are formed between
A group represented by the formula: U³is represented by the general formula (VII): -R³³−X²⁶-E²²−X²²- (VII) (In the formula, R³³is a linear or branched alkylene group having 1 to 6 carbon atoms; X
²²and X²⁶are each independently a direct bond, an oxygen atom, and an alkylene glycol
E is selected from the group²²is a —NHCO— group (wherein, X²²is acid
is a hydrogen atom or an alkylene glycol group, and X²⁶is a direct bond, and E²²
is X²²and forms a urethane bond), -CONH- group (however, in this case
, X²²is a direct bond, and X²⁶is an oxygen atom or an alkylene glycol group
Yes, E²²is X²⁶urethane bond) or saturated or unsaturated
Diisocyanates derived from aliphatic, alicyclic and aromatic diisocyanates
Divalent group (in this case, X²²and X²⁶are each independently an oxygen atom
and alkylene glycol groups, E²²is X²²and X²⁶Noai
a group represented by the formula: (wherein n is 0 or an integer of 1 to 10) in which one or more polymerizable groups represented by the formula:
a polysiloxane macromonomer bonded to the siloxane backbone via a siloxane bond;
(B) silicon-containing alkyl methacrylate, (C) N-vinylpyrrolidone (C-1), and the N-vinylpyrrolidone (C-1)
Hydrophilic monomers containing an acryloyl group, a vinyl group or an allyl group other than (C
-2) a hydrophilic monomer consisting of (D) an alkyl (meth)acrylate and a fluorine-containing alkyl (meth)acrylate;
(E) at least one monomer selected from the group consisting of an acryloyl group, a vinyl group, and an allyl group;
a crosslinkable monomer (E-1) containing a group and a methacryloyl group, and at least two
A low molecular weight crosslinkable monomer (E-2) containing a methacryloyl group.
Polymerization components based on mer are heated and/or irradiated with ultraviolet light to polymerize them using a mold method.
a copolymer containing the polysiloxane macromonomer (A) and a silicon-containing alkyl methacrylate;
The ratio of the total of (A) and (B) to the hydrophilic monomer (C) [the total of (A) and (B)]
(total/(C) (weight ratio)] is 30/70 to 70/30, and
Reaction of a silicone macromonomer (A) with a silicon-containing alkyl methacrylate (B)
The weight ratio of the mixture [(A)/(B)] is 25/75 to 75/25, and the ratio of the N-vinylpyrrolidone (C-1) to the hydrophilic monomer (C-2) [(
and the weight ratio of the monomer (C-1)/(C-2) is 50/50 to 100/0, and the amount of the monomer (D) is 0 to 20% by weight of the polymerization components.

BEST MODE FOR CARRYING OUT THE INVENTION The ophthalmic lens material of the present invention comprises a polysiloxane macromonomer (A) represented by the general formula (I): ^A1 - ^U1 -(- ^S1 - ^U2- ) _n - ^S2 - ^U3 - ^A2 (I) (wherein ^A1 , ^A2 , ^U1 , ^U2 , ^U3 , ^S1 , ^S2 and n are the same as defined above), a silicon-containing alkyl methacrylate (B), a hydrophilic monomer (C) consisting of N-vinylpyrrolidone (C-1) and a hydrophilic monomer (C-2) other than the N-vinylpyrrolidone (C-1) that contains an acryloyl group, a vinyl group or an allyl group, at least one monomer (D) selected from alkyl (meth)acrylates and fluorine-containing alkyl (meth)acrylates, and a crosslinkable monomer (C) containing a methacryloyl group and at least one group selected from an acryloyl group, a vinyl group and an allyl group.
E-1) and a crosslinking monomer containing at least two methacryloyl groups (E-2)
The copolymer is obtained by polymerizing a polymer component consisting mainly of a low molecular weight crosslinkable monomer (E) consisting of (A) and (B) by a template method under heating and/or ultraviolet irradiation.

The polysiloxane macromonomer (A) is a component that has elastic bonds called urethane bonds, reinforces the material without impairing its flexibility or oxygen permeability through the siloxane moiety, imparts elastic resilience to eliminate brittleness, and improves mechanical strength. Furthermore, the polysiloxane macromonomer (A) has silicone chains in its molecular chain, which imparts high oxygen permeability.

The polysiloxane macromonomer (A) has polymerizable groups at both ends of the molecule and is copolymerized with other copolymerization components via these polymerizable groups, and therefore has the excellent property of imparting to the resulting ophthalmic lens material not only a physical reinforcing effect due to molecular entanglement but also a reinforcing effect due to chemical bonds (covalent bonds). In other words, the polysiloxane macromonomer (A) acts as a high molecular weight crosslinking monomer.

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

In general formula (I), ^A1 is, as described above, a group represented by general formula (II): ^Y21 - ^Z21 - ^R31- (II) (wherein ^Y21 , ^Z21 and ^R31 are the same as defined above), and ^A2 is a group represented by general formula (III): ^-R34 - ^Z22 - ^Y22 (III) (wherein ^Y22 , ^Z22 and ^R34 are the same as defined above).

Both Y ²¹ and Y ²² are polymerizable groups, but an acryloyl group is particularly preferred because it can be easily copolymerized with the hydrophilic monomer (C).

Z ²¹ and Z ²² are both an oxygen atom or a direct bond, preferably an oxygen atom.

R ³¹ and R ³⁴ each represent a direct bond or a linear, branched or aromatic alkylene group having 1 to 12 carbon atoms, and are preferably an ethylene group, a propylene group or a butylene group.

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

In ^U1 and ^U3 , ^E21 and ^E22 , as described above, respectively represent a -CONH- group, an -NHCO- group, or a divalent group derived from a diisocyanate selected from the group consisting of saturated or unsaturated aliphatic, alicyclic, and aromatic diisocyanates. Here, examples of the divalent group derived from a diisocyanate selected from the group consisting of saturated or unsaturated aliphatic, alicyclic, and aromatic diisocyanates include divalent groups derived from saturated aliphatic diisocyanates such as ethylene diisocyanate, 1,3-diisocyanate propane, and hexamethylene diisocyanate; divalent groups derived from alicyclic diisocyanates such as 1,2-diisocyanate cyclohexane, bis(4-isocyanate cyclohexyl)methane, and isophorone diisocyanate; Examples include divalent groups derived from aromatic diisocyanates such as tolylene diisocyanate and 1,5-diisocyanato naphthalene; and divalent groups derived from unsaturated aliphatic diisocyanates such as 2,2'-diisocyanato diethyl fumarate. Among these, the divalent groups derived from hexamethylene diisocyanate, tolylene diisocyanate, and isophorone diisocyanate are preferred because they are relatively easy to obtain and can easily impart strength to the polymer.

In ^U1 , when ^E21 is an -NHCO- group, ^X21 is a direct bond, ^X25 is an oxygen atom or an alkylene glycol group, and ^E21 is ^X25
and form a urethane bond represented by the formula: ^-NHCOO- .
When R 32 is an ONH- group, X ²¹ is an oxygen atom or an alkylene glycol group, X ²⁵ is a direct bond, and E ²¹ forms a urethane bond represented by the formula: -OCONH- with X ^21. Furthermore, when E ²¹ is a divalent group derived from a diisocyanate, X ²¹ and X ²⁵ are each independently selected from an oxygen atom and an alkylene glycol group preferably having 1 to 6 carbon atoms, and E ²¹ forms two urethane bonds between X ²¹ and X ^{25. R 32} is a divalent group derived from a diisocyanate having 1 to 6 carbon atoms.
is a linear or branched alkylene group.

U²In E²⁴As mentioned above, saturated or unsaturated aliphatic,
represents a divalent group derived from a diisocyanate selected from the group consisting of cyclic and aromatic diisocyanates;
Here, the compound is selected from the group consisting of saturated or unsaturated aliphatic, alicyclic and aromatic compounds.
Examples of the divalent group derived from diisocyanate include the above-mentioned U¹and U³
Among these, the divalent groups are relatively readily available.
Hexamethylene diisocyanate-derived resins are easy to apply and provide strength.
a divalent group derived from tolylene diisocyanate and isophorone diisocyanate
A divalent group derived from cyanate is preferred.²⁴is X²⁷and X²⁸Between
Two urethane bonds are formed.²⁷and X²⁸are each independently
an oxygen atom or an alkylene glycol group preferably having 1 to 6 carbon atoms;
R³⁷and R³⁸each independently has a linear or branched chain having 1 to 6 carbon atoms
is an alkylene group.

U³In this case, R³³is a linear or branched alkylene group having 1 to 6 carbon atoms.
It is a phenyl group.²²When is a —NHCO— group, X²²is an oxygen atom or
is an alkylene glycol group, and X²⁶is a direct bond, and E²²is X²²and the formula
: Forms a urethane bond represented by -NHCOO-.²²Ga-CON
When it is a H-group, X²²is a direct bond, and X²⁶is an oxygen atom or an arsenic atom
is an alkylene glycol group, and E²²is X²⁶and represented by the formula: -OCONH-
Forms a urethane bond.²²is a divalent group derived from the diisocyanate
If so, then X²²and X²⁶are each independently an oxygen atom and preferably
E is selected from alkylene glycol groups having 1 to 6 carbon atoms;²²is X²²and X^2
6Two urethane bonds are formed between the

Here, the alkylene glycol preferably having 1 to 6 carbon atoms represented by X ²¹ , X ²⁵ , X ²⁷ , X ²⁸ , X ²² and X ²⁶ may be, for example, a group represented by the general formula (V
III): -O-( _{CxH2x -} O) _y- (VIII) (wherein x is an integer of 1 to 4, and y is an integer of 1 to 5). In general formula (VIII), when y is an integer of 6 or more, oxygen permeability and mechanical strength tend to decrease. Therefore, in the present invention, y is preferably an integer of 1 to 5, particularly an integer of 1 to 3.

As described above, both S ¹ and S ² are groups represented by formula (V).

In the general formula (V), R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²
As described above, ⁸ is independently an alkyl group having 1 to 6 carbon atoms, a fluorine-substituted alkyl group, or a phenyl group.

Specific examples of the fluorine-substituted alkyl group include a 3,3,3-trifluoro-n-propyl group, a 3,3,3-trifluoroisopropyl group, a 3,
3,3-trifluoro-n-butyl group, 3,3,3-trifluoroisobutyl group, 3,3,3-trifluoro-sec-butyl group, 3,3,3-trifluoro-
t-butyl group, 3,3,3-trifluoro-n-pentyl group, 3,3,3-trifluoroisopentyl group, 3,3,3-trifluorothiopentyl group, 3,3,
In the present invention, when a polysiloxane macromonomer (A) having such a fluorine-substituted alkyl group is used and the blending amount thereof is increased, the lipid contamination resistance of the resulting ophthalmic lens material tends to be improved.

K is an integer of 1 to 1500, L is 0 or an integer of 1 to 1499,
+L is an integer from 1 to 1500. When K+L is greater than 1500,
The molecular weight of the polysiloxane macromonomer (A) becomes large, and the compatibility between the polysiloxane macromonomer (A) and the hydrophilic monomer (C) becomes poor, and the polysiloxane macromonomer (A) does not dissolve sufficiently during blending, or becomes cloudy during polymerization, and a uniform, transparent ophthalmic lens material tends to be difficult to obtain. Furthermore, if the molecular weight is 0, not only will the oxygen permeability of the obtained ophthalmic lens material be low, but also:
The total value of K+L is preferably an integer of 2 to 1,000, more preferably an integer of 3 to 500.

Furthermore, n is 0 or an integer of 1 to 10, but if n is greater than 10, the molecular weight of the polysiloxane macromonomer (A) becomes large, and compatibility with the hydrophilic monomer (C) deteriorates, resulting in insufficient dissolution during blending or clouding during polymerization, making it difficult to obtain a uniform, transparent ophthalmic lens material. n is preferably 0 or an integer of 1 to 5.

Representative examples of the polysiloxane macromonomer (A) include those represented by the formula: (hereinafter referred to as macromonomer (A-1)), a macromonomer represented by the formula: These may be used alone or in combination of two or more.

The silicon-containing alkyl methacrylate (B) is a component that further improves the oxygen permeability of the resulting ophthalmic lens material.

One of the major features of the present invention is that the polymerizable groups in the polysiloxane macromonomer (A), i.e., ^Y21 in general formula (II) representing ^A1 in general formula (I) and ^Y22 in general formula (III) representing ^A2 in general formula (I), are both groups selected from acryloyl groups, vinyl groups, and allyl groups, while the polymerizable group in the silicon-containing alkyl methacrylate (B) is a methacryloyl group. Since the polysiloxane macromonomer (A) and the silicon-containing alkyl methacrylate (B) have different polymerizable groups, silicone segments are introduced into the main chain in a block manner, and the hydrophilic monomer (C) described below is easily polymerized.
The hydrophilic segment derived from the polysiloxane macromonomer (A) and the hydrophilic monomer (C) can be introduced into the silicone segment in a block manner.
Both have a polymerizable group selected from an acryloyl group, a vinyl group, and an allyl group, and therefore can be effectively copolymerized.
When the silicon-containing alkyl methacrylate (B) and the silicon-containing alkyl methacrylate (C) have the same polymerizable group, they are both silicon-containing components, which results in the problem of forming particularly large domains.

Representative examples of the silicon-containing alkyl methacrylate (B) include, for example, trimethylsiloxydimethylsilylmethyl methacrylate, trimethylsiloxydimethylsilylpropyl methacrylate, methylbis(trimethylsiloxy)silylpropyl methacrylate, tris(trimethylsiloxy)silylpropyl methacrylate, mono[methylbis(trimethylsiloxy)siloxy]bis(trimethylsiloxy)silylpropyl methacrylate, tris[methylbis(trimethylsiloxy)siloxy]silylpropyl methacrylate, methylbis(trimethylsiloxy)siloxy (siloxy)silylpropyl glyceryl methacrylate, tris(trimethylsiloxy)silylpropyl glyceryl methacrylate, mono[methylbis(trimethylsiloxy)siloxy]bis(trimethylsiloxy)silylpropyl glyceryl methacrylate, trimethylsilylethyl tetramethyldisiloxypropyl glyceryl methacrylate, trimethylsilylmethyl methacrylate, trimethylsilylpropyl methacrylate, trimethylsilylpropyl glyceryl methacrylate, trimethylsiloxydimethylsilylpropyl glyceryl methacrylate,
Examples include methylbis(trimethylsiloxy)silylethyltetramethyldisiloxymethyl methacrylate, tetramethyltriisopropylcyclotetrasiloxanylpropyl methacrylate, and tetramethyltriisopropylcyclotetrasiloxybis(trimethylsiloxy)silylpropyl methacrylate, and these can be used alone or in combination of two or more.

The hydrophilic monomer (C) is a component that imparts flexibility and surface water wettability to the resulting ophthalmic lens material, improves wearing comfort, and also imparts low friction.

In the present invention, the hydrophilic monomer (C) is N-vinylpyrrolidone (C-
Another major feature is that N-vinylpyrrolidone (C-1) is used in combination with a hydrophilic monomer (C-2) containing an acryloyl group, a vinyl group or an allyl group other than N-vinylpyrrolidone (C-1).That is, if N-vinylpyrrolidone (C-1) is used alone, the compatibility with silicon-containing components such as polysiloxane macromonomer (A) and silicon-containing alkyl methacrylate (B) is poor, and the transparency of the obtained ophthalmic lens material is reduced, but at the same time, by using the hydrophilic monomer (C-2), the compatibility with silicon-containing components is improved.On the other hand, if N-vinylpyrrolidone (C-1) is not used, the desired low friction, easy lubrication and stain resistance cannot be imparted to the ophthalmic lens material.For these reasons, N-vinylpyrrolidone (C-1) is used in combination with a hydrophilic monomer (C-2) containing an acryloyl group, a vinyl group or an allyl group.
The combined use of N-vinylpyrrolidone (C-1) and a hydrophilic monomer (C-2) is essential, and the polymerizable group of the hydrophilic monomer (C-2) is an acryloyl group, a vinyl group, or an allyl group in consideration of copolymerizability with N-vinylpyrrolidone (C-1).

Representative examples of the hydrophilic monomer (C-2) include acrylamide, N,
acrylamide monomers such as N-dimethylacrylamide, N,N-diethylacrylamide, N,N-dimethylaminopropylacrylamide, N-isopropylacrylamide, and acryloylmorpholine; hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxybutyl acrylate; (alkyl)aminoalkyl acrylates such as 2-dimethylaminoethyl acrylate and 2-butylaminoethyl acrylate; alkylene glycol monoacrylates such as ethylene glycol monoacrylate and propylene glycol monoacrylate; polyalkylene glycol monoacrylates such as polyethylene glycol monoacrylate and polypropylene glycol monoacrylate; ethylene glycol allyl ether;
Ethylene glycol vinyl ether; acrylic acid; aminostyrene; hydroxystyrene; vinyl acetate; glycidyl acrylate; allyl glycidyl ether;
Vinyl propionate; N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-
4-methyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-
vinyl-6-methyl-2-pyrrolidone, N-vinyl-3-ethyl-2-pyrrolidone, N-vinyl-4,5-dimethyl-2-pyrrolidone, N-vinyl-5,5-dimethyl-2-pyrrolidone, N-vinyl-3,3,5-trimethyl-2-pyrrolidone, N-vinyl-2-piperidone, N-vinyl-3-methyl-2-piperidone,
N-vinyl-4-methyl-2-piperidone, N-vinyl-5-methyl-2-piperidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-
2-piperidone, N-vinyl-3,5-dimethyl-2-piperidone, N-vinyl-4,4-dimethyl-2-piperidone, N-vinyl-2-caprolactam, N-
Vinyl-3-methyl-2-caprolactam, N-vinyl-4-methyl-2-caprolactam, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-
Ethyl-2-caprolactam, N-vinyl-3,5-dimethyl-2-caprolactam, N-vinyl-4,6-dimethyl-2-caprolactam, N-vinyl-3,
N-vinyl lactams such as 5,7-trimethyl-2-caprolactam; N-vinyl amides such as N-vinylformamide, N-vinyl-N-methylformamide, N-vinyl-N-ethylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, and N-vinylphthalimide;
These may be used alone or in combination of two or more.

Among the hydrophilic monomers (C-2), acrylamide, N,N-dimethylacrylamide,
At least one selected from N,N-diethylacrylamide, N-isopropylacrylamide, acryloylmorpholine, 2-hydroxyethyl acrylate, 2-dimethylaminoethyl acrylate and vinyl acetate is preferred, and N,N-dimethylacrylamide is particularly preferred.

In addition, in a system using a component that is hydrolyzed by an acid or a base, such as vinyl acetate, the ophthalmic lens can be treated with an acid or a base after production to impart further flexibility and surface water wettability to the ophthalmic lens.

The ratio of N-vinylpyrrolidone (C-1) to hydrophilic monomer (C-2) [(C
If the amount of N-vinylpyrrolidone (C-1)/(C-2) (weight ratio) is small, the surface water wettability and low friction of the ophthalmic lens material may be impaired. Therefore, the weight ratio should be 50/50 or more, preferably 55/45 or more, and more preferably 60/4
If the proportion of N-vinylpyrrolidone (C-1) is too high, the polymerization system becomes cloudy, the transparency of the ophthalmic lens material decreases, and the hardness of the material itself increases, which may adversely affect the wearing comfort. Therefore, the ratio is 100/0 or less, preferably 95/5 or less, and more preferably 90/10 or less.

The proportions of the polysiloxane macromonomer (A), silicon-containing alkyl methacrylate (B) and hydrophilic monomer (C), which are essential components for obtaining the ophthalmic lens material of the present invention, are set as follows:

The ratio of the total of the polysiloxane macromonomer (A) and the silicon-containing alkyl methacrylate (B) to the hydrophilic monomer (C) [total of (A) and (B)/(C) (weight ratio)] should be 30/70 or more, preferably 35/65 or more, and more preferably 40/70 or more, since if the amount of the hydrophilic monomer (C) is large, the oxygen permeability of the ophthalmic lens material depends on the water content, making it impossible to obtain high oxygen permeability.
If the ratio is 60 or more and the total amount of the polysiloxane macromonomer (A) and the silicon-containing alkyl methacrylate (B) is large, the flexibility of the ophthalmic lens material is lost, and the material becomes hard and stiff to the touch or has a sticky surface, which adversely affects the wearing comfort. Therefore, the ratio is 70/30 or less, preferably 67/33 or less, and more preferably 65/35 or less.

The ratio of the total of the polysiloxane macromonomer (A) and the silicon-containing alkyl methacrylate (B) to the hydrophilic monomer (C) [total of (A) and (B)/(C) (weight ratio)] is a required condition simultaneously with the ratio of the polysiloxane macromonomer (A) to the silicon-containing alkyl methacrylate (B) [(A
When the amount of the silicon-containing alkyl methacrylate (B) is large, the stickiness of the surface of the ophthalmic lens material becomes significant and the shape retention of the material decreases. Therefore, the weight ratio of the silicon-containing alkyl methacrylate (B) to the surface of the ophthalmic lens material is set to 25/75 or more, preferably 30/70 or more, and more preferably 30/70 or more.
If the amount of polysiloxane macromonomer (A) is too large, the ophthalmic lens material loses flexibility and becomes hard and brittle, so the ratio is 75/25 or less, preferably 73/27 or less, and more preferably 70/30 or less.

If it is desired to further impart desired properties to the resulting ophthalmic lens material, a monomer (D) is used.

The monomer (D) is at least one selected from alkyl (meth)acrylates and fluorine-containing alkyl (meth)acrylates.

Alkyl (meth)acrylate is a component that adjusts the hardness of the ophthalmic lens material, thereby imparting hardness or softness to the material.

Representative examples of alkyl (meth)acrylates include, 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, t-butyl (meth)acrylate, pentyl (meth)
linear, branched or cyclic alkyl(meth)acrylates such as acrylate, t-pentyl(meth)acrylate, hexyl(meth)acrylate, heptyl(meth)acrylate, nonyl(meth)acrylate, stearyl(meth)acrylate, cyclopentyl(meth)acrylate, and cyclohexyl(meth)acrylate;
These may be used alone or in combination of two or more.

In this specification, the term "(meth)acrylate" means "acrylate and/or methacrylate", and the same applies to other (meth)acrylate derivatives.

The fluorine-containing alkyl (meth)acrylate is a component that improves the lipid contamination resistance of the ophthalmic lens material.

Representative examples of fluorine-containing alkyl (meth)acrylates include those represented by the general formula (X): CH ₂ ═CR ⁴ COOC _s H _(2s−t+1) F _t (X) (wherein R ⁴ is a hydrogen atom or CH ₃ , s is an integer of 1 to 15, and t is an integer of 1 to (2s+1)).
1) represents an integer of 1).

Specific examples of the compound represented by the general formula (X) 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 (
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-tridecafluorooctyl (meth)acrylate, 2,2,3,3,4
, 4,5,5,6,6,7,7,7-tridecafluoroheptyl (meth)acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,1
0-Hexadecafluorodecyl (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
, 9,9,10,10,11,11-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, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,1
1,11,12,12-eicosafluorododecyl (meth)acrylate, etc., which may be used alone or in combination of two or more.

The amount of monomer (D) is desirably 20% by weight or less, preferably 10% by weight or less, of the polymerization components so that the effects of the polysiloxane macromonomer (A), silicon-containing alkyl methacrylate (B), and hydrophilic monomer (C) are fully exhibited. When monomer (D) is added, the amount is desirably 0.01% by weight or more, preferably 0.1% by weight or more, of the polymerization components so that the effects of the monomer (D) are fully exhibited.

The low molecular weight crosslinkable monomer (E) is a component that further improves the mechanical strength of the ophthalmic lens material and imparts durability.

One of the major features of the present invention is that, as the low-molecular-weight crosslinkable monomer (E), a crosslinkable monomer (E-1) containing at least one group selected from an acryloyl group, a vinyl group, and an allyl group and a methacryloyl group, and a crosslinkable monomer (E-2) containing at least two methacryloyl groups are used in combination.

Typical examples of the crosslinkable monomer (E-1) include allyl methacrylate, vinyl methacrylate, 4-vinylbenzyl methacrylate, 3-vinylbenzyl methacrylate, and methacryloyloxyethyl acrylate, which may be used alone or in combination of two or more.

Representative examples of the crosslinkable monomer (E-2) include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, dipropylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane trimethacrylate,
2,2-bis(p-methacryloyloxyphenyl)hexafluoropropane,
2,2-bis(m-methacryloyloxyphenyl)hexafluoropropane,
2,2-bis(o-methacryloyloxyphenyl)hexafluoropropane,
2,2-bis(p-methacryloyloxyphenyl)propane, 2,2-bis(
[0033] Examples of such bis(m-methacryloyloxyphenyl)propane, 2,2-bis(o-methacryloyloxyphenyl)propane, 1,4-bis(2-methacryloyloxyhexafluoroisopropyl)benzene, 1,3-bis(2-methacryloyloxyhexafluoroisopropyl)benzene, 1,2-bis(2-methacryloyloxyhexafluoroisopropyl)benzene, 1,4-bis(2-methacryloyloxyisopropyl)benzene, 1,3-bis(2-methacryloyloxyisopropyl)benzene, 1,2-bis(2-methacryloyloxyisopropyl)benzene, and the like can be used alone or in combination of two or more.

In order to obtain the desired mechanical properties, it is important to shorten the distance between crosslinking points, and furthermore, taking into consideration the polymerizability of the crosslinkable monomer, a low molecular weight compound is preferred.

The low molecular weight crosslinkable monomer (E) used in the present invention is a low molecular weight crosslinkable monomer having at least one group selected from an acryloyl group, a vinyl group, and an allyl group, and a methacryloyl group.
The crosslinking monomer (E-1) has different polymerizable groups, and the crosslinking monomer (E-2) has the same polymerizable group, that is, at least two methacryloyl groups.The polysiloxane macromonomer (A) that acts as a high molecular weight crosslinking monomer is used in combination with these crosslinking monomers (E-1) and (E-2).This polysiloxane macromonomer (A) has a group selected from acryloyl group, vinyl group and allyl group, so it can effectively connect the segments that are made up of the monomers that have these acryloyl group, vinyl group and allyl group.Here, for example, when ethylene glycol dimethacrylate is used as crosslinking monomer (E-2), the segments that contain methacryloyl group are connected to each other,
Furthermore, when allyl methacrylate is used as the crosslinking monomer (E-1), the segment containing an acryloyl group, a vinyl group, and an allyl group is effectively linked to the segment consisting of a monomer having a methacryloyl group. Moreover, both ethylene glycol dimethacrylate and allyl methacrylate are less toxic than compounds such as vinyl methacrylate, making them extremely suitable monomers for ophthalmic lens materials.

In this way, the polysiloxane macromonomer (A
By using three types of monomers, namely, (1) the copolymer (B) and (2) the low molecular weight crosslinking monomers (E) allyl methacrylate and ethylene glycol dimethacrylate, it is possible to impart an effective crosslinked structure to the polymer without imparting toxicity.
Therefore, in order to obtain an ophthalmic lens material that has excellent mechanical properties and is highly safe, it is particularly preferred that, among the low-molecular-weight crosslinkable monomers (E), the crosslinkable monomer (E-1) be allyl methacrylate and the crosslinkable monomer (E-2) be ethylene glycol dimethacrylate.

The amount of low-molecular-weight crosslinkable monomer (E) is desirably 1 part or less, preferably 0.8 parts or less, per 100 parts by weight (hereinafter referred to as parts) of the total amount of polysiloxane macromonomer (A), silicon-containing alkyl methacrylate (B), hydrophilic monomer (C), and monomer (D) so as to prevent the ophthalmic lens material from becoming brittle; and in order to further improve the mechanical strength of the ophthalmic lens material and fully exhibit the effect of imparting durability, the amount is desirably 0.05 parts or more, preferably 0.1 parts or more, per 100 parts of the total amount of polysiloxane macromonomer (A), silicon-containing alkyl methacrylate (B), hydrophilic monomer (C), and monomer (D).

In the present invention, as described above, a low-molecular-weight crosslinkable monomer (E) consisting of two types of monomers having different polymerizable groups and a polysiloxane macromonomer (A), which is a high-molecular-weight crosslinkable monomer, are simultaneously used as crosslinking components, which significantly improves the copolymerizability of the silicon-containing alkyl methacrylate (B), hydrophilic monomer (C), and monomer (D), each having a different polymerizable group, thereby improving various physical properties of the resulting ophthalmic lens material. Therefore, it is more preferable that the proportion of polymerizable groups in each monomer be specified, for example, by the following conditions:

The total number of moles of acryloyl groups, vinyl groups, and allyl groups in the hydrophilic monomer (C) and the monomer (D) is α, the total number of moles of methacryloyl groups in the silicon-containing alkyl methacrylate (B) and the monomer (D) is β, and the total number of moles of polysiloxane macromonomer (A) and low-molecular-weight crosslinkable monomer (E) is β.
The total number of moles of acryloyl groups, vinyl groups, and allyl groups in the low molecular weight crosslinkable monomer (E) is represented by γ, and the total number of moles of methacryloyl groups in the low molecular weight crosslinkable monomer (E) is represented by δ.
Then, these α, β, γ and δ are α/γ=20 to 80 and β/δ=1.
It is preferable that the range of 5 to 30 is satisfied.

The ratio α/γ is set to 20 or more, preferably 20 or less, from the viewpoint of increasing the crosslink density in the polymer containing an acryloyl group, a vinyl group, and/or an allyl group, thereby eliminating the risk of the resulting ophthalmic lens material becoming too hard or elongation decreasing.
It is desirable that the molecular weight is 5 or more, and in order to prevent a large amount of monomers having an acryloyl group, a vinyl group and/or an allyl group from remaining uncrosslinked, which may increase the amount of residual monomers and cause the surface of the ophthalmic lens material to become sticky or the frictional properties to increase, it is desirable that the molecular weight is 80 or less, preferably 75 or less.

The ratio β/δ is preferably 15 or more, more preferably 16 or more, in order to prevent excessive crosslinking of methacryloyl groups and a decrease in the flexibility of the ophthalmic lens material. In addition, the domain of the polymer containing methacryloyl groups becomes large,
In order to prevent the transparency of the ophthalmic lens material from decreasing, the viscosity should be 30 or less, preferably 2
It is desirable that it be 8 or less.

In the present invention, it is more preferable that the amount of the low-molecular-weight crosslinkable monomer (E) is 1 part or less per 100 parts of the total amount of the polysiloxane macromonomer (A), silicon-containing alkyl methacrylate (B), hydrophilic monomer (C) and monomer (D), and that α/γ = 20 to 80 and β/δ = 15 to 30, since this further improves the copolymerizability of the polymerization components and further improves various physical properties of the ophthalmic lens material.

Furthermore, the crosslinking point ratio, which is the ratio of (α/γ) to (β/δ), is the ratio of the ease of forming acryloyl crosslinking points, vinyl crosslinking points, or allyl crosslinking points to methacryloyl crosslinking points when all polymerizable groups of the crosslinking components are crosslinked by monomers of the same polymerizable group.Such a crosslinking point ratio ((α/γ)/(β/δ)) is preferably close to 1 in terms of the uniformity of the copolymer, but in reality, considering the low reactivity of allyl groups in particular, it is preferably 1 to 3.Depending on the ratio of the monomer having an acryloyl group, vinyl group, or allyl group to the monomer having a methacryloyl group, if such a crosslinking point ratio is too large, a non-uniform crosslinked structure is likely to occur, which tends to reduce the transparency of the ophthalmic lens material and increase the stickiness and friction of the surface.On the other hand, if the crosslinking point ratio is too small,
The number of methacryloyl crosslinking points increases, which tends to decrease the water content and flexibility of the ophthalmic lens material and increase stress relaxation. Therefore, the crosslinking point ratio is desirably 1 or more, preferably 1.1 or more, and 3 or less, preferably 2.9 or less.

The ophthalmic lens material of the present invention is a composition comprising the polysiloxane macromonomer (A), the silicon-containing alkyl methacrylate (B), the hydrophilic monomer (C), the monomer (D
The polymerizable component is a copolymer obtained by polymerizing a polymerizable component mainly composed of a polysiloxane macromonomer (A) and a low molecular weight crosslinking monomer (E). In order to improve various physical properties of the ophthalmic lens material, the polymerizable component further contains a polysiloxane macromonomer (A).
), silicon-containing alkyl methacrylate (B), hydrophilic monomer (C), monomer (D), and low-molecular-weight crosslinkable monomer (E) may contain a monomer having an unsaturated double bond copolymerizable therewith (hereinafter referred to as other monomer (F)).
When the other monomer (F) is used, the total amount of the main components, polysiloxane macromonomer (A), silicon-containing alkyl methacrylate (B), hydrophilic monomer (C), monomer (D) and low-molecular crosslinking monomer (E), is 70% by weight or more of the polymerization components, preferably 80% by weight or more, in consideration of the excellent oxygen permeability, mechanical strength, flexibility, surface water wettability, wearing comfort and low friction of the ophthalmic lens material.
It is desirable that the content is 0% by weight or more.

When another monomer (F) is used, the ratio of α to γ (α/γ) is 20
It is preferable to adjust the amount of other monomer (F) so that the α/γ ratio is in the range of 1 to 80, the ratio of β to δ (β/δ) is in the range of 15 to 30, and the crosslinking point ratio ((α/γ)/(β/δ)) is in the range of 1 to 3.

For example, in order to adjust the hardness of an ophthalmic lens material to give it hardness or softness,
Hardness adjusting monomers can be used as other monomers (F).

Representative examples of hardness adjusting monomers include alkoxyalkyl(meth)acrylates such as 2-ethoxyethyl(meth)acrylate, 3-ethoxypropyl(meth)acrylate, 2-methoxyethyl(meth)acrylate, and 3-methoxypropyl(meth)acrylate; alkylthioalkyl(meth)acrylates such as ethylthioethyl(meth)acrylate and methylthioethyl(meth)acrylate;
acrylates; styrene; α-methylstyrene; alkylstyrenes such as methylstyrene, ethylstyrene, propylstyrene, butylstyrene, t-butylstyrene, isobutylstyrene, and pentylstyrene; methyl-α-methylstyrene, ethyl-α-methylstyrene, propyl-α-methylstyrene, butyl-α-
Examples include alkyl-α-methylstyrenes such as methylstyrene, t-butyl-α-methylstyrene, isobutyl-α-methylstyrene, and pentyl-α-methylstyrene, and these can be used alone or in combination of two or more.

The amount of hardness adjusting monomer in the polymerization components is desirably 1% by weight or more, preferably 3% by weight or more, in order to sufficiently impart the desired hardness and softness to the ophthalmic lens material, and is desirably 30% by weight or less, preferably 20% by weight or less, in order to prevent a decrease in the oxygen permeability and mechanical strength of the ophthalmic lens material.

For example, in order to further improve the oxygen permeability of the ophthalmic lens material, a silicon-containing alkyl acrylate can be used as the other monomer (F).

Representative examples of the silicon-containing alkyl acrylate include, for example, trimethylsiloxydimethylsilylmethyl acrylate, trimethylsiloxydimethylsilylpropyl acrylate, methylbis(trimethylsiloxy)silylpropyl acrylate, tris(trimethylsiloxy)silylpropyl acrylate, mono[methylbis(trimethylsiloxy)siloxy]bis(trimethylsiloxy)
Silylpropyl acrylate, tris[methylbis(trimethylsiloxy)siloxy]silylpropyl acrylate, methylbis(trimethylsiloxy)silylpropyl glyceryl acrylate, tris(trimethylsiloxy)silylpropyl glyceryl acrylate, mono[methylbis(trimethylsiloxy)siloxy]bis(trimethylsiloxy)silylpropyl glyceryl acrylate, trimethylsilylethyl tetramethyldisiloxypropyl glyceryl acrylate, trimethylsilylmethyl acrylate, trimethylsilylpropyl acrylate,
Trimethylsilylpropylglyceryl acrylate, trimethylsiloxydimethylsilylpropylglyceryl acrylate, methylbis(trimethylsiloxy)
Examples include silylethyl tetramethyldisiloxymethyl acrylate, tetramethyltriisopropylcyclotetrasiloxanylpropyl acrylate, and tetramethyltriisopropylcyclotetrasiloxybis(trimethylsiloxy)silylpropyl acrylate, and these can be used alone or in combination of two or more.

The amount of silicon-containing alkyl acrylate in the polymerization components is desirably 1% by weight or more, preferably 3% by weight or more, in order to sufficiently improve the oxygen permeability of the ophthalmic lens material, and is desirably 30% by weight or less, preferably 20% by weight or less, in order to prevent a decrease in the surface water wettability of the ophthalmic lens material.

For example, in order to further improve the oxygen permeability and mechanical strength of the ophthalmic lens material, a silicon-containing styrene derivative can be used as another monomer (F).

Examples of the silicon-containing styrene derivative include those represented by the general formula (IX): (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 silicon-containing styrene derivatives represented by general formula (IX), if p or r is an integer of 16 or greater, purification and synthesis become difficult, and the hardness of the resulting ophthalmic lens material tends to decrease, while if q is an integer of 2 or greater, synthesis of the silicon-containing styrene derivative tends to become difficult.

Representative examples of the silicon-containing styrene derivatives represented by the general formula (IX) include, for example, tris(trimethylsiloxy)silylstyrene, bis(trimethylsiloxy)methylsilylstyrene, (trimethylsiloxy)dimethylsilylstyrene, tris(trimethylsiloxy)siloxydimethylsilylstyrene, [bis(trimethylsiloxy)methylsiloxy]dimethylsilylstyrene, (trimethylsiloxy)dimethylsilylstyrene, heptamethyltrisiloxanylstyrene, nonamethylsiloxysilylstyrene, and the like. Methyltetrasiloxanylstyrene, pentadecamethylheptasiloxanylstyrene, heneicosamethyldecasiloxanylstyrene, heptacosamethyltridecasiloxanylstyrene, hentriacontamethylpentadecasiloxanylstyrene, trimethylsiloxypentamethyldisiloxymethylsilylstyrene, tris(pentamethyldisiloxy)silylstyrene, tris(trimethylsiloxy)siloxybis(trimethylsiloxy)silylstyrene, bis(heptamethyltrisiloxy)silylstyrene bis(trimethylsiloxy)siloxy]methylstyrene, tris[methylbis(trimethylsiloxy)siloxy]silylstyrene, trimethylsiloxybis[tris(trimethylsiloxy)siloxy]silylstyrene, heptakis(trimethylsiloxy)trisilylstyrene, nonamethyltetrasiloxyundecylmethylpentasiloxymethylsilylstyrene, tris[tris(trimethylsiloxy)siloxy]silylstyrene, (tristrimethylsiloxyhexamethyl)tetrasiloxy[tris(trimethylsiloxy) [0033] Examples of such styrene compounds include styrene, bis(tridecamethylhexasiloxy)methylsilylstyrene, nonakis(trimethylsiloxy)tetrasilylstyrene, bis(tridecamethylhexasiloxy)methylsilylstyrene, heptamethylcyclotetrasiloxanylstyrene, heptamethylcyclotetrasiloxybis(trimethylsiloxy)silylstyrene, tripropyltetramethylcyclotetrasiloxanylstyrene, and trimethylsilylstyrene, and these can be used alone or in combination of two or more.

The amount of the silicon-containing styrene derivative in the polymerization components is 1% by weight or more, preferably 3% by weight or more, in order to sufficiently improve the oxygen permeability and mechanical strength of the ophthalmic lens material.
% by weight or more, and in order to prevent the surface water wettability of the ophthalmic lens material from decreasing, it is desirable that the content be 30% by weight or less, preferably 20% by weight or less.

For example, for the purpose of further improving the flexibility and surface water wettability of the ophthalmic lens material, a hydrophilic monomer having a methacryloyl group can be used as the other monomer (F).

Representative examples of hydrophilic monomers having a methacryloyl group include methacrylamide-based monomers such as methacrylamide, N,N-dimethylmethacrylamide, N,N-diethylmethacrylamide, N,N-dimethylaminopropylmethacrylamide, N-isopropylmethacrylamide, and methacryloylmorpholine; hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate;
(Alkyl)aminoalkyl methacrylates such as 2-dimethylaminoethyl methacrylate and 2-butylaminoethyl methacrylate; alkylene glycol monomethacrylates such as ethylene glycol monomethacrylate and propylene glycol monomethacrylate; polyethylene glycol monomethacrylate,
Examples include polyalkylene glycol monomethacrylates such as polypropylene glycol monomethacrylate; and methacrylic acid, which may be used alone or in combination of two or more.

The amount of hydrophilic monomer having a methacryloyl group in the polymerization components is desirably 1% by weight or more, preferably 3% by weight or more, in order to sufficiently improve the flexibility and surface water wettability of the ophthalmic lens material, and is desirably 30% by weight or less, preferably 20% by weight or less, in order to prevent a decrease in the oxygen permeability of the ophthalmic lens material.

For example, for the purpose of imparting ultraviolet absorbing properties to an ophthalmic lens material or coloring the material, polymerizable ultraviolet absorbing monomers, polymerizable dyes and polymerizable ultraviolet absorbing dyes can be used as the other monomers (F).

Specific examples of the polymerizable ultraviolet absorbing monomer include 2-hydroxy-4-(meth)acryloyloxybenzophenone, 2-hydroxy-4-(meth)acryloyloxy-5-t-butylbenzophenone, 2-hydroxy-4-(meth)acryloyloxy-5-t-butylbenzophenone,
benzophenone-based polymerizable ultraviolet-absorbing monomers such as 2-(meth)acryloyloxy-2',4'-dichlorobenzophenone and 2-hydroxy-4-(2'-hydroxy-3'-(meth)acryloyloxypropoxy)benzophenone;
-(2'-hydroxy-5'-(meth)acryloyloxyethylphenyl)-
2H-benzotriazole, 2-(2'-hydroxy-5'-(meth)acryloyloxyethylphenyl)-5-chloro-2H-benzotriazole, 2-(
2'-hydroxy-5'-(meth)acryloyloxypropylphenyl)-2
benzotriazole-based polymerizable ultraviolet-absorbing monomers such as 2-(2'-hydroxy-5'-(meth)acryloyloxypropyl-3'-t-butylphenyl)-5-chloro-2H-benzotriazole; salicylic acid derivative-based polymerizable ultraviolet-absorbing monomers such as 2-hydroxy-4-methacryloyloxymethyl phenyl benzoate; 2-cyano-3-phenyl-3-(3'-
(meth)acryloyloxyphenyl)propenylic acid methyl ester, and the like, which can be used alone or in combination of two or more.

Specific examples of the polymerizable dye include 1-phenylazo-4-(meth)
Acryloyloxynaphthalene, 1-phenylazo-2-hydroxy-3-(meth)acryloyloxynaphthalene, 1-naphthylazo-2-hydroxy-3-
(meth)acryloyloxynaphthalene, 1-(α-anthryl azo)-2-hydroxy-3-(meth)acryloyloxynaphthalene, 1-((4'-(phenylazo)-phenyl)azo)-2-hydroxy-3-(meth)acryloyloxynaphthalene, 1-(2',4'-xylyl azo)-2-(meth)acryloyloxynaphthalene, 1-(o-tolylazo)-2-(meth)acryloyloxynaphthalene, 2-(m-(meth)acryloylamido-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
,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
azo-based polymerizable dyes such as 1,5-triazine, 2-amino-4-(p-phenylazoanilino)-6-isopropenyl-1,3,5-triazine, and 4-phenylazo-7-(meth)acryloylamide-1-naphthol; 1,5-bis((meth)acryloylamino)-9,10-anthraquinone, 1-(4'-vinylbenzoylamide)-9,10-anthraquinone, 4-amino-1-(4'-vinylbenzoylamide)-9,10-anthraquinone, 5-amino-1-(4'-vinylbenzoylamide)-9,10-anthraquinone, 8-amino-1-(4'
-vinylbenzoylamido)-9,10-anthraquinone, 4-nitro-1-(
4'-vinylbenzoylamido)-9,10-anthraquinone, 4-hydroxy-1-(4'-vinylbenzoylamido)-9,10-anthraquinone, 1-(
3'-vinylbenzoylamido)-9,10-anthraquinone, 1-(2'-vinylbenzoylamido)-9,10-anthraquinone, 1-(4'-isopropenylbenzoylamido)-9,10-anthraquinone, 1-(3'-isopropenylbenzoylamido)-9,10-anthraquinone, 1-(2'-isopropenylbenzoylamido)-9,10-anthraquinone, 1,4-bis(4'-vinylbenzoylamido)-9,10-anthraquinone, 1,4-bis(4'-isopropenylbenzoylamido)-9,10-anthraquinone, 1,5'-bis(4'-vinylbenzoylamido)-9,10-anthraquinone, 1,5-bis(4'-isopropenylbenzoylamido)-9,10-anthraquinone, 1-
Methylamino-4-(3'-vinylbenzoylamido)-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)acryloylamido-anilino)-4-(3'-(3"-sulfo-4"-aminoanthraquinon-1"-yl)-amino-anilino)-6-chloro-1,3,5-triazine, 2-(3'-
(meth)acryloylamido-anilino)-4-(3'-(3"-sulfo-4"
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-triazine and other anthraquinone-based polymerizable dyes; o-nitroanilinomethyl (meth)acrylate and other nitro-based polymerizable dyes; and phthalocyanine-based polymerizable dyes such as (meth)acryloylated tetraamino copper phthalocyanine and (meth)acryloylated (dodecanoylated tetraamino copper phthalocyanine). These can be used alone or in combination of two or more.

Specific examples of the polymerizable ultraviolet absorbing dye include 2,4-dihydroxy-3(p-styreneazo)benzophenone, 2,4-dihydroxy-5-(p
-styreneazo)benzophenone, 2,4-dihydroxy-3-(p-(meth)
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)acryloyloxyethylphenylazo)benzophenone,
-(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-
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-(meth)acryloyloxyethylamino)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-dihydroxy-5-
benzophenone-based polymerizable ultraviolet absorbing dyes such as (o-(N-ethyl-N-(meth)acryloylamino)phenylazo)benzophenone, and 2-hydroxy-4
and benzoic acid-based polymerizable ultraviolet absorbing dyes such as phenyl-(p-styreneazo)benzoate. These may be used alone or in combination of two or more kinds.

The amounts of the polymerizable UV-absorbing monomer, polymerizable dye, and polymerizable UV-absorbing dye are greatly affected by the lens thickness, so they are desirably 3 parts or less, preferably 0.01 to 2 parts, per 100 parts of the total amount of polymerizable components. If these amounts exceed 3 parts, the mechanical strength of the ophthalmic lens material tends to decrease. Furthermore, considering the toxicity of the UV-absorbing monomer and dye, they tend to be unsuitable as materials for ophthalmic lenses such as contact lenses that come into direct contact with biological tissues and intraocular lenses that are implanted in the body. Furthermore, especially in the case of dyes, if the amount is too large, the color of the lens tends to darken, transparency tends to decrease, and the lens tends to have difficulty transmitting visible light.

To obtain the copolymer that constitutes the ophthalmic lens material of the present invention, the amounts of the polymerization components, which are the polysiloxane macromonomer (A), the silicon-containing alkyl methacrylate (B), the hydrophilic monomer (C), the monomer (D) and the low-molecular-weight crosslinkable monomer (E), and, if necessary, other monomers (F), are appropriately adjusted so that they fall within the above-mentioned ranges, and the components are polymerized by a template method by heating and/or irradiating with ultraviolet light.

When the polymerization components are heated and polymerized by the mold method, the polymerization components and a radical polymerization initiator are blended into a mold corresponding to the shape of the desired ophthalmic lens, and the mold is gradually heated to polymerize the polymerization components, and the resulting molded product is subjected to mechanical processing such as cutting, polishing, etc. as necessary. Cutting may be performed over the entire surface of at least one or both surfaces of the molded product (copolymer), or may be performed on a portion of at least one or both surfaces of the molded product (copolymer).
In order to broaden the range of uses of the product, such as special lenses, it is particularly preferable that the ophthalmic lens material of the present invention is a molded product (copolymer) in which at least one surface or a part thereof has been cut. Cutting at least one surface of such a molded product (copolymer) means performing blank molding,
That is, the concept includes cutting a blank obtained by polymerization using a casting method into a desired ophthalmic lens shape. The polymerization may be carried out by, for example, a bulk polymerization method or a solution polymerization method using a solvent or the like.

Specific examples of the radical polymerization initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, etc., which can be used alone or in combination of two or more. The amount of the radical polymerization initiator is about 0.001 to 2 parts, preferably 0.001 to 2 parts, per 100 parts of the polymerization components.
It is desirable that it be 1 to 1 part.

The heating temperature when heating the polymerization components in the mold is desirably 50°C or higher, preferably 60°C or higher, from the viewpoints of shortening the polymerization time and reducing residual monomer components, and is desirably 150°C or lower, preferably 140°C or lower, from the viewpoints of suppressing volatilization of each polymerization component and preventing deformation of the mold.
The heating time for heating the polymerization components in the mold is desirably 10 minutes or more, preferably 20 minutes or more, from the viewpoint of shortening the polymerization time and reducing the amount of residual monomer components, and is desirably 120 minutes or less, preferably 60 minutes or less, from the viewpoint of preventing deformation of the mold. Note that such heating may be carried out by increasing the temperature stepwise.

When the polymerization components are heated to polymerize, the polymerization components are selected from the group consisting of polysiloxane macromonomers (
The ratio of the total of (A) and the silicon-containing alkyl methacrylate (B) to the hydrophilic monomer (C) [total of (A) and (B)/(C) (weight ratio)] is 30/70.
and the ratio of the polysiloxane macromonomer (A) to the silicon-containing alkyl methacrylate (B) is [
(A)/(B) (weight ratio)] is 25/75 to 75/25, preferably 40/60
60/40, and N-vinylpyrrolidone (C-1) and a hydrophilic monomer (
The ratio of (C-1) to (C-2) [(C-1)/(C-2) (weight ratio)] is 50/50 to 100
It is particularly desirable that the ratio of the monomer (D) is 0 to 20% by weight, preferably 0 to 10% by weight, of the polymerizable components.

When polymerizing the polymerization components by the casting method with ultraviolet irradiation, the polymerization components and a photopolymerization initiator are mixed in a mold corresponding to the shape of the desired ophthalmic lens, and then the mold is irradiated with ultraviolet light to polymerize the polymerization components, and the obtained molded body is subjected to mechanical processing such as cutting and polishing as necessary. Cutting may be performed on at least one or both surfaces of the molded body (copolymer), or the molded body (
The cutting may be performed on at least one surface or a portion of both surfaces of a molded product (copolymer) such as a special lens. In consideration of broadening the range of uses of the product, it is particularly preferable that the ophthalmic lens material of the present invention be a molded product (copolymer) in which at least one surface or a portion thereof has been cut. The cutting of at least one surface of such a molded product (copolymer) includes blank molding, as in the case of a molded product (copolymer) obtained by heating the polymerized components, i.e., cutting a blank obtained by polymerization using a casting method into the desired ophthalmic lens shape. The polymerization may be performed by bulk polymerization or solution polymerization using a solvent or the like. Furthermore, although the polymerization is performed by ultraviolet irradiation as described above in the present invention, electron beam irradiation can be used instead of ultraviolet irradiation, in which case the polymerized components are polymerized without a photopolymerization initiator.

Specific examples of the photopolymerization initiator include benzoin-based photopolymerization initiators such as methyl orthobenzoyl benzoate, methyl benzoyl formate, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin-n-butyl ether;
-hydroxy-2-methyl-1-phenylpropan-1-one, p-isopropyl-α-hydroxyisobutylphenone, p-t-butyltrichloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone, α,α-dichloro-
Examples include phenone-based photopolymerization initiators such as 4-phenoxyacetophenone and N,N-tetraethyl-4,4-diaminobenzophenone; 1-hydroxycyclohexyl phenyl ketone; 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime; thioxanthone-based photopolymerization initiators such as 2-chlorothioxanthone and 2-methylthioxanthone; dibenzosubalone; 2-ethylanthraquinone; benzophenone acrylate; benzophenone; and benzil.
These may be used alone or in combination of two or more. A photosensitizer may be used together with the photopolymerization initiator. The amount of the photopolymerization initiator and the photosensitizer is about 0.001 to 2 parts, preferably 0.01 to 100 parts of the polymerization components.
It is desirable that it be a department.

In order to improve the uniformity of the components in the polymerization components, the polymerization can be carried out in the presence of a diluent. As such a diluent, a solvent capable of dissolving the polymerization components is used, and the mixed solution of the polymerization components to which the diluent has been added is made uniform, which has the advantage that phase separation is less likely to occur during polymerization and the resulting ophthalmic lens material is less likely to become cloudy.

Representative examples of the diluent include alcohols having 1 to 10 carbon atoms, such as ethanol, propanol, butanol, pentanol, hexanol, octanol, and decanol.
Examples of the diluent include alcohols containing 12 carbon atoms, ketones having 2 to 4 carbon atoms such as acetone and methyl ethyl ketone, acetonitrile, chloroform, etc. These can be used alone or in combination of two or more. The diluent can be appropriately selected depending on the type of polymerization component.

The amount of the diluent is preferably 0.5 parts or more, and more preferably 1 part or more, per 100 parts of the polymerization components in order to fully exhibit the effect of suppressing phase separation.
It is desirable that the amount is 00 parts or less, preferably 80 parts or less.

The ultraviolet irradiance at a wavelength of 365 nm when irradiating the polymerizable components in the mold with ultraviolet light is desirably 0.5 mW/ ^cm2 or more, preferably 1 mW/ ^cm2 or more, from the viewpoints of shortening the polymerization time, reducing residual monomer components, and reducing stickiness, and is desirably 20 mW/ ^cm2 or less, preferably 15 mW/ ^cm2 or less, from the viewpoint of preventing deterioration of the material. The irradiation time when irradiating the polymerizable components in the mold with ultraviolet light is desirably 1 minute or more, preferably 5 minutes, from the viewpoints of reducing residual monomer components, improving crosslink density, and reducing stickiness.
The time is preferably 80 minutes or less, more preferably 70 minutes or less, in order to prevent scission of the polymer main chain and functional groups and deterioration of the material.

When the polymerization components are polymerized by ultraviolet irradiation, the polymerization components are selected from a polysiloxane macromonomer (A) and a silicon-containing alkyl methacrylate (B) in consideration of reducing residual monomer components and improving the low friction and water wettability of the material surface.
The ratio of the total of (A) and (B) to the hydrophilic monomer (C) [total of (A) and (B)/(C)
(weight ratio)] is 40/60 to 70/30, preferably 45/55 to 65/35, and the ratio of the polysiloxane macromonomer (A) to the silicon-containing alkyl methacrylate (B) [(A)/(B) (weight ratio)] is 35/65 to 75/2
5, preferably 35/65 to 60/40, and N-vinylpyrrolidone (C
the ratio of the monomer (C-1) to the hydrophilic monomer (C-2) [(C-1)/(C-2) (weight ratio)] is 50/50 to 100/0, preferably 60/40 to 85/15, and the amount of the monomer (D) is 0 to 20% by weight, preferably 0 to 10% by weight of the polymerization components;
It is particularly desirable that the

In either case where the polymerization component is polymerized by heating or by irradiating it with ultraviolet light or electron beams, when producing an intraocular lens, the support part of the lens may be produced separately from the lens and then attached to the lens later, or may be molded integrally with the lens at the same time.

In order to impart hydrophilicity and lipid contamination resistance to the surface of an ophthalmic lens, the surface of the ophthalmic lens may be subjected to a plasma treatment, for example, in an oxygen gas atmosphere, an inert gas atmosphere, or air. When such a plasma treatment is performed, the plasma state between the electrodes of the plasma generating device may be under reduced pressure of about 1.3 to 1.3 × 10 ² Pa, or may be under normal pressure.

The ophthalmic lens material of the present invention thus obtained has various properties and preferably has the following physical properties, for example:

The dynamic friction force of the ophthalmic lens material is desirably 0.025 N or less, preferably 0.023 N or less. The smaller the dynamic friction force, the lower the friction property of the ophthalmic lens material.

It is desirable that the contact angle of the ophthalmic lens material is 35° or less, preferably 34° or less at 25° C. The smaller the contact angle, the better the surface water wettability of the ophthalmic lens material.

The methods for measuring the dynamic friction force and contact angle of the ophthalmic lens material are as described below.

As described above, the ophthalmic lens material of the present invention not only has high oxygen permeability and high mechanical strength, but also has other properties such as excellent surface water wettability and low surface friction, and therefore can be suitably used for, for example, contact lenses, intraocular lenses, artificial corneas, etc.

Next, the ophthalmic lens material of the present invention will be explained in more detail based on examples, but the present invention is not limited to these examples.

Examples 1 to 8 and Comparative Examples 1 to 8 Ophthalmic lens components prepared by mixing the polymerization components and polymerization initiators shown in Tables 1 and 2 were poured into a mold having a contact lens shape (made of polypropylene, corresponding to a contact lens with a diameter of about 13 mm and a thickness of 0.1 mm) or a mold having a film shape (
The film was poured into a polypropylene tube (approximately 15 mm in diameter, suitable for a 0.2 mm thick film).

Next, this mold was irradiated with a black light at a wavelength of 365 nm and an illumination intensity of 2 mW.
The coated film was photopolymerized by irradiating it with ultraviolet light at 1/cm ² for 60 minutes to obtain a copolymer.

The resulting copolymer was released from the mold and then immersed in physiological saline to absorb water and carry out a hydration treatment, thereby obtaining an ophthalmic lens material.

Examples 9 to 10 An ophthalmic lens component prepared by mixing the polymerization components and polymerization initiators shown in Table 1 was poured into a mold (made of polypropylene, diameter approximately 13 mm, thickness 0.1 mm) having a contact lens shape.
The solution was poured into a mold (made of polypropylene, approximately 15 mm in diameter and corresponding to a 0.2 mm thick film) or a film-shaped mold (made of polypropylene, approximately 15 mm in diameter and corresponding to a 0.2 mm thick film).

The mold was then heated in a circulation dryer set at 100° C. for 40 minutes to carry out thermal polymerization, thereby obtaining a copolymer.

The resulting copolymer was released from the mold and then immersed in physiological saline to absorb water and carry out a hydration treatment, thereby obtaining an ophthalmic lens material.

Examples 11 to 13 and Comparative Example 9 An ophthalmic lens component prepared by mixing the polymerization components and polymerization initiators shown in Table 3 was poured into a mold (made of polypropylene, diameter approximately 13 mm, thickness 0.1 mm) having a contact lens shape.
The solution was poured into a mold (made of polypropylene, approximately 15 mm in diameter and corresponding to a 0.2 mm thick film) or a film-shaped mold (made of polypropylene, approximately 15 mm in diameter and corresponding to a 0.2 mm thick film).

Next, this mold was irradiated with a black light at a wavelength of 365 nm and an illumination intensity of 2 mW.
The coated film was photopolymerized by irradiating it with ultraviolet light at 1/cm ² for 60 minutes to obtain a copolymer.

The resulting copolymer was released from the mold and then immersed in physiological saline to absorb water and perform a hydration treatment, thereby obtaining an ophthalmic lens material.

Test Example 1 The ophthalmic lens materials obtained in Examples 1 to 13 and Comparative Examples 1 to 9 (diameter: about 13 mm) were
The transparency and surface lubricity of the contact lenses (0.1 mm thick, 0.1 mm diameter) were investigated according to the following methods. The results are shown in Tables 4 to 6.

(a) Transparency The appearance of the contact lens was visually observed and evaluated based on the following evaluation criteria.

(Evaluation criteria) A: No cloudiness, excellent transparency, and ideal for contact lenses.

B: Slight cloudiness is observed, but the transparency is acceptable for contact lenses.

C: Cloudiness and poor transparency make it difficult to use as a contact lens.

D: The material is extremely opaque and has poor transparency, making it unsuitable for use as a contact lens.

(b) Surface Lubricity: The contact lenses were folded in half and held between the fingers, and the lubricity (adhesion between the lenses and the fingers) was examined when the lenses were rubbed with the fingers. The water wettability of the lens surface was also visually observed and evaluated based on the following criteria.

(Evaluation criteria) A: Excellent water wettability and good lens-to-lens sliding, making it ideal for contact lenses.

B: There is a slight creak when the lenses are rubbed together, but they are still usable as contact lenses.

C: There is no adhesion between the lens and the fingers, but the lenses do not slide easily and may become stuck.

D: The surface is sticky and the lens adheres strongly to the fingers.

Test Example 2: The ophthalmic lens materials obtained in Examples 1 to 13 and Comparative Examples 1 to 9 (diameter: about 15 mm) were
0.2 mm thick film) friction, surface water wettability, flexibility, stain resistance,
The oxygen permeability, water content and refractive index were measured according to the following methods, and the results are shown in Tables 4 to 6.

(c) Frictional Properties: A film was fixed to the smooth surface of a cylindrical metal jig with a diameter of 11.28 mm and a weight of 40 g, and the film was placed on a glass plate wetted with distilled water so that the film was in contact with the glass surface. This was pulled at a constant speed using a tensile tester (manufactured by Instron Corporation), and the dynamic friction force (N) was measured.

The smaller the dynamic friction force, the better the surface lubricity and the lower the friction.

(d) Surface Water Wettability Using a contact angle meter (G-I, 2MG, manufactured by Elma Sales Co., Ltd.), the contact angle (°) of the film was measured by the air bubble method in saline at 25° C. The contact angle values shown in Tables 4 to 6 were obtained by attaching a 2 μL air bubble to the film immersed in saline using a syringe, and averaging the left and right contact angles between the air bubble and the film.

The smaller the contact angle, the better the surface water wettability.

(e) Flexibility The periphery of the film was fixed, and its center was fixed to a device that applies a load using a spherical jig with a tip diameter of 1/16 inch. A load of about 20 g was applied to this film and stopped, and the stress ( _S0 (g/ ^mm2 )) immediately after stopping was measured. This was further measured for 3
After leaving it for 0 seconds, the stress (S (g/mm ² )) was measured. Using these stress values S ₀ and S, the stress relaxation rate (%) was calculated according to the following formula.

Stress relaxation rate (%) = {( _S0 - S)/ _S0 } × 100 If the stress relaxation rate is 15% or more, the film will have poor resilience and poor shape recovery, and will not have the flexibility appropriate for an ophthalmic lens material.

(f) Stain Resistance A film was placed in a glass bottle containing 2 mL of an artificial eyelid solution (pH 7 buffer solution) consisting of 0.3 g of oleic acid, 0.3 g of linoleic acid, 4.0 g of tripalmitic acid, 1.0 g of cetyl alcohol, 0.3 g of palmitic acid, 4.0 g of spermaceti, 0.4 g of cholesterol, 0.4 g of cholesterol palmitate, and 14.0 g of egg yolk lecithin, and the bottle was shaken at 37°C for 5 hours.

After 5 hours, the film was removed and immersed in 1 mL of a mixed solution of ethanol and diethyl ether (ethanol:diethyl ether=3:1 (volume ratio)) to extract the lipid components attached to the film.
To 100 μL of the solution, concentrated sulfuric acid was added, and then 3 mg of vanillin and 2 mL of phosphoric acid were added, and the amount of lipid attached to the film (mg/cm ² ) was quantified.

If the amount of lipid adhesion is 1 mg/cm ² or more, lipid stains are likely to adhere and the stain resistance is poor.

(g) Oxygen permeability (Dk _0.2 ) Using a Seikaken-type film oxygen permeability meter (manufactured by Rika Seiki Kogyo Co., Ltd.), the oxygen permeability coefficient of a 0.2 mm thick film was measured in physiological saline at 35° C. The unit of the oxygen permeability coefficient is (cm ² /sec) (mLO ₂ /(mL×hPa)).
The values in Tables 4 to 6 are obtained by multiplying the measured values by 10 ¹¹ .

(h) Moisture content The weight (W (g)) of the hydrated film in an equilibrium moisture state was measured, and the weight ( _W (g)) of the film after the hydration treatment was measured after drying in a dryer.
Using these measured values W ₀ and W 1 , the water content (wt %) was calculated according to the following formula:

Water content (wt%) = {(W - _W0 )/W} x 100 (i) Refractive index The refractive index (unitless) of the film was measured using an Atago refractometer (manufactured by Atago Co., Ltd., 1T) in an atmosphere of 25°C and 50% humidity.

Test Example 3 The residual monomer ratios of the copolymers (plates) obtained in Examples 2, 4 to 6, and 12 and Comparative Examples 1, 5, and 9 were calculated according to the following method. The results are shown in Tables 4 to 6.

(J) Residual Monomer Rate Photopolymerization was carried out by irradiating with ultraviolet light, and the resulting copolymer was released from the mold. The copolymer (plate, approximately 0.2 g) was then immersed in 10 mL of acetonitrile and allowed to stand at 50°C for 24 hours for extraction.

The resulting extract was analyzed by high performance liquid chromatography, and the proportion of residual monomers (N-vinylpyrrolidone and tris(trimethylsiloxy)silylpropyl methacrylate) relative to the blended amount was calculated using the following formula:

Residual monomer rate (wt %) = {V x (A - b)} / (a x W x w x 100) V: Amount of extraction solvent (mL) A: Peak area of monomer a: Slope of calibration curve b: Intercept of calibration curve W: Weight of plate (g) w: Amount of monomer at blending (wt %) Examples 14 to 15 Ophthalmic lens components prepared by mixing the polymerization components and polymerization initiators shown in Table 7 were poured into a block-shaped mold (made of polypropylene, corresponding to a block with a diameter of approximately 12 mm and a thickness of approximately 5 mm).

Next, this mold was irradiated with a black light at a wavelength of 365 nm and an illumination intensity of 2 mW.
The mixture was photopolymerized by irradiating it with ultraviolet light at 1/cm ² for 60 minutes, and the resulting copolymer was then released from the mold.

Example 16 An ophthalmic lens component prepared by mixing the polymerization components and polymerization initiators shown in Table 7 was poured into a mold having a lens shape (made of polypropylene, suitable for a lens having a diameter of about 13 mm and a thickness of about 0.2 mm).

The mold was then heated in a circulating dryer set at 100° C. for 30 minutes to carry out thermal polymerization, and the resulting copolymer was then removed from the mold.

Test Example 4 The transparency and surface lubricity of the copolymers obtained in Examples 14 to 16 were examined by the method of Test Example 1, and the Rockwell hardness and machinability were also examined by the following methods. The results are shown in Table 8.

For the copolymer of Example 16, the Rockwell hardness was not measured because the sample was too thin.

(K) Rockwell hardness (30X) Rockwell superficial hardness tester (manufactured by Akashi Seisakusho Co., Ltd., model ASD)
The Rockwell hardness of the copolymer was measured using the following method.

If the Rockwell hardness is -40 or more, the machined surface is nearly smooth and is suitable for use as an ophthalmic lens material, and if it is -30 or more, the machined surface has excellent smoothness and is particularly preferred for use as an ophthalmic lens material.

(l) Machinability After the surface of the copolymer was machined using a cutting lathe, the surface roughness was observed using an optical microscope and evaluated based on the following criteria.

(Evaluation criteria) A: The surface is extremely smooth and has excellent cutting properties.

B: The surface is almost smooth.

C: Punctures, cracks or fissures are observed on the cut surface, which appears whitish.

D: Soft and impossible to cut.

The abbreviations in the table represent the following compounds.

SK6006: Macromonomer (A-1) SK5001: Tris(trimethylsiloxy)silylpropyl methacrylate DMAA: N,N-dimethylacrylamide DEAA: N,N-diethylacrylamide 2HEA: 2-hydroxyethyl acrylate NVP: N-vinylpyrrolidone EDMA: Ethylene glycol dimethacrylate AMA: Allyl methacrylate MMA: Methyl methacrylate Dar: 2-hydroxy-2-methyl-1-phenylpropan-1-one ABI: 2,2'-azobis(2,4-dimethylvaleronitrile) The amount of each ophthalmic lens component shown in Tables 1 to 3 and 7 is the amount (parts) relative to 100 parts of the total amount of polymerization components other than ethylene glycol dimethacrylate and allyl methacrylate, which are the low molecular weight crosslinkable monomers (E).

In addition, Tables 1 to 3 and 7 also show the following values of (1) to (7).

(A) + (B)/(C) (weight ratio) (A)/(B) (weight ratio) (C-1)/(C-2) (weight ratio) α/γ (mole ratio) β/δ (mole ratio) (α/γ)/(β/δ) (mole ratio) The results shown in Tables 4 and 6 show that the ophthalmic lens materials of the present invention obtained in Examples 1 to 13 all possess excellent transparency and surface lubricity, high oxygen permeability, a high refractive index, and an appropriate water content, as well as low friction with a dynamic friction force of 0.025 N or less, excellent flexibility and resilience with a stress relaxation rate of 13% or less, excellent stain resistance with a lipid deposition amount of less than 1 mg/ ^cm2 , and excellent surface water wettability with a contact angle of around 30°, and furthermore, the residual monomer rates are quite low, at around 2 wt% for N-vinylpyrrolidone and around 0.3 wt% for tris(trimethylsiloxy)silylpropyl methacrylate. Therefore, it is clear that the ophthalmic lens materials of the present invention obtained in Examples 1 to 13 are all extremely suitable as materials for ophthalmic lenses.

In contrast, from the results shown in Tables 5 and 6, the ophthalmic lens materials obtained in Comparative Examples 1 to 9 all had poor surface lubricity, poor transparency, high friction, poor flexibility, poor stain resistance, and poor surface water wettability, particularly N-
It is clear that the material does not have all the excellent properties of the material of the present invention, such as a high residual rate of vinylpyrrolidone, and is therefore unsuitable as a material for ophthalmic lenses.

Furthermore, from the results shown in Table 8, it can be seen that the ophthalmic lens materials of the present invention obtained in Examples 14 to 16 all have excellent transparency and surface lubricity, high Rockwell hardness, and excellent machinability.
It can be seen that the ophthalmic lens materials of the present invention obtained in Example 6 are all extremely suitable as materials for ophthalmic lenses.

INDUSTRIAL APPLICABILITY The ophthalmic lens material of the present invention has not only high oxygen permeability and high mechanical strength, but also excellent surface water wettability and low surface friction.

Therefore, the ophthalmic lens material of the present invention can be suitably used for, for example, contact lenses, intraocular lenses, artificial corneas, etc.

─────────────────────────────────────────────────────── Continued from the front page (51) Int.Cl. ⁷ Identification symbol FI // A61F 2/16 A61F 2/16 (Note) This publication is based on the gazette published internationally by the International Bureau (WIPO). The effect of the international publication of the Japanese language patent application (Japanese language utility model registration application) related to this publication arises pursuant to Article 184-10, Paragraph 1 of the Patent Act (Article 48-13, Paragraph 2 of the Utility Model Act), and is unrelated to this publication.

Claims (9)

[Claims] [Claim 1] (A) General formula (I): A¹-U¹-(-S¹-U²−)_n-S²-U³-A² (I) [In the formula, A¹is represented by general formula (II): Y²¹-Z²¹-R³¹- (II) (In the formula, Y²¹is an acryloyl group, a vinyl group or an allyl group, Z²¹is an oxygen source
a bond or direct bond, R³¹is a direct bond or a straight chain or branched chain having 1 to 12 carbon atoms.
or an alkylene group having an aromatic ring); A²is represented by general formula (III): -R³⁴-Z²²-Y²² (III) (In the formula, Y²²is an acryloyl group, a vinyl group or an allyl group, Z²²is an oxygen source
a bond or direct bond, R³⁴is a direct bond or a straight chain or branched chain having 1 to 12 carbon atoms.
or an alkylene group having an aromatic ring) (wherein the general formula (
II) Y in²¹and Y in general formula (III)²²may be the same or different
(It may be possible); U¹is represented by general formula (IV): -X²¹-E²¹−X²⁵-R³²- (IV) (In the formula, X²¹and X²⁵are each independently a direct bond, an oxygen atom, and an alkyl group.
alkylene glycol groups, E²¹is a -NHCO- group (wherein
, X²¹is a direct bond, and X²⁵is an oxygen atom or an alkylene glycol group
Yes, E²¹is X²⁵and forms a urethane bond), -CONH- group (only
In this case, X²¹is an oxygen atom or an alkylene glycol group, and X²⁵
is a direct bond, and E²¹is X²¹(forming a urethane bond with the
or a diisocyanate selected from the group consisting of unsaturated aliphatic, alicyclic and aromatic diisocyanates.
A divalent group derived from a carboxylate (in this case, X²¹and X²⁵are independent
is selected from an oxygen atom and an alkylene glycol group;²¹is X²¹and
X²⁵Two urethane bonds are formed between R³²has 1 to 6 carbon atoms
(representing a linear or branched alkylene group); S¹and S²are each independently represented by general formula (V): (In the formula, R²³, R²⁴, R²⁵, R²⁶, R²⁷and R²⁸are each unique
an alkyl group having 1 to 6 carbon atoms, a fluorine-substituted alkyl group, or a phenyl group;
group, K is an integer of 1 to 1500, L is 0 or an integer of 1 to 1499, and K+L
is an integer from 1 to 1500); U²is represented by general formula (VI): -R³⁷−X²⁷-E²⁴−X²⁸-R³⁸- (VI) (In the formula, R³⁷and R³⁸are each independently a linear or
a branched alkylene group; X²⁷and X²⁸are each independently an oxygen atom
or an alkylene glycol group; E²⁴is saturated or unsaturated aliphatic, alicyclic
A divalent group derived from a diisocyanate selected from the group consisting of aryl and aromatic diisocyanates (provided that
In this case, E²⁴is X²⁷and X²⁸Two urethane bonds are formed between
A group represented by the formula: U³is represented by the general formula (VII): -R³³−X²⁶-E²²−X²²- (VII) (In the formula, R³³represents a linear or branched alkylene group having 1 to 6 carbon atoms;
X²²and X²⁶are each independently a direct bond, an oxygen atom, and an alkylene group.
Selected from recall groups, E²²is a —NHCO— group (wherein, X²²teeth
is an oxygen atom or an alkylene glycol group, and X²⁶is a direct bond, and E^2
2is X²²and forms a urethane bond), -CONH- group (however, in this case
If, X²²is a direct bond, and X²⁶is an oxygen atom or an alkylene glycol group
and E²²is X²⁶urethane bond) or saturated or unsaturated
Derived from diisocyanates selected from the group consisting of saturated aliphatic, alicyclic and aromatic diisocyanates
(In this case, X²²and X²⁶are each independently oxygen atoms
and alkylene glycol groups, E²²is X²²and X²⁶Noa
a group represented by the formula: (wherein n is 0 or an integer of 1 to 10) in which one or more polymerizable groups represented by the formula:
Polysiloxane macromonomers attached to the siloxane backbone via tungstate bonds
, (B) Silicon-containing alkyl methacrylate (C) N-vinylpyrrolidone (C-1) and the N-vinylpyrrolidone (C-1)
) other than a hydrophilic monomer containing an acryloyl group, a vinyl group, or an allyl group (
C-2) Hydrophilic monomer consisting of (D) alkyl (meth)acrylate and fluorine-containing alkyl (meth)acrylate
(E) at least one monomer selected from the group consisting of an acryloyl group, a vinyl group, and an allyl group;
and a methacryloyl group, and at least two
and a low molecular weight crosslinkable monomer (E-2) containing a methacryloyl group.
Polymerization is performed by heating and/or irradiating ultraviolet light on the polymer component, which is primarily composed of dimethyl silane.
a copolymer of the polysiloxane macromonomer (A) and a silicon-containing alkylmethacrylate;
The ratio of the total of the acrylate (B) and the hydrophilic monomer (C) [(A) and (B)]
the ratio of the polysiloxane macromonomer (A) to the silicon-containing alkyl methacrylate (C) (weight ratio) is 30/70 to 70/30;
The ratio of (A) to (B) (weight ratio) is 25/75 to 75/25.
and The ratio of the N-vinylpyrrolidone (C-1) to the hydrophilic monomer (C-2) [
an ophthalmic lens material in which the weight ratio of (C-1)/(C-2) is 50/50 to 100/0, and the amount of the monomer (D) is 0 to 20% by weight of the polymerization components. 2. The ophthalmic lens material according to claim 1, which is obtained by cutting at least one surface or a part of the surface of the copolymer. [Claim 3] The copolymer is obtained by polymerizing polymerization components by heating them under conditions of a heating temperature of 50 to 150°C for a heating time of 10 to 120 minutes, wherein the polymerization components comprise a ratio of the total of the polysiloxane macromonomer (A) and the silicon-containing alkyl methacrylate (B) to the hydrophilic monomer (C) [total of (A) and (B)/(C) (weight ratio)] of 30/70 to 70/30, a ratio of the polysiloxane macromonomer (A) to the silicon-containing alkyl methacrylate (B) [(A)/(B) (weight ratio)] of 25/75 to 75/25, and a ratio of N-vinylpyrrolidone (C-1) to the hydrophilic monomer (C-2) [(C
2. The ophthalmic lens material according to claim 1, wherein the weight ratio of the monomer (C-1)/(C-2) is 50/50 to 100/0, and the amount of the monomer (D) is 0 to 20% by weight of the polymerization components. 4. The copolymer is a copolymer obtained by subjecting the polymerized components to ultraviolet irradiance of 0.
the polymerization components are a polysiloxane macromonomer ( ^A ) and a silicon-containing alkyl methacrylate (B) in a ratio of 40/60 to 70/30 based on the total weight of the polysiloxane macromonomer (A) and the silicon-containing alkyl methacrylate (B) to the hydrophilic monomer (C) [total of (A) and (B)/(C) (weight ratio)], and a polysiloxane macromonomer (A) in a ratio of 35/65 to 75/25 based on the total weight of the polysiloxane macromonomer (A) and the silicon-containing alkyl methacrylate (B) [(A)/(B) (weight ratio)], and a N-vinylpyrrolidone (C-1) in a ratio of 35/65 to 75/25 based on the total weight of the hydrophilic monomer (C) [(C
2. The ophthalmic lens material according to claim 1, wherein the weight ratio of the monomer (C-1)/(C-2) is 50/50 to 100/0, and the amount of the monomer (D) is 0 to 20% by weight of the polymerization components. 5. The method of claim 1, wherein the amount of the low molecular weight crosslinking monomer (E) is in the range of 1:100 to 1:1000 of the polysiloxane macromonomer (A), the silicon-containing alkyl methacrylate (B), and the hydrophilic monomer (C).
and the ophthalmic lens material according to claim 1, wherein the total amount α of the number of moles of acryloyl groups, the number of moles of vinyl groups, and the number of moles of allyl groups in the hydrophilic monomer (C) and the monomer (D), the total amount β of the number of moles of methacryloyl groups in the silicon-containing alkyl methacrylate (B) and the monomer (D), the total amount γ of the number of moles of acryloyl groups, the number of moles of vinyl groups, and the number of moles of allyl groups in the polysiloxane macromonomer (A) and the low molecular weight crosslinking monomer (E), and the total amount δ of the number of moles of methacryloyl groups in the low molecular weight crosslinking monomer (E) satisfy the following relationships: α/γ=20 to 80, and β/δ=15 to 30. [Claim 6] The ophthalmic lens material according to claim 5, wherein the ratio of (α/γ) to (β/δ) is (α/γ)/(β/δ)=1 to 3. 7. The ophthalmic lens material according to claim 1, wherein the crosslinkable monomer (E-1) is allyl methacrylate and the crosslinkable monomer (E-2) is ethylene glycol dimethacrylate. 8. The ophthalmic lens material according to claim 1, wherein the hydrophilic monomer (C-2) is at least one selected from the group consisting of acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, acryloylmorpholine, 2-hydroxyethyl acrylate, 2-dimethylaminoethyl acrylate, and vinyl acetate. 9. The ophthalmic lens material according to claim 1, wherein the hydrophilic monomer (C-2) is N,N-dimethylacrylamide.