JPH11133201A - Optical material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the optical material superior in transparence and permeability to oxygen and surface wettability and staining resistance and high in reflective index and impact resistance by using a polymer obtained by polymerizing a polymerizable component containing a specified monomer. SOLUTION: The optical material is a polymer obtained by polymerizing the polymerizable component containing the monomer represented by the formula in which R<1> is an H atom or a trimethylsilyl group; R<2> is a 1-5 C alkylene group; R<3> is a -Si(CH3 )n OSi(CH3 )3 }3 group; and (n) is 0, 1, 2, or 3. In the case that R<1> is a trimethylsilyl group, the obtained polymer is formed into a desirable lens shape and then, brought into contact with water or alcohol to convert the protective trimethylsilyl group derived from this monomer into a carboxyl group, thus permitting the function, such as surface wettability, to be later given to the optical material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an optical material. More specifically, the present invention relates to an optical material that can be suitably used for an ophthalmic lens such as a contact lens and an intraocular lens, an artificial cornea, goggles, and eyeglasses.

[0002]

2. Description of the Related Art Conventionally, among optical materials, various materials using silicone-based monomers such as siloxanyl methacrylate have been proposed in order to obtain oxygen-permeable hard contact lenses having excellent oxygen permeability. .

[0003] However, disadvantages of silicone-based materials such as siloxanyl methacrylate include poor surface wettability and susceptibility to contamination by lipid stains. Contact lenses made of such materials are consequently worn. In some cases, it was inferior and sometimes caused corneal damage.

[0004] In order to improve the disadvantages of such materials having poor surface wettability and lipid contaminating properties, for example, various materials have been proposed which are polymerized by adding a hydrophilic monomer such as hydroxyethyl methacrylate or methacrylic acid. I have. However, these hydrophilic monomers are incompatible with highly hydrophobic monomers such as silicone-based monomers, and even if a uniform and transparent copolymer cannot be obtained or if they can be dissolved, they may be mutually soluble. Since the amount of soluble monomers is limited, it is difficult to develop functions such as oxygen permeability, strength, and hardness, and it has been extremely difficult to obtain a satisfactory material.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above prior art, and has excellent transparency, oxygen permeability, surface wettability, and stain resistance, and has a high refractive index and a high refractive index. An object of the present invention is to provide an optical material having high impact strength.

[0006]

According to the present invention, there is provided a compound represented by the general formula (I):

[0007]

Embedded image

Wherein R ¹ is a hydrogen atom or a trimethylsilyl group, R ² is an alkylene group having 1 to 5 carbon atoms, and R ³ is a general formula: —Si (CH ₃ ) _n (OSi (CH ₃ ) ₃ ) _{3 The} present invention relates to an optical material comprising a polymer obtained by polymerizing a polymerization component containing a monomer represented by _-n (wherein, n represents an integer of 0 or 1 to 3).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, the optical material of the present invention has the general formula (I):

[0010]

Embedded image

Wherein R ¹ is a hydrogen atom or a trimethylsilyl group, R ² is an alkylene group having 1 to 5 carbon atoms, and R ³ is a general formula: —Si (CH ₃ ) _n (OSi (CH ₃ ) ₃ ) _{3 -n} (wherein n represents a group represented by 0 or an integer of 1 to 3)) (hereinafter, referred to as monomer (A)). It consists of a polymer.

The monomer (A) is a monomer having both a silicon atom and a carboxyl group in one molecule. By the action of the monomer (A), the resulting optical material has excellent transparency and excellent transparency. Oxygen permeability, surface wettability and stain resistance, as well as high refractive index and high impact resistance.

In the general formula (I) representing the monomer (A), R ¹ represents a hydrogen atom or a trimethylsilyl group. When R ¹ is a trimethylsilyl group, the obtained polymer can be used to obtain a desired polymer. By contacting with water or alcohol after forming the lens shape, the trimethylsilyl group derived from the monomer (A) is converted into a carboxyl group based on the deprotection of the trimethylsilyl group derived from the monomer (A) at least on the lens surface. be able to. By such an action, functions such as surface wettability and stain resistance can be imparted to the optical material later, and these functions are larger than when R ¹ is a hydrogen atom. A further advantage arises that it can be expressed.

Specific examples of the monomer (A) include, for example, β-trimethylsilylmethyl itaconate monoester, β-trimethylsilylethyl itaconate monoester, β-trimethylsilylpropyl itaconate monoester, β-trimethylsilylbutyl itaconate monoester, β-tristrimethylsiloxysilylmethyl itaconate monoester, β-tristrimethylsiloxysilylethyl itaconate monoester, β-tristrimethylsiloxysilylpropyl itaconate monoester, β-tristrimethylsiloxysilylbutyl itaconate monoester, β-tristrimethylsiloxysilylpropyl itaconate monoester Pentamethyltrisiloxymethylitaconate monoester, β-pentamethyltrisiloxyethylitaconate monoester, β
-Pentamethyltrisiloxypropyl itaconate monoester, β-pentamethyltrisiloxybutyl itaconate monoester, α-trimethylsilyl-β-trimethylsilylmethyl itaconate, α-trimethylsilyl-β-trimethylsilylethyl itaconate, α-trimethylsilyl-β -Trimethylsilylpropyl itaconate, α-trimethylsilyl-β-trimethylsilylbutyl itaconate, α-trimethylsilyl-β-tristrimethylsiloxysilylmethyl itaconate, α-
Trimethylsilyl-β-tristrimethylsiloxysilylethyl itaconate, α-trimethylsilyl-β-tristrimethylsiloxysilylpropyl itaconate,
α-trimethylsilyl-β-tristrimethylsiloxysilylbutyl itaconate, α-trimethylsilyl-β
-Pentamethyltrisiloxymethylitaconate, α-
Trimethylsilyl-β-pentamethyltrisiloxyethyl itaconate, α-trimethylsilyl-β-pentamethyltrisiloxypropyl itaconate, α-trimethylsilyl-β-pentamethyltrisiloxybutyl itaconate, and the like. A mixture of more than one species can be used. Among them, the obtained optical materials are notable for having excellent transparency, excellent oxygen permeability, surface wettability and stain resistance, and a high effect of imparting a high refractive index and high impact strength. ,
formula:

[0015]

Embedded image

Β-trimethylsilylpropyl itaconate monoester represented by the formula:

[0017]

Embedded image

Α-trimethylsilyl-β-
Trimethylsilylpropyl itaconate is particularly preferred.

The amount of the monomer (A) should be 1% by weight or more, preferably 5% by weight of the polymerization component in order to sufficiently exhibit the above-mentioned excellent effects by using the monomer (A). In order to eliminate the possibility that the monomer (A) is unlikely to be sufficiently and uniformly dissolved with respect to the monomer (B) described later, for example, 90% by weight or less, preferably 80% by weight of the polymerization component. It is desirable that the content be not more than weight%.

The optical material of the present invention is composed entirely of the monomer (A) (the amount of the monomer (A) is 100%).
(% By weight) may be a polymer obtained by polymerizing a polymerization component, but in the present invention, the monomer (B) is used together with the monomer (A) as long as the object of the present invention is not impaired. ) Can be used.

The monomer (B) can be appropriately selected according to the properties of the target optical material, and can be used by appropriately adjusting the amount so that the total amount of the polymerization components becomes 100% by weight. In consideration of the amount of (A), it is desirable to use the polymer component in an amount of 99% by weight or less, preferably 95% by weight or less, and more preferably 10% by weight or more, preferably 20% by weight or more. desirable. As the monomer (B), for example, when a non-water-containing optical material is to be obtained, a hydrophobic monomer or macromonomer is mainly selected, and when a water-containing optical material is to be obtained. May be mainly selected from hydrophilic monomers and macromonomers. In addition, if an optical material with excellent mechanical strength is to be obtained, a reinforcing monomer or macromonomer should be selected to obtain an optical material with excellent water and solvent resistance. In this case, a crosslinkable monomer for forming a crosslinked structure may be selected.

Specifically, for example, when it is desired to further impart oxygen permeability to the obtained optical material and to further reinforce the mechanical strength of the optical material, for example, one or two polymerizable groups may be used. Polysiloxane macromonomer linked to the siloxane main chain via a single urethane bond, polysiloxane macromonomer linked directly to the siloxane main chain with a polymerizable group, siloxane main chain linked to a polymerizable group via an alkylene group A polysiloxane macromonomer such as a polysiloxane macromonomer bonded to is used as the monomer (B).

The polysiloxane macromonomer is, for example, of the formula:

[0024]

Embedded image

The urethane bond-containing polysiloxane macromonomer represented by the following formula (hereinafter referred to as macromonomer a)
Formula such as ^{(II): A 1 - (} U 2) m2 -S 3 - (T 4) m4 - (U 5) m5 -A 6 (II) ( wherein, A ¹ is the general formula: Y ¹¹ - R ¹² − (wherein, Y ¹¹ is an acryloyloxy group, a methacryloyloxy group, a vinyl group or an allyl group, and R ¹² is a group having 1 to 1 carbon atoms.
A ⁶ represents a linear or branched alkylene group; A ⁶ represents a general formula: —R ⁶² —Y ⁶¹ (where R ⁶² represents a linear or branched C 1-6 alkyl group) A chain alkylene group, Y ⁶¹ represents an acryloyloxy group, a methacryloyloxy group, a vinyl group or an allyl group), and U ² represents a general formula: -X ²¹ -E ²² -X ²³ -R ^24- ( In the formula, X ²¹ is a covalent bond, an oxygen atom or a group having 1 to 6 carbon atoms.
Alkylene glycol group, E ²² is -NHCO- group or a saturated aliphatic, ends from a diisocyanate selected from cycloaliphatic and aromatic systems -CONH- group and -NH
A divalent group which is a CO- group, X ²³ is an oxygen atom, and has 1 carbon atom.
To 6 alkylene glycol groups or a general formula:

[0026]

Embedded image

(Wherein R ²³⁵ is a trivalent hydrocarbon group having 1 to 6 carbon atoms, R ²³² is a linear or branched alkylene group having 1 to 6 carbon atoms, and E ²³⁴ is a —CONH— group. Alternatively, the terminal derived from a diisocyanate selected from a saturated aliphatic system, an alicyclic system and an aromatic system has a -CONH- group and a -NHCO-
X ²³³ represents a covalent bond, an oxygen atom or an alkylene glycol group having 1 to 6 carbon atoms, and Y ²³¹ represents an acryloyloxy group, a methacryloyloxy group, a vinyl group or an allyl group. ²³³ is a covalent bond when the adjacent E ²³⁴ is a —CONH— group, and an oxygen atom or an alkylene glycol having 1 to 6 carbon atoms when the adjacent E ²³⁴ is a divalent group derived from diisocyanate. And E ²³⁴ forms a urethane bond between the adjacent oxygen atom and X ²³³ ))
R ²⁴ represents a linear or branched alkylene group having 1 to 6 carbon atoms (provided that X ²¹ is a covalent bond when the adjacent E ²² is a —NHCO— group) And when adjacent E ²² is a divalent group derived from diisocyanate, it is an oxygen atom or an alkylene glycol group having 1 to 6 carbon atoms, and E ²² is adjacent X ²¹ and X ²³
Groups represented by by forming a urethane bond)) during the, U ⁵ has the general ^{formula: -R 54 -X 53 -E 52 -X} 51 - ( wherein, R ⁵⁴ is 1 to 6 carbon atoms straight A chain or branched alkylene group, X ⁵³ is an oxygen atom, an alkylene glycol group having 1 to 6 carbon atoms or a general formula:

[0028]

Embedded image

Wherein R ⁵³⁵ is a trivalent hydrocarbon group having 1 to 6 carbon atoms, R ⁵³² is a linear or branched alkylene group having 1 to 6 carbon atoms, and E ⁵³⁴ is a —CONH— group. Alternatively, the terminal derived from a diisocyanate selected from a saturated aliphatic system, an alicyclic system and an aromatic system has a -CONH- group and a -NHCO-
X ⁵³³ represents a covalent bond, an oxygen atom or an alkylene glycol group having 1 to 6 carbon atoms, and Y ⁵³¹ represents an acryloyloxy group, a methacryloyloxy group, a vinyl group or an allyl group. ⁵³³ is a covalent bond when the adjacent E ⁵³⁴ is a —CONH— group, and is an oxygen atom or an alkylene glycol having 1 to 6 carbon atoms when the adjacent E ⁵³⁴ is a divalent group derived from diisocyanate. And E ⁵³⁴ forms a urethane bond between the adjacent oxygen atom and X ⁵³³ ))
A group represented by, E ⁵² is -CONH- group or a saturated aliphatic, ends from a diisocyanate selected from alicyclic and aromatic bivalent is a -CONH- group and a -NHCO- group The group X ⁵¹ represents a covalent bond, an oxygen atom or an alkylene glycol group having 1 to 6 carbon atoms (provided that X
⁵¹ is a covalent bond when adjacent E ⁵² is a —CONH— group, and an oxygen atom or an alkylene glycol having 1 to 6 carbon atoms when adjacent E ⁵² is a divalent group derived from diisocyanate. And E ⁵² is an adjacent X ⁵¹
And forming a urethane bond between the X ⁵³⁾⁾
S ³ is a group represented by the general formula:

[0030]

Embedded image

Wherein R ³¹ , R ³² , R ³³ , R ³⁵ and R
³⁶ are independently straight or branched alkyl group or a phenyl group part or all of 1 to 6 carbon atoms which may be substituted with a fluorine atom of the hydrogen atoms, one R ³⁴ is a hydrogen atom A part or all of which may be substituted with a fluorine atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group or a general formula:

[0032]

Embedded image

(Wherein, R ³⁴⁶ and R ³⁴² are each independently a linear or branched alkylene group having 1 to 6 carbon atoms, X ³⁴⁵ and X ³⁴³ are a covalent bond, an oxygen atom or 6 is an alkylene glycol group, E ³⁴⁴ is -CON
The terminal derived from H-group or diisocyanate selected from saturated aliphatic, alicyclic and aromatic is -CONH-
Y ³⁴¹ represents an acryloyloxy group, a methacryloyloxy group, a vinyl group or an allyl group (provided that X ³⁴⁵ and X ³⁴³ represent that the adjacent E ³⁴⁴ is —CONH— And when adjacent E ³⁴⁴ is a divalent group derived from diisocyanate, it is an oxygen atom or an alkylene glycol group having 1 to 6 carbon atoms.
³⁴⁴ represents a group represented by the following formula (which forms a urethane bond between adjacent X ³⁴⁵ and X ³⁴³ ), provided that all of R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ are At the same time, m31 is a linear or branched alkyl group having 1 to 6 carbon atoms in which part or all of the hydrogen atoms are substituted with a fluorine atom, or a phenyl group). An integer of 1 to 100, m32 is 0 to (10
0- (m31)) (provided that (m31) +
(M32) is a group represented by indicating)) an integer from 1 to 100, T ⁴ has the general formula: -U ⁴¹ -S ⁴² - (wherein, U ⁴¹ the general formula: -R ⁴¹¹ -X ⁴¹² -E ⁴¹³ —X ⁴¹⁴ —R ⁴¹⁵ — (wherein, R ⁴¹¹ and R ⁴¹⁵ each independently have 1 carbon atom)
X ⁴¹² and X ⁴¹⁴ are each independently an oxygen atom or an alkylene glycol group having 1 to 6 carbon atoms; E ⁴¹³ is a saturated aliphatic or alicyclic group; And a divalent group having a terminal derived from a diisocyanate selected from an aromatic group and having --CONH-- and --NHCO-- groups (provided that E ⁴¹³ represents an adjacent X ⁴¹²
And X ⁴¹⁴ form a urethane bond)), S ⁴² is a group represented by the general formula:

[0034]

Embedded image

(Wherein R ⁴²¹ , R ⁴²² , R ⁴²³ , R ⁴²⁵ and R ⁴²⁶ each independently represent a straight-chain having 1 to 6 carbon atoms in which part or all of the hydrogen atoms may be replaced by fluorine atoms. A chain or branched alkyl or phenyl group,
R ⁴²⁴ represents a linear or branched alkyl group having 1 to 6 carbon atoms which may be partially or entirely substituted with a fluorine atom, a phenyl group or a general formula:

[0036]

Embedded image

(Wherein R ⁴²⁴⁶ and R ⁴²⁴² are each independently a linear or branched alkylene group having 1 to 6 carbon atoms, X ⁴²⁴⁵ and X ⁴²⁴³ are a covalent bond, an oxygen atom or An alkylene glycol group of 6, E ⁴²⁴⁴ is —C
The terminal derived from an ONH— group or a diisocyanate selected from a saturated aliphatic system, an alicyclic system and an aromatic system is —CON
A divalent group of H- and -NHCO-, Y ⁴²⁴¹ represents an acryloyloxy group, a methacryloyloxy group, a vinyl group or an allyl group (provided that X ⁴²⁴⁵ and X ⁴²⁴³
Is a covalent bond when the adjacent E ⁴²⁴⁴ is a —CONH— group, and is an oxygen atom or an alkylene having 1 to 6 carbon atoms when the adjacent E ⁴²⁴⁴ is a divalent group derived from diisocyanate. A glycol group,
⁴²⁴⁴ represents a group represented by the following ^formula (which forms a urethane bond between adjacent X ⁴²⁴⁵ and X ⁴²⁴³ ) (provided that R ⁴²¹ , R ⁴²² , R ⁴²³ , R ⁴²⁴ , R ⁴²⁵ and R ⁴²⁶ are all At the same time, when a hydrogen atom is partly or wholly substituted with a fluorine atom, a linear or branched alkyl group having 1 to 6 carbon atoms or a phenyl group is excluded, and m421 is excluded. An integer of 1 to 100, and m422 represents an integer of 0 to (100- (m421)) (however,
(M421) + (m422) represents an integer of 1 to 100))) or a general formula:

[0038]

Embedded image

(Wherein T ⁴³ is a general formula:

[0040]

Embedded image

(Wherein, R ⁴³¹ , R ⁴³⁵ and R ⁴³⁷ are each independently a linear or branched alkylene group having 1 to 6 carbon atoms, and X ⁴³² , X ⁴³⁴ and X ⁴³⁶ are each independently An oxygen atom or an alkylene glycol group having 1 to 6 carbon atoms, T ⁴³³ has the formula:

[0042]

Embedded image

A group represented by the following formula (provided that a urethane bond is formed between adjacent X ⁴²³ , X ⁴³⁴ and X ⁴³⁶ ), and S ⁴⁴ is a group represented by the following general formula:

[0044]

Embedded image

(Wherein R ⁴⁴¹ , R ⁴⁴² , R ⁴⁴³ , R ⁴⁴⁵ and R ⁴⁴⁶ each independently represent a straight-chain having 1 to 6 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms. A chain or branched alkyl or phenyl group,
R ⁴⁴⁴ is a linear or branched alkyl group having 1 to 6 carbon atoms which may be partially or entirely substituted with a fluorine atom, a phenyl group or a general formula:

[0046]

Embedded image

( ^Wherein R ⁴⁴⁴⁶ and R ⁴⁴⁴² each independently represent a linear or branched alkylene group having 1 to 6 carbon atoms, X ⁴⁴⁴⁵ and X ^{4443 each} represent a covalent bond, an oxygen atom or An alkylene glycol group of 6, E ⁴⁴⁴⁴ represents —C
The terminal derived from an ONH— group or a diisocyanate selected from a saturated aliphatic system, an alicyclic system and an aromatic system is —CON
A divalent group of H- and -NHCO-, Y ⁴⁴⁴¹ represents an acryloyloxy group, a methacryloyloxy group, a vinyl group or an allyl group (provided that X ⁴⁴⁴⁵ and X ⁴⁴⁴³
Is a covalent bond when the adjacent E ⁴⁴⁴⁴ is a —CONH— group, and is an oxygen atom or an alkylene having 1 to 6 carbon atoms when the adjacent E ⁴⁴⁴⁴ is a divalent group derived from diisocyanate. A glycol group,
⁴⁴⁴⁴ represents a group represented by the following formula (forming a urethane bond between adjacent X ⁴⁴⁴⁵ and X ⁴⁴⁴³ ), provided that all of R ⁴⁴¹ , R ⁴⁴² , R ⁴⁴³ , R ⁴⁴⁴ , R ⁴⁴⁵ and R ⁴⁴⁶ are represented by At the same time, except for a linear or branched alkyl group having 1 to 6 carbon atoms in which part or all of the hydrogen atoms are substituted with a fluorine atom, or a phenyl group), m441 is An integer of 1 to 100, m442 represents an integer of 0 to (100- (m441)) (however,
(M441) + (m442) represents an integer of 1 to 100))), and S ⁴⁵ represents a general formula:

[0048]

Embedded image

(Wherein, R ⁴⁵¹ , R ⁴⁵² , R ⁴⁵³ , R ⁴⁵⁵ and R ⁴⁵⁶ each independently represent a straight-chain having 1 to 6 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms. A chain or branched alkyl or phenyl group,
R ⁴⁵⁴ is a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group or a general formula, wherein a part or all of hydrogen atoms may be substituted by a fluorine atom.

[0050]

Embedded image

(Wherein, R ⁴⁵⁴⁶ and R ⁴⁵⁴² are each independently a linear or branched alkylene group having 1 to 6 carbon atoms, X ⁴⁵⁴⁵ and X ⁴⁵⁴³ are a covalent bond, an oxygen atom or An alkylene glycol group of 6, E ⁴⁵⁴⁴ is —C
The terminal derived from an ONH— group or a diisocyanate selected from a saturated aliphatic system, an alicyclic system and an aromatic system is —CON
A divalent group represented by an H-group and an -NHCO- group, Y ^4541, represents an acryloyloxy group, a methacryloyloxy group, a vinyl group or an allyl group (provided that X ⁴⁵⁴⁵ and X ^{4543 are present).}
Is a covalent bond when the adjacent E ⁴⁵⁴⁴ is a —CONH— group, and is an oxygen atom or an alkylene having 1 to 6 carbon atoms when the adjacent E ⁴⁵⁴⁴ is a divalent group derived from diisocyanate. A glycol group,
⁴⁵⁴⁴ represents a group represented by the following formula (forming a urethane bond between adjacent X ⁴⁵⁴⁵ and X ⁴⁵⁴³ ), provided that all of R ⁴⁵¹ , R ⁴⁵² , R ⁴⁵³ , R ⁴⁵⁴ , R ⁴⁵⁵ and R ⁴⁵⁶ are At the same time, excluding the case where the hydrogen atom is a linear or branched alkyl group having 1 to 6 carbon atoms in which part or all of the hydrogen atoms are substituted with a fluorine atom, or the case where it is a phenyl group), m451 is An integer of 1 to 100, and m452 represents an integer of 0 to (100- (m451)) (however,
(M451) + (m452) represents an integer of 1 to 100)), and U ⁴⁶ is a general formula: —R ⁴⁶¹ —X ⁴⁶² —E ⁴⁶³ —X ⁴⁶⁴ — (wherein R ⁴⁶¹ is the number of carbon atoms) A linear or branched alkylene group having 1 to 6 carbon atoms, X ⁴⁶² is an oxygen atom, an alkylene glycol group having 1 to 6 carbon atoms or a general formula:

[0052]

Embedded image

(Wherein, R ⁴⁶²⁵ is a trivalent hydrocarbon group having 1 to 6 carbon atoms, R ⁴⁶²² is a linear or branched alkylene group having 1 to 6 carbon atoms, and E ⁴⁶²⁴ is a —CONH— group) Alternatively, the terminal derived from a diisocyanate selected from a saturated aliphatic system, an alicyclic system and an aromatic system has a -CONH- group and a -NHCO-
X ⁴⁶²³ represents a covalent bond, an oxygen atom or an alkylene glycol group having 1 to 6 carbon atoms, and Y ⁴⁶²¹ represents an acryloyloxy group, a methacryloyloxy group, a vinyl group or an allyl group. ⁴⁶²³ is a covalent bond when the adjacent E ⁴⁶²⁴ is a —CONH— group, and is an oxygen atom or an alkylene glycol having 1 to 6 carbon atoms when the adjacent E ⁴⁶²⁴ is a divalent group derived from diisocyanate. And E ⁴⁶²⁴ forms a urethane bond between the adjacent oxygen atom and X ⁴⁶²³ ))
E ⁴⁶³ represents a -CONH- group or a divalent group having a terminal derived from a diisocyanate selected from a saturated aliphatic system, an alicyclic system and an aromatic system having a -CONH- group and a -NHCO- group. A group X ⁴⁶⁴ represents a covalent bond, an oxygen atom or an alkylene glycol group having 1 to 6 carbon atoms (provided that X ⁴⁶⁴ represents a covalent bond when the adjacent E ⁴⁶³ is a —CONH— group; If E ⁴⁶³ is a divalent group derived from a diisocyanate, an oxygen atom or an alkylene glycol group having 1 to 6 carbon atoms, E ⁴⁶³ is
Group represented by to form a urethane bond are)) in between the adjacent X ⁴⁶² and X ^464, A ⁴⁷ has the general formula: -R ⁴⁷² -Y ⁴⁷¹ (wherein, R ⁴⁷² is 1 to 6 carbon atoms straight A chain or branched alkylene group, Y ⁴⁷¹ represents an acryloyloxy group, a methacryloyloxy group, a vinyl group or an allyl group)
M2 represents 0 or 1, m4 represents 0, 1, 2 or 3, m5 represents 0 or 1, provided that m2, m5 and m46 represent All the same))).

The polysiloxane macromonomer can be used alone or as a mixture of two or more kinds, and the amount thereof may be appropriately adjusted according to the properties of the desired optical material.

For example, when the oxygen permeability of the obtained optical material is to be further improved, for example, a silicon-containing monomer such as a silicon-containing alkyl (meth) acrylate, a silicon-containing styrene derivative, or an alkylvinylsilane is used as the monomer (B). ).

Examples of the silicon-containing alkyl (meth) acrylate include, for example, pentamethyldisiloxanylmethyl (meth) acrylate, trimethylsiloxydimethylsilylpropyl (meth) acrylate, methylbis (trimethylsiloxy) silylpropyl (meth) acrylate, tris (Trimethylsiloxy) silylpropyl (meth) acrylate, mono [methylbis (trimethylsiloxy) siloxy] bis (trimethylsiloxy) silylpropyl (meth) acrylate, tris [methylbis (trimethylsiloxy) siloxy] silylpropyl (meth) acrylate, methyl [ Bis (trimethylsiloxy)] silylpropylglyceryl (meth) acrylate, tris (trimethylsiloxy) silylpropylglyceryl (meth) acryl Over DOO, mono [methylbis (trimethylsiloxy) siloxy] bis (trimethylsiloxy) silyl propyl glyceryl (meth) acrylate,
Trimethylsilylethyltetramethyldisiloxanylpropyl glyceryl (meth) acrylate, trimethylsilylmethyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, trimethylsilylpropyl glyceryl (meth) acrylate, pentamethyldisiloxanylpropyl glyceryl (meth) acrylate,
Methyl bis (trimethylsiloxy) silylethyltetramethyldisiloxanylmethyl (meth) acrylate, tetramethyltriisopropylcyclotetrasiloxanylpropyl (meth) acrylate, tetramethyltriisopropylcyclotetrasiloxybis (trimethylsiloxy) silylpropyl (meth) A) acrylates and organopolysiloxane-containing alkyl (meth) acrylates such as acrylate and trimethylsiloxydimethylsilylpropyl (meth) acrylate.

The silicon-containing styrene derivative includes, for example, a compound represented by the following general formula (III):

[0058]

Embedded image

(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 case of the silicon-containing styrene derivative represented by the general formula (III), when p or r is an integer of 16 or more, its synthesis and purification become difficult, and the hardness of the obtained optical material is further reduced. Tends to decrease. Also, if q is 2
When the integer is the above integer, the synthesis of the silicon-containing styrene derivative tends to be difficult.

Representative examples of the silicon-containing styrene derivative represented by the general formula (III) include, for example, tris (trimethylsiloxy) silylstyrene, bis (trimethylsiloxy) methylsilylstyrene, dimethylsilylstyrene, trimethylsilylstyrene, and tris (trimethyl). Siloxy) siloxanyldimethylsilylstyrene,
[Bis (trimethylsiloxy) methylsiloxanyl] dimethylsilylstyrene, pentamethyldisiloxanylstyrene, heptamethyltrisiloxanylstyrene, nonamethyltetrasiloxanylstyrene, pentadecamethylheptasiloxanylstyrene, henico Samethyl decasiloxanyl styrene, heptacosa methyl trideca siloxanyl styrene, hentria contamethyl pentadeca siloxanyl styrene, trimethyl siloxy pentamethyl disiloxy methyl silyl styrene, tris (pentamethyl disiloxy) silyl styrene, ( Tristrimethylsiloxy) siloxanylbis (trimethylsiloxy) silylstyrene, bis (heptamethyltrisiloxy) methylsilylstyrene, tris (methylbistrimethylsiloxysiloxy) silyl Styrene, trimethylsiloxybis (tristrimethylsiloxysiloxy) silylstyrene, heptakis (trimethylsiloxy) trisiloxanylstyrene, tris (tristrimethylsiloxysiloxy) silylstyrene, (tristrimethylsiloxyhexamethyl) tetrasiloxy (tristrimethylsiloxy) siloxy Trimethylsiloxysilylstyrene, nonakis (trimethylsiloxy) tetrasiloxanylstyrene, bis (tridecamethylhexasiloxy) methylsilylstyrene, heptamethylcyclotetrasiloxanylstyrene, heptamethylcyclotetrasiloxybis (trimethylsiloxy) silylstyrene, And tripropyltetramethylcyclotetrasiloxanylstyrene.

Examples of the alkyl vinyl silane include trimethyl vinyl silane.

Among the silicon-containing monomers, tris (trimethylsiloxy) silylpropyl (meth) is excellent in compatibility with other polymerization components and has a great effect of improving the oxygen permeability of the obtained optical material. Acrylates and tris (trimethylsiloxy) silylstyrene are particularly preferred.

The above-mentioned silicon-containing monomers can be used alone or as a mixture of two or more kinds, and the amount thereof may be appropriately adjusted according to the properties of the desired optical material.

In order to improve the hydrophilicity of the obtained optical material and to impart water content to the optical material,
For example, a hydrophilic monomer having a hydroxyl group, an amide group, a carboxyl group, an amino group, a glycol residue, a pyrrolidone skeleton, or the like is used as the monomer (B).

As the hydrophilic monomer, for example, 2
Hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, and hydroxypropyl (meth) acrylate; 2-dimethylaminoethyl (meth) acrylate, 2-butylaminoethyl (meth) acrylate, and the like (Alkyl) aminoalkyl (meth) acrylates; alkyl (meth) acrylamides such as N, N-dimethylacrylamide; polyglycol mono (meth) acrylates such as propylene glycol mono (meth) acrylate; vinylpyrrolidone; (meth) acrylic acid Maleic anhydride; fumaric acid; fumaric acid derivatives; aminostyrene; hydroxystyrene.

Among the above-mentioned hydrophilic monomers, vinylpyrrolidone, alkyl (meth) acrylamide, and (meth) are excellent in compatibility with other polymerization components and have a great effect of improving the hydrophilicity of the obtained optical material. ) Acrylic acid and hydroxyalkyl (meth) acrylate are particularly preferred.

The above hydrophilic monomers can be used alone or as a mixture of two or more kinds, and the amount thereof may be appropriately adjusted according to the properties of the intended optical material.

Further, when the mechanical strength and durability (shape stability) of the obtained optical material are to be improved and water resistance and solvent resistance are to be imparted to the optical material, copolymerizable copolymers may be used. It is preferable to use a crosslinkable monomer which is a polyfunctional polymerizable compound having two or more saturated double bonds as the monomer (B).

Examples of the crosslinking monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and dipropylene glycol di (meth) acrylate. Acrylate, allyl (meth) acrylate,
Vinyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, methacryloyloxyethyl acrylate, divinylbenzene, diallyl phthalate, diallyl adipate, triallyl isocyanurate, α-methylene-N-vinylpyrrolidone, 4-vinylbenzyl (meta ) Acrylate, 3-vinylbenzyl (meth) acrylate, 2,2-bis (p- (meth) acryloyloxyphenyl) hexafluoropropane,
2,2-bis (m- (meth) acryloyloxyphenyl) hexafluoropropane, 2,2-bis (o- (meth) acryloyloxyphenyl) hexafluoropropane, 2,2-bis (p- (meth) acryloyl Oxyphenyl) propane, 2,2-bis (m- (meth) acryloyloxyphenyl) propane, 2,2-bis (o
-(Meth) acryloyloxyphenyl) propane,
1,4-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene, 1,3-bis (2-
(Meth) acryloyloxyhexafluoroisopropyl) benzene, 1,2-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene,
4-bis (2- (meth) acryloyloxyisopropyl) benzene, 1,3-bis (2- (meth) acryloyloxyisopropyl) benzene, 1,2-bis (2-
(Meth) acryloyloxyisopropyl) benzene and the like.

Among the above-mentioned crosslinkable monomers, ethylene glycol is preferred because it has excellent compatibility with other polymerization components and has a large effect of improving the mechanical strength and durability (shape stability) of the obtained optical material. Di (meth) acrylate and 4-vinylbenzyl (meth) acrylate are particularly preferred.

The crosslinkable monomers may be used alone or in combination of two or more. The amount may be appropriately adjusted according to the properties of the desired optical material. When used, 0.01% by weight or more of the polymerization component, especially 0.1% by weight, is required in order to sufficiently exhibit the effect of improving the durability (shape stability).
It is preferably at least 1% by weight, and in order to eliminate the possibility that the optical material becomes brittle, it is preferably at most 20% by weight, particularly preferably at most 10% by weight of the polymerization component.

In order to further improve the contamination resistance of the obtained optical material, a fluorine-containing monomer which is a polymerizable compound in which a part of hydrogen atoms of a hydrocarbon group is substituted with a fluorine atom may be used. Is used as the monomer (B).

Examples of the fluorine-containing monomer include a compound represented by the following general formula (IV): CH ₂ ＣＲCR ⁴ COOC _s H _{(2s-t-u + 1)} F _t (OH) _u (IV) (where R ⁴ is A hydrogen atom or CH ₃ , s is an integer of 1 to 15, t is an integer of 1 to (2s + 1), and u is an integer of 0 to 2).

Representative examples of the monomer represented by the general formula (IV) include, for example, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3
-Tetrafluoro-t-pentyl (meth) acrylate, 2,2,3,4,4,4-hexafluorobutyl (meth) acrylate, 2,2,3,4,4,4-hexafluoro-t-hexyl (Meth) acrylate, 2,
3,4,5,5,5-hexafluoro-2,4-bis (trifluoromethyl) pentyl (meth) acrylate, 2,2,3,3,4,4-hexafluorobutyl (meth) acrylate, 2 , 2,2,2 ', 2', 2 '
-Hexafluoroisopropyl (meth) acrylate,
2,2,3,3,4,4,4-heptafluorobutyl (meth) acrylate, 2,2,3,3,4,4,5,
5-octafluoropentyl (meth) acrylate,
2,2,3,3,4,4,5,5,5-nonafluoropentyl (meth) acrylate, 2,2,3,3,4
4,5,5,6,6,7,7-dodecafluoroheptyl (meth) acrylate, 3,3,4,4,5,5,6
6,7,7,8,8-dodecafluorooctyl (meth)
Acrylate, 3,3,4,4,5,5,6,6,7,
7,8,8,8-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,
7,8,8,9,9,10,10-hexadecafluorodecyl (meth) acrylate, 3,3,4,4,5
5,6,6,7,7,8,8,9,9,10,10,1
0-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,
5,5,6,6,7,7,8,8,9,9,10,1
0,11,11,11-nonadecafluoroundecyl (meth) acrylate, 3,3,4,4,5,5,6
6,7,7,8,8,9,9,10,10,11,1
1,12,12-eicosafluorododecyl (meth) acrylate, 2-hydroxy-4,4,5,5,6
7,7,7-octafluoro-6-trifluoromethylheptyl (meth) acrylate, 2-hydroxy-4,
4,5,5,6,6,7,7,8,9,9,9-dodecafluoro-8-trifluoromethylnonyl (meth) acrylate, 2-hydroxy-4,4,5,5,6 6,
7, 7, 8, 8, 9, 9, 10, 11, 11, 11-hexadecafluoro-10-trifluoromethylundecyl (meth) acrylate and the like.

Among the above fluorine-containing monomers, 2,2,2-trifluoroethyl (meth) acrylate and 2,2,2,2,2,2,2,2-trifluoroethyl (meth) acrylate are highly effective in improving the stain resistance of the obtained optical material. ', 2', 2'-Hexafluoroisopropyl (meth) acrylate is particularly preferred.

The above-mentioned fluorine-containing monomers can be used alone or as a mixture of two or more kinds, and the amount thereof may be appropriately adjusted according to the properties of the desired optical material.

For example, when the hardness of the obtained optical material is to be adjusted so as to impart hardness or softness, for example, alkyl (meth) acrylates and alkylstyrenes which are polymerizable compounds having an alkyl group are used. And styrene and other hardness controlling monomers are monomers (B)
Used as

The 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) acrylate, t-pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, nonyl (meth) acrylate, stearyl (meth)
Acrylate, cyclopentyl (meth) acrylate,
Linear, branched or cyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate; for example, 2-ethoxyethyl (meth) acrylate, 3-
Alkoxyalkyl (meth) acrylates such as ethoxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, and 3-methoxypropyl (meth) acrylate; for example, ethylthioethyl (meth)
Examples include acrylates and alkylthioalkyl (meth) acrylates such as methylthioethyl (meth) acrylate.

Examples of the alkylstyrenes include α-methylstyrene; alkylstyrenes such as methylstyrene, ethylstyrene, propylstyrene, butylstyrene, t-butylstyrene, isobutylstyrene, and pentylstyrene; methyl-α-methylstyrene; Alkyl-α-methyl such as ethyl-α-methylstyrene, propyl-α-methylstyrene, butyl-α-methylstyrene, t-butyl-α-methylstyrene, isobutyl-α-methylstyrene, pentyl-α-methylstyrene Styrene and the like.

Among the above-mentioned hardness controlling monomers,
For example, when a soft optical material such as a soft contact lens is to be obtained, a material having a glass transition temperature (hereinafter, referred to as Tg) of 40 ° C. or lower when a homopolymer is used is preferably used. . For example, when a hard optical material such as a hard contact lens is to be obtained, when a homopolymer is used, its Tg is 40%.
Those higher than ℃ are preferably used. Further, styrene, alkyl (meth) acrylate and alkyl styrene are particularly preferred in that they have excellent compatibility with other polymerization components and copolymerizability.

The hardness adjusting monomer may be used alone or
More than one species can be used as a mixture, and the amount may be appropriately adjusted according to the material of the target optical material.

For further improving the surface hydrophilicity and transparency of the obtained optical material, for example, the following general formula (V):

[0083]

Embedded image

(Wherein R ₁ is a general formula:

[0085]

Embedded image

(Wherein, R ₃ represents a hydrogen atom or a methyl group)

[0087]

Embedded image

Wherein R ₂ is an alkylene group having 1 to 5 carbon atoms, and X is

[0089]

Embedded image

A monomer represented by the general formula (VI):

[0091]

Embedded image

(Wherein R ₄ is a general formula:

[0093]

Embedded image

(Wherein, R ₅ represents an alkylene group having 1 to ₅ carbon atoms, and R ₆ represents a hydrogen atom or a methyl group) or a general formula:

[0095]

Embedded image

(Wherein R ₇ is a direct bond or a group having 1 to 1 carbon atoms)
A) a monomer represented by the formula (VII):

[0097]

Embedded image

(Wherein Z ¹ and Z ² are each independently a general formula:

[0099]

Embedded image

(Wherein R ₈ is a hydrogen atom or a methyl group,
R ₉ represents an alkylene group having 1 to 10 carbon atoms), a general formula:

[0101]

Embedded image

(Wherein R ₁₀ represents an alkylene group having 1 to ₁₀ carbon atoms) or a general formula: H ₂ C ＝ CH—O—R ₁₁ — (wherein, R ₁₁ represents 1 carbon atom) Represents an alkylene group of 10 to 10)
And the like) are used as the monomer (B).

Examples of the monomer represented by the general formula (V) include 2-phthaloyloxymethyl methacrylate, 2-phthaloyloxyethyl methacrylate,
2-phthaloyloxypropyl methacrylate, 3-phthaloyloxymethyl methacrylate, 3-phthaloyloxyethyl methacrylate, 3-phthaloyloxypropyl methacrylate, 4-phthaloyloxymethyl methacrylate, 4-phthaloyloxyethyl methacrylate, 4-phthaloyloxypropyl methacrylate,
2-hexahydrophthaloyloxymethyl methacrylate, 2-hexahydrophthaloyloxyethyl methacrylate, 2-hexahydrophthaloyloxypropyl methacrylate, 3-hexahydrophthaloyloxymethyl methacrylate, 3-hexahydrophthaloyloxyethyl methacrylate, 3-hexahydrophthaloyloxypropyl methacrylate, 4-hexahydrophthaloyloxymethyl methacrylate, 4-hexahydrophthaloyloxyethyl methacrylate, 4-hexahydrophthaloyloxypropyl methacrylate, 2-phthaloyloxymethyl acrylate, 2- Phthaloyloxyethyl acrylate, 2-phthaloyloxypropyl acrylate, 3-phthaloyloxymethyl acrylate, 3-phthaloy Oxyethyl acrylate, 3-phthaloyloxypropyl acrylate, 4-phthaloyloxymethyl acrylate, 4-phthaloyloxyethyl acrylate, 4-phthaloyloxypropyl acrylate, 2-hexahydrophthaloyloxymethyl acrylate, 2-hexahydro Phthaloyloxyethyl acrylate, 2-hexahydrophthaloyloxypropyl acrylate, 3-hexahydrophthaloyloxymethyl acrylate, 3-hexahydrophthaloyloxyethyl acrylate, 3-hexahydrophthaloyloxypropyl acrylate, 4-hexahydro Phthaloyloxymethyl acrylate, 4-hexahydrophthaloyloxyethyl acrylate, 4-hexahydrophthaloyloxypropyl acrylate, -Methacryloyloxymethyl trimellitic acid, 4-methacryloyloxyethyl trimellitic acid, 4-methacryloyloxypropyl trimellitic acid, 4-acryloyloxymethyl trimellitic acid, 4-acryloyloxyethyl trimellitic acid, 4-acryloyloxypropyl trimer Merritic acid, 2-phthaloyloxymethylstyrene, 2-hexahydrophthaloyloxymethylstyrene, 7-methacryloyloxymethylnaphthoic acid, 7-methacryloyloxyethylnaphthoic acid, 7-methacryloyloxypropylnaphthoic acid, and the like. Can be used alone or in combination of two or more. Among them, the formula: from the viewpoint that excellent transparency and surface hydrophilicity can be more effectively imparted to the optical material.

[0104]

Embedded image

2-phthaloyloxyethyl methacrylate represented by the formula:

[0106]

Embedded image

2-hexahydrophthaloyloxyethyl methacrylate represented by the following formula is particularly preferred.

Examples of the monomer represented by the general formula (VI) include (4- (meth) acryloyloxymethyl) trimellitic anhydride, (4- (meth) acryloyloxyethyl) trimellitic anhydride, Examples thereof include 4- (meth) acryloyloxypropyl) trimellitic anhydride and (4-vinylbenzyl) trimellitic anhydride, and these can be used alone or in combination of two or more. Among them, the formula: from the viewpoint that excellent transparency and surface hydrophilicity can be more effectively imparted to the optical material.

[0109]

Embedded image

The (4-methacryloyloxyethyl) trimellitic anhydride represented by the following formula is particularly preferred.

Examples of the monomer represented by the general formula (VII) include

[0112]

Embedded image

These are used alone or in combination with
A mixture of more than one species can be used. Among these, the formula: from the viewpoint that excellent surface hydrophilicity and transparency can be more effectively imparted to the optical material.

[0114]

Embedded image

The compound represented by the following formula is particularly preferred.

In the case where the obtained optical material is to be provided with an ultraviolet absorbing property or the optical material is to be colored,
For example, a polymerizable ultraviolet absorber, a polymerizable dye, a polymerizable ultraviolet absorbing dye, or the like is used as the monomer (B).

Specific examples of the polymerizable ultraviolet absorber include, for example, 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- (meth) acryloyloxy-5-t-butylbenzophenone, Benzophenone-based polymerizable ultraviolet absorption such as hydroxy-4- (meth) acryloyloxy-2 ', 4'-dichlorobenzophenone, 2-hydroxy-4- (2'-hydroxy-3'-(meth) acryloyloxypropoxy) benzophenone Agent; 2- (2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl)
-2H-benzotriazole, 2- (2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl)
-5-chloro-2H-benzotriazole, 2- (2 '
-Hydroxy-5 '-(meth) acryloyloxypropylphenyl) -2H-benzotriazole, 2-
Benzotriazole polymerizable ultraviolet absorbers such as (2'-hydroxy-5 '-(meth) acryloyloxypropyl-3'-t-butylphenyl) -5-chloro-2H-benzotriazole; 2-hydroxy-4- Salicylic acid derivative-based polymerizable ultraviolet absorbers such as phenyl methacryloyloxymethylbenzoate; other 2-cyano-3-
Polymerizable ultraviolet absorbers such as phenyl-3- (3 '-(meth) acryloyloxyphenyl) propenyl acid methyl ester, etc., and these can be used alone or in combination of two or more.

Specific examples of the polymerizable dye include, for example, 1-phenylazo-4- (meth) acryloyloxynaphthalene, 1-phenylazo-2-hydroxy-3-
(Meth) acryloyloxynaphthalene, 1-naphthylazo-2-hydroxy-3- (meth) acryloyloxynaphthalene, 1- (α-anthrylazo) -2-hydroxy-3- (meth) acryloyloxynaphthalene,
1-((4 '-(phenylazo) -phenyl) azo)-
2-hydroxy-3- (meth) acryloyloxynaphthalene, 1- (2 ', 4'-xylylazo) -2- (meth) acryloyloxynaphthalene, 1- (o-tolylazo) -2- (meth) acryloyloxynaphthalene ,
2- (m- (meth) acryloylamide-anilino)-
4,6-bis (1 '-(o-tolylazo) -2'-naphthylamino) -1,3,5-triazine, 2- (m-vinylanilino) -4- (4'-nitrophenylazo)-
Anilino) -6-chloro-1,3,5-triazine, 2
-(1 '-(o-tolylazo) -2'-naphthyloxy) -4- (m-vinylanilino) -6-chloro-1,
3,5-triazine, 2- (p-vinylanilino) -4
-(1 '-(o-tolylazo) -2'naphthylamino)
-6-chloro-1,3,5-triazine, N- (1'-
(O-tolylazo) -2'-naphthyl) -3-vinylphthalic acid monoamide, N- (1 '-(o-tolylazo)-
2'-naphthyl) -6-vinylphthalic acid monoamide, 3
-Vinylphthalic acid- (4 '-(p-sulfophenylazo) -1'-naphthyl) monoester, 6-vinylphthalic acid- (4'-(p-sulfophenylazo) -1'-naphthyl) monoester, 3 -(Meth) acryloylamide-4-phenylazophenol, 3- (meth) acryloylamide-4- (8'-hydroxy-3 ', 6'-
Disulfo-1'-naphthylazo) -phenol, 3-
(Meth) acryloylamido-4- (1'-phenylazo-2'-naphthylazo) -phenol, 3- (meth)
Acryloylamide-4- (p-tolylazo) -phenol, 2-amino-4- (m- (2'-hydroxy-
1'-naphthylazo) anilino) -6-isopropenyl-1,3,5-triazine, 2-amino-4- (N-methyl-p- (2'-hydroxy-1'-naphthylazo)
Anilino) -6-isopropenyl-1,3,5-triazine, 2-amino-4- (m- (4'-hydroxy-
1'-phenylazo) anilino) -6-isopropenyl-1,3,5-triazine, 2-amino-4- (N-methyl-p- (4'-hydroxyphenylazo) anilino) -6-isopropenyl- 1,3,5-triazine,
2-amino-4- (m- (3'-methyl-1'-phenyl-5'-hydroxy-4'-pyrazolylazo) anilino) -6-isopropenyl-1,3,5-triazine,
2-amino-4- (N-methyl-p- (3'-methyl-
1'-phenyl-5'-hydroxy-4'-pyrazolylazo) anilino) -6-isopropenyl-1,3,5-
Azo-based polymerization such as triazine, 2-amino-4- (p-phenylazoanilino) -6-isopropenyl-1,3,5-triazine, 4-phenylazo-7- (meth) acryloylamide-1-naphthol Sex dye; 1,5-
Bis ((meth) acryloylamino) -9,10-anthraquinone, 1- (4'-vinylbenzoylamide)-
9,10-anthraquinone, 4-amino-1- (4'-
Vinyl benzoylamide) -9,10-anthraquinone, 5-amino-1- (4'-vinylbenzoylamide) -9,10-anthraquinone, 8-amino-1-
(4'-vinylbenzoylamide) -9,10-anthraquinone, 4-nitro-1- (4'-vinylbenzoylamide) -9,10-anthraquinone, 4-hydroxy-1- (4'-vinylbenzoylamide) -9,10-
Anthraquinone, 1- (3'-vinylbenzoylamide) -9,10-anthraquinone, 1- (4'-isopropenylbenzoylamide) -9,10-anthraquinone, 1- (3'-isopropenylbenzoylamide)-
9,10-anthraquinone, 1- (2'-isopropenylbenzoylamide) -9,10-anthraquinone,
1,4-bis (4'-vinylbenzoylamide) -9,
10-anthraquinone, 1,4-bis- (4'-isopropenylbenzoylamide) -9,10-anthraquinone, 1,5'-bis- (4'-vinylbenzoylamide) -9,10-anthraquinone, 5-bis-
(4'-isopropenylbenzoylamide) -9,10
-Anthraquinone, 1-methylamino-4- (3'-vinylbenzoylamide) -9,10-anthraquinone,
1-methylamino-4- (4'-vinylbenzoyloxyethylamino) -9,10-anthraquinone, 1-amino-4- (3'-vinylphenylamino) -9,10
-Anthraquinone-2-sulfonic acid, 1-amino-4-
(4'-vinylphenylamino) -9,10-anthraquinone-2-sulfonic acid, 1-amino-4- (2'-vinylbenzylamino) -9,10-anthraquinone-2
-Sulfonic acid, 1-amino-4- (3 '-(meth) acryloylaminophenylamino) -9,10-anthraquinone-2-sulfonic acid, 1-amino-4- (3'-
(Meth) acryloylaminobenzylamino) -9,1
0-anthraquinone-2-sulfonic acid, 1- (β-ethoxycarbonylallylamino) -9,10-anthraquinone, 1- (β-carboxyallylamino) -9,10
-Anthraquinone, 1,5-di- (β-carboxyallylamino) -9,10-anthraquinone, 1,5-di-
(Β-isopropoxycarbonylallylamino) -5
Benzoylamide-9,10-anthraquinone, 2-
(3 '-(meth) acryloylamide-anilino) -4
-(3 '-(3 "-sulfo-4" -aminoanthraquinone-1 "-yl) -amino-anilino) -6-chloro-
1,3,5-triazine, 2- (3 '-(meth) acryloylamide-anilino) -4- (3'-(3 "-sulfo-4" -aminoanthraquinone-1 "-yl) -amino-anilino ) -6-Hydrazino-1,3,5-triazine, 2,4-bis-((4 "-methoxyanthraquinone-1" -yl) -amino) -6- (3'-vinylanilino) -1,3, 5-triazine, 2- (2'-vinylphenoxy) -4- (4 '-(3 "-sulfo-4" -aminoanthraquinone-1 "-yl-amino) -anilino) -6-chloro-1,3 Anthraquinone-based polymerizable dyes such as 1,5-triazine; nitro-based polymerizable dyes such as o-nitroanilinomethyl (meth) acrylate; (meth) acryloylated tetraamino copper phthalocyanine;
Examples include phthalocyanine-based polymerizable dyes such as (meth) acryloylated (dodecanoylated tetraamino copper phthalocyanine), and these can be used alone or in combination of two or more.

Specific examples of the polymerizable ultraviolet absorbing dye include, for example, 2,4-dihydroxy-3 (p-styrenoazo) benzophenone, 2,4-dihydroxy-5
(P-stylenoazo) benzophenone, 2,4-dihydroxy-3- (p- (meth) acryloyloxymethylphenylazo) benzophenone, 2,4-dihydroxy-5- (p- (meth) acryloyloxymethylphenylazo) benzophenone , 2,4-dihydroxy-3-
(P- (meth) acryloyloxyethylphenylazo) benzophenone, 2,4-dihydroxy-5- (p
-(Meth) acryloyloxyethylphenylazo) benzophenone, 2,4-dihydroxy-3- (p- (meth) acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy-5- (p- (meth)
Acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy-3- (o- (meth) acryloyloxymethylphenylazo) benzophenone,
2,4-dihydroxy-5- (o- (meth) acryloyloxymethylphenylazo) benzophenone, 2,4
-Dihydroxy-3- (o- (meth) acryloyloxyethylphenylazo) benzophenone, 2,4-dihydroxy-5- (o- (meth) acryloyloxyethylphenylazo) benzophenone, 2,4-dihydroxy-3- ( o- (meth) acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy-
5- (o- (meth) acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy-3-
(P- (N, N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-5- (p- (N, N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-3- (o- (N, N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-5- (o
-(N, N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-3- (p- (N-ethyl-N- (meth) acryloyloxyethylamino) phenylazo) benzophenone, , 4-Dihydroxy-5- (p- (N-ethyl-
N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-3
-(O- (N-ethyl-N- (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,
4-dihydroxy-5- (o- (N-ethyl-N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-3- (p
-(N-ethyl-N- (meth) acryloylamino) phenylazo) benzophenone, 2,4-dihydroxy-
5- (p- (N-ethyl-N-di (meth) acryloylamino) phenylazo) benzophenone, 2,4-dihydroxy-3- (o- (N-ethyl-N- (meth) acryloylamino) phenylazo) benzophenone , 2,
Benzophenone-based polymerizable ultraviolet absorbing dyes such as 4-dihydroxy-5- (o- (N-ethyl-N-di (meth) acryloylamino) phenylazo) benzophenone, and 2-hydroxy-4- (p-styrenoazo) benzoic acid Examples include benzoic acid-based polymerizable ultraviolet absorbing dyes such as phenyl acid, and these can be used alone or in combination of two or more.

The amounts of the polymerizable ultraviolet absorbent, the polymerizable dye and the polymerizable ultraviolet absorbing dye may be appropriately adjusted according to the properties of the target optical material, but are greatly affected by the thickness of the material. It is preferable to take this into consideration. In addition,
Considering that the physical properties of the optical material, such as mechanical strength, do not decrease, and considering the biocompatibility of ultraviolet absorbers and dyes, such as contact lenses that come into direct contact with living tissue and intraocular lenses that are embedded in living organisms These amounts are preferably 3% by weight or less, more preferably 0.1 to 2% by weight of the polymerization component, in order to eliminate the possibility of becoming unsuitable as a material for a suitable ophthalmic lens. In addition, particularly in the case of pigments, if the amount is too large, the color of the material becomes too dark, the transparency is reduced, and it is appropriately adjusted in consideration of the fact that the material is difficult to transmit visible light. preferable.

In the present invention, among the monomers (B), one or more of the monomers other than the polysiloxane macromonomer are selected and used as the macromonomer, and this is used as the macromonomer (B). One of them may be blended with the polymerization component.

The polymerizable component containing the monomer (A) and, if necessary, the monomer (B) may be used for an ophthalmic lens such as a contact lens or an intraocular lens, an artificial cornea,
The composition is appropriately adjusted according to the intended use of the optical material such as goggles and eyeglasses, and then subjected to polymerization.

In the present invention, a desired amount of the polymerization component containing the monomer (A) and, if necessary, the monomer (B) is adjusted, for example, within the range described above, and a radical polymerization initiator is added thereto. The polymer can be obtained by performing polymerization in a usual manner.

The ordinary method is, for example, to add a radical polymerization initiator and then gradually heat the mixture in a temperature range from room temperature to about 130 ° C., or use microwaves, ultraviolet rays, radiation (γ
This is a method in which polymerization is carried out by irradiating electromagnetic waves such as
In the case of heat polymerization, the temperature may be raised stepwise. The polymerization may be performed by a bulk polymerization method, a solution polymerization method using a solvent or the like, or may be performed by another method.

Representative examples of the radical polymerization initiator include, for example, azobisisobutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, t
-Butyl hydroperoxide, cumene hydroperoxide and the like, and these can be used alone or in combination of two or more. In the case where the polymerization is carried out using a light beam or the like, it is preferable to further add a photopolymerization initiator or a sensitizer. The amount of the polymerization initiator or the sensitizer is about 0.001 to 2 parts, preferably about 0.0, to 100 parts (parts by weight, hereinafter the same) of the total amount of the polymerization components.
It is preferably 1 to 1 part.

As an example of the optical material, when molding as an ophthalmic lens such as a contact lens or an intraocular lens, a molding method commonly used by those skilled in the art can be employed. Examples of such a molding method include a cutting method and a mold method. In the cutting method, polymerization is performed in an appropriate mold or container, and a rod-shaped, block-shaped, or plate-shaped material (polymer) is obtained.
This is a method of processing into a desired shape by mechanical processing such as polishing. The mold method is a method of preparing a mold corresponding to a desired shape of an ophthalmic lens, performing polymerization of the polymerization component in the mold to obtain a molded product, and mechanically performing finishing as needed. It is.

When the optical material of the present invention is obtained as a soft material at a temperature around room temperature, for example, when molding an ophthalmic lens, it is generally preferable to adopt a molding method by a mold method. Such a casting method includes, for example, a spin casting method and a static casting method.

In addition to these methods, for example, a soft optical material is impregnated with a monomer that gives a hard polymer, and then the monomer is polymerized, the whole is hardened, a cutting process is performed, and a desired shape is formed. A method of removing a hard polymer from a molded article processed into a material to obtain a molded article (for example, an ophthalmic lens) made of a soft material (Japanese Patent Laid-Open No. 62-27)
Japanese Patent Application Laid-Open No. 80241 and Japanese Patent Application Laid-Open No. 1-111854) can also be preferably applied to the present invention.

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

[0130]

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

Examples 1 to 5 and Comparative Examples 1 and 2 (Production of Oxygen-permeable Hard Optical Material) 2,2'-azobis was used as a polymerization initiator with respect to the polymerization components shown in Table 1 and 100 parts of the polymerization components. (2,4-dimethylvaleronitrile) (hereinafter referred to as V-65)
One part was mixed uniformly to give a clear solution. This was poured into a glass test tube having an inner diameter of 15 mm, and a sealed oxygen stopper was provided.

Next, the test tube was transferred into a circulating thermostatic water bath, and polymerized at 35 ° C. for 40 hours and at 50 ° C. for 8 hours.
The polymerization was completed by heating in a temperature range of 0 ° C. while gradually raising the temperature for about 16 hours to obtain a rod-shaped polymer having a diameter of about 15 mm. The polymers obtained in Examples 1 to 5 were all transparent and could be suitably used as optical materials.

The obtained rod-shaped polymer was cut into a desired thickness and subjected to cutting and polishing to prepare a test piece. The physical properties of this test piece include oxygen permeability coefficient, contact angle,
The refractive index and impact strength were examined according to the following methods. Table 1 shows the results.

(A) Oxygen Permeability Coefficient (DK _0.2 ) The oxygen permeability coefficient of the test piece was measured in a physiological saline solution at 35 ° C. using a Kakenhi type film oxygen permeability meter manufactured by Rika Seiki Kogyo.

The unit of the oxygen permeability coefficient is ml
(STP) · cm ² / (cm ³ · sec · mmHg), and the numerical values in Table 1 are values obtained by multiplying the oxygen permeability coefficient by 10 ¹¹ when the thickness of the test piece is 0.2 mm.

(B) Contact Angle Using a goniometer, the contact angle (degree) of a dry test piece having a thickness of 4 mm was measured at a temperature of 25 ° C. by a bubble method.

(C) Refractive index (η _D ) Using an ATAGO refractometer 1T (manufactured by ATAGO Co., Ltd.),
0.0mm, Refractive index of 4mm thick test piece (no unit)
Was measured under the conditions of a temperature of 25 ° C. and a relative humidity of 50%.

(D) Impact strength A steel ball with a load of 6.75 g was dropped on a 0.5 mm thick test piece in a constant temperature and humidity room at a temperature of 25 ° C. and a relative humidity of 50%, and the test piece was broken. The height (mm) at that time was measured and defined as impact resistance.

The abbreviations of the polymerization components in Table 1 and Table 2 described below are as shown below.

SiIA: Formula:

[0141]

Embedded image

Β-trimethylsilylpropyl itaconate monoester TMA-SiIA represented by the formula:

[0143]

Embedded image

Α-trimethylsilyl-β-
Trimethylsilylpropyl itaconate SiSt: Tris (trimethylsiloxy) silylstyrene SiMA: Tris (trimethylsiloxy) silylpropyl methacrylate 6FMA: 2,2,2,2 ', 2', 2'-hexafluoroisopropyl methacrylate NVP: N-vinyl- 2-pyrrolidone MAA: methacrylic acid DMAA: N, N-dimethylacrylamide VBMA: 4-vinylbenzyl methacrylate EDMA: ethylene glycol dimethacrylate

[0145]

[Table 1]

From the results shown in Table 1, all of the test pieces obtained in Examples 1 to 5 have excellent oxygen permeability, small contact angle, excellent surface hydrophilicity, and relatively high refractive index. It can be seen that the material has impact strength. Moreover, comparing the test piece of Example 1 using the monomer (A) with the test piece of Comparative Example 1 using only the monomer (B) without using the monomer (A) in Example 1, Further, the test pieces of Examples 2 and 3 using the monomer (A) and the test pieces of Comparative Examples 2 and 3 using the monomer (B) without using the monomer (A) in Examples 2 and 3 And Examples 1 and 2,
The test piece No. 3 has a higher refractive index than the test pieces of Comparative Examples 1 and 2, and has a smaller contact angle, so that it has excellent surface hydrophilicity and high impact strength.

Example 6 and Comparative Example 3 (Production of a soft hydrogel optical material) Except that 0.15 part of V-65 was used as a polymerization initiator for 100 parts of the polymerization component and 100 parts of the polymerization component shown in Table 2. A rod-shaped polymer having a diameter of about 15 mm was obtained in the same manner as in Examples 1 to 5 and Comparative Examples 1 and 2. All of the polymers obtained in Example 6 were transparent and could be suitably used as optical materials.

Test pieces were prepared from the obtained rod-shaped polymer in the same manner as in Examples 1 to 5 and Comparative Examples 1 and 2. As physical properties of the test piece, a water content, a linear swelling rate, and a lipid adhesion amount were examined according to the following methods. Table 2 shows the results.

(E) Moisture Content The weight (Wo) of a test piece having a diameter of 12 mm and a thickness of 0.5 mm
(G)), the test piece was immersed in water at 20 ° C., and the weight of the test piece in an equilibrium hydrated state (W (g))
Was measured. Using these measured values, 2
The water content (% by weight) at 0 ° C. was calculated.

[Water content (% by weight)] = {(W−Wo) / W} × 100

(F) Linear swelling ratio A test piece having a diameter of 12 mm and a thickness of 0.2 mm was immersed in water at 20 ° C., and the diameter of the test piece (D (m
m)) was measured. Using this measured value, the linear swelling ratio (%) at 20 ° C. was calculated based on the following equation.

[Linear swelling ratio (%)] = {(D-12) / D} × 100

(G) Amount of Lipid Attached First, artificial eye oil (pH 7 buffer) consisting of the following components was prepared.

Component Amount (g) Oleic acid 0.3 Linoleic acid 0.3 Tripalmitin 4.0 Cetyl alcohol 1.0 Palmitic acid 0.3 Sperm acetyl 4.0 Cholesterol 0.4 Cholesterol palmitate 0.4 Egg yolk lecithin 14 .0

Next, a diameter of 12.7 m was contained in the artificial eye oil.
m, a test piece having a thickness of 1 mm was immersed at 37 ° C. for 5 hours, washed with running water, and then the lipid adhering to the test piece was mixed with a mixed solvent of ethanol and ether (ethanol: ether =
(3: 1 (volume ratio)) 1 ml.

Concentrated sulfuric acid 1 was added to 200 μl of the obtained lipid extract.
and then add 3 mg of vanillin and 2 ml of phosphoric acid
After mixing, UV spectrophotometer (manufactured by Shimadzu Corporation, UV
-2400PC), and the absorbance of this solution at a wavelength of 540 nm was measured.

On the other hand, as a control, the absorbance was measured in the same manner as described above except that physiological saline was used instead of the artificial eye oil.

Further, the absorbance at various concentrations was measured using the artificial eye oil, and a calibration curve was prepared in accordance with the absorbance of the control.

The absorbance of the lipid extract of the test piece was compared with the calibration curve to determine the amount of lipid adhered per unit area (mg / cm ² ).

[0160]

[Table 2]

From the results shown in Table 2, the monomer (A)
In the test piece obtained in Example 6 in which is used, compared with the test piece of Comparative Example 3 in which only the monomer (B) was used without using the monomer (A), the amount of attached lipid was particularly small, It turns out that it is excellent in lipid contamination resistance.

[0162]

The optical material of the present invention has excellent transparency,
Moreover, it has excellent oxygen permeability, surface wettability and stain resistance, and has a high refractive index and high impact strength.

Therefore, the optical material of the present invention can be suitably used for, for example, ophthalmic lenses such as contact lenses and intraocular lenses, artificial cornea, goggles, and spectacles.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // C08F 290/06 C08F 290/06

Claims (3)

[Claims] 1. A compound of the general formula (I): (Wherein R ¹ is a hydrogen atom or a trimethylsilyl group, R ²
Is an alkylene group having 1 to 5 carbon atoms, and R ³ is a general formula: —Si (CH ₃ ) _n (OSi (CH ₃ ) ₃ ) _3-n (wherein, n represents 0 or an integer of 1 to 3) An optical material comprising a polymer obtained by polymerizing a polymerization component containing a monomer represented by the following formula: 2. The optical material according to claim 1, wherein the amount of the monomer represented by the general formula (I) is 1% by weight or more of the polymerization component. 3. The optical material according to claim 1, wherein the polymerization component contains a monomer having an unsaturated double bond copolymerizable with the monomer represented by the general formula (I).