JP3027421B2 - Graft copolymer, contact lens solution containing the same, and method for hydrophilizing a contact lens using such a solution - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a graft copolymer, a solution for contact lenses containing the same, and a method for hydrophilizing a contact lens using such a solution. A novel graft copolymer useful for modifying the surface of a non-water-containing contact lens such as a hard contact lens and a non-water-containing soft contact lens using the same, and a technique therefor. The present invention relates to a contact lens solution that can be used as a surface hydrophilizing agent.

[0002]

BACKGROUND ART Non-water-containing contact lenses conventionally used include hard contact lenses containing methyl methacrylate as a main component and high oxygen-permeable hard lenses containing siloxanyl methacrylate and fluoroalkyl methacrylate as a main component. There are contact lenses and non-hydrous soft contact lenses made of silicone rubber containing polydimethylsiloxane as a main component or butyl rubber containing butyl acrylate as a main component.

[0003] Since these contact lenses are non-water-containing, their surfaces are hydrophobic. Among them, high oxygen-permeable non-water-containing contact lenses, which have recently attracted attention, have particularly strong hydrophobic properties. have. This is because, in order to increase the oxygen permeability of a lens, the silicone component and the fluorine component in the lens forming material generally tend to increase, in other words, the higher the oxygen permeability of a lens, the more the silicone component And the content of fluorine components is high, and as a result, the lens surface has strong hydrophobicity. And, due to the hydrophobicity of such a lens surface, when a non-water-containing contact lens is worn, lipid stains often adhere to the lens, causing a fogging phenomenon on the lens, resulting in poor visibility. There was a problem that it would.

[0004] Therefore, as a method for making the hydrophobic surface of the contact lens hydrophilic, a plasma surface treatment, a chemical treatment with an acid, an alkali, or the like has been considered. There is a problem in durability, and reworking requires considerable labor.

On the other hand, a contact lens is immersed in a solution containing a hydrophilic polymer, and the polymer is adhered to the surface of the contact lens, thereby modifying the surface of the contact lens.
There is a way to use a solution. According to this method, if necessary, the hydrophilicity-imparting treatment can be performed relatively easily and repeatedly, so that the hydrophilicity of the lens surface can be maintained.

For example, Japanese Patent Publication No. 48-37910 discloses a contact lens solution containing a water-soluble polymer such as polyvinyl alcohol, hydroxyethyl cellulose, polyvinyl pyrrolidone and the like. However, such a treatment solution is effective for relatively weakly hydrophobic lenses such as a hard contact lens made of methyl methacrylate and a high oxygen permeable hard contact lens containing methyl methacrylate as a main component, but a silicone component. And non-containing contact lenses containing a large amount of fluorine components, since the surface of the lens is strongly hydrophobic, the water-soluble polymer contained in the solution hardly adheres to the lens surface, and is no longer effective. There is a disadvantage that it will.

Japanese Unexamined Patent Publication (Kokai) No. 63-246718 discloses a lens solution for surface treatment of a contact lens made of a polymer substance having an ionic charge.
However, if this solution is used, the contact lens surface must have an ionic charge that is opposite to the ionic charge of the polymer material in the solution, and the ionic charge density will be of some magnitude. Since it is necessary to have an appropriate surface treatment, it is necessary to perform an extra treatment for increasing the charge density on the surface of the contact lens prior to the hydrophilic treatment, and there is a problem that the treatment becomes complicated. Furthermore, as is clear from the examples described in this publication, the treatment time is as long as 5 minutes, and there are some drawbacks such as the effect of the hydrophilicity is not so large.

[0008]

The present invention has been made in view of such circumstances, and an object of the present invention is to provide a non-hydrous contact lens having high oxygen permeability for a long period of time. In order to be able to be worn on the lens, in other words, to reduce the adhesion of lipid stains to the lens, the hydrophilic treatment of the contact lens is effectively performed more safely, easily and in a shorter time. An object of the present invention is to provide a graft copolymer, a solution for contact lenses containing the same, and a treatment method using such a solution.

[0009]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that 2-hydroxyethyl methacrylate or 2-hydroxyethyl methacrylate using a predetermined polymer type polymerization initiator having a hydrophobic group. -A graft copolymer obtained by polymerizing a monomer mixture containing hydroxyethyl methacrylate as a main component has a good surface activity, and is well adsorbed on the hydrophobic surface of a contact lens, whereby such a hydrophobic surface is obtained. The fact that the graft copolymer is water-insoluble, along with the fact that it can be effectively used to modify Very simple contact lens surface by immersing the lens, taking it out immediately and rinsing it thoroughly with a poor solvent such as tap water Found the fact that hydrophilic can be made, it was accomplished the present invention.

That is, in order to solve the above-mentioned problems, the present invention provides 40 to 60 mol% of N-vinyl lactam,
2-hydroxyethyl methacrylate using a binary N-vinyl lactam polymer type polymerization initiator obtained by copolymerizing at least one kind of peroxide-containing fumarate represented by the following formula 5 with 60 to 40 mol%: Alternatively, the gist of the present invention is a graft copolymer obtained by polymerizing a monomer mixture containing 2-hydroxyethyl methacrylate as a main component.

[0011]

Embedded image (However, R ₁ is a linear alkyl group having 18 or less carbon atoms,
Branched alkyl or cyclic alkyl group, or a carbon atoms indicated from 6 to 18 aromatic radical,, R ₂ is 13 carbon atoms
The following linear alkyl groups, branched alkyl groups or cyclic alkyl groups, or phenyl groups are shown)

Further, in the present invention, 40 to 60 mol% of N-vinyl lactam, at least one of the peroxide-containing fumarate represented by the above formula (5), alkyl-fluoroalkyl fumarate and alkyl-silicon containing A molar ratio of at least one of fumaric acid diesters selected from the group consisting of alkyl fumarate, fluoroalkyl-silicon-containing alkyl fumarate, bis (fluoroalkyl) fumarate and bis (silicon-containing alkyl) fumarate in a molar ratio of 9: 1 to 1: 1 2-hydroxyethyl methacrylate or 2 using a tertiary N-vinyl lactam polymer type polymerization initiator obtained by copolymerizing 60 to 40 mol% of those obtained by combining at a ratio of 1: 9.
The gist of the present invention is also a graft copolymer obtained by polymerizing a monomer mixture containing -hydroxyethyl methacrylate as a main component.

Further, the present invention relates to a method for producing styrene of 40-90.
2-hydroxyethyl methacrylate or 2-hydroxyethyl methacrylate, using a styrene-based polymer type polymerization initiator obtained by copolymerizing at least one mol% of at least one kind of peroxide-containing fumarate represented by Chemical Formula 5 with 60 to 10 mol%. 2
The gist of the present invention is also a graft copolymer obtained by polymerizing a monomer mixture containing -hydroxyethyl methacrylate as a main component.

In the present invention, a solution mainly composed of at least one polymer selected from the above three types of graft copolymers and a solvent for dissolving the polymer is referred to as a contact lens solution. To do
At this time, advantageously, as a solvent for dissolving the polymer, the following chemical formula 6: HO— (CH ₂ CH ₂ O) _n —R ₃ (chemical formula 6) (where R ₃ is a hydrogen or methyl group, and n is A mixed solvent consisting of 20 to 100% by weight of an ethylene glycol compound represented by the following formula (representing an integer of 1 to 20) and 80 to 0% by weight of water is advantageously used.

Also, such a contact lens solution is applied to a contact lens to be surface-hydrophilized, wets the surface, and is dissolved in the solution for such a surface. By bringing the poor solvent of the polymer into contact, an effective hydrophilicity of the contact lens surface is achieved.

[0016]

The three kinds of graft copolymers according to the present invention have a hydrophobic group in the backbone polymer, and the branched polymer has 2-hydroxyethyl methacrylate or 2-hydroxyethyl methacrylate exhibiting hydrophilicity. Because it is composed of a polymer containing methacrylate as a main component, it has excellent surface activity.

The contact lens solution according to the present invention contains at least one kind of such a graft copolymer. However, since such a graft copolymer is water-insoluble, it is difficult to use a so-called poor solvent. The polymer is characterized in that when diluted by pouring some water, the polymer is aggregated. Therefore, by using such a contact lens solution and immersing a hydrophobic contact lens in the solution to wet the entire surface of the lens with the solution, the graft copolymer has the hydrophobic property. The groups are oriented on the contact lens surface and become adsorbed. That is, the contact lens solution of the present invention has a property of satisfactorily wetting a hydrophobic contact lens surface due to its surface activity. Then, by performing a treatment such as immediately rinsing the contact lens with a poor solvent such as water, the graft copolymer that has been dissolved is aggregated because it is insoluble in water, and is strongly adsorbed on the lens surface, Thus, the surface of the contact lens is satisfactorily made hydrophilic.

In short, the contact lens solution according to the present invention is obtained by dipping a hydrophobic contact lens,
By performing a very simple operation of immediately rinsing it with a poor solvent such as water after taking it out, the hydrophobic contact lens surface can be satisfactorily made hydrophilic. Therefore, even for a highly oxygen-permeable, non-water-containing contact lens having a strong hydrophobicity, by performing such a treatment prior to wearing the lens, the surface can be made hydrophilic, and lipid contamination can be advantageously achieved. This makes it possible to effectively prevent the adhesion of the particles, so that it is possible to wear them comfortably for a long time without feeling foreign substances.

Further, in the contact lens solution according to the present invention, the polymer which is a branch component of the graft copolymer to be dissolved is made of 2-hydroxyethyl methacrylate and a monomer selected from a predetermined monomer group. The polymer obtained by polymerizing the above compound makes it possible to further improve the adsorptivity of the graft copolymer to a contact lens.

In the contact lens solution according to the present invention, the solvent for dissolving the graft copolymer is prepared by mixing 20 to 100% by weight of the ethylene glycol compound represented by the formula (6) with water When the content is 80 to 0% by weight, the graft copolymer can be advantageously dissolved without changing the specification of the contact lens.

[0021]

In the first and second graft copolymers according to the present invention, binary or ternary N-vinyl lactam polymer type polymerization initiators as precursors thereof are used. In the synthesis, N-vinyl lactam is copolymerized in any case, and such N-vinyl tactam is specifically exemplified by N-vinyl-2-pyrrolidone, N-vinyl-3-
Methyl-2-pyrrolidone, N-vinyl-5-methyl-2
-Pyrrolidone, N-vinyl-3,3,5-trimethyl-
2-pyrrolidone, N-vinyl-5-phenyl-2-pyrrolidone, N-vinyl-3-benzyl-2-pyrrolidone,
N-vinylpiperidone, N-vinylcaprolactam, N
-Vinylcaprylactam and the like, and among these, they may be used alone or in combination of two or more. Among them, N-vinyl-2-pyrrolidone is a typical general-purpose monomer and can be easily obtained, so that it is particularly preferably used in the present invention.

In the present invention, the desired N-
In order to obtain a vinyl lactam polymer type polymerization initiator,
The peroxide-containing fumarate represented by the above formula (5) is copolymerized with the N-vinyl lactam. Specific examples of the peroxide-containing fumarate include t-butyl peroxy-methyl fumarate, t-butyl peroxy-ethyl fumarate, and t-butyl peroxy-ethyl fumarate.
Butyl peroxy-isopropyl fumarate, t-butyl peroxy-n-butyl fumarate, t-butyl peroxy-n-pentyl fumarate, t-butyl peroxy-n-hexyl fumarate, t-butyl peroxy-
n-octyl fumarate, t-butyl peroxy-2-
Ethylhexyl fumarate, t-butyl peroxy-lauryl fumarate, t-butyl peroxy-stearyl fumarate, t-butyl peroxy-phenyl fumarate, t-butyl peroxy-cyclohexyl fumarate, t-pentyl peroxy-methyl fumarate, t −
Pentyl peroxy-ethyl fumarate, t-pentyl peroxy-isopropyl fumarate, t-pentyl peroxy-n-butyl fumarate, t-pentyl peroxy-n-pentyl fumarate, t-pentyl peroxy-n-hexyl fumarate, t -Pentyl peroxy-n-octyl fumarate, t-pentyl peroxy-
2-ethylhexyl fumarate, t-pentyl peroxy-lauryl fumarate, t-pentyl peroxy-stearyl fumarate, t-pentyl peroxy-phenyl fumarate, t-hexyl peroxy-methyl fumarate, t-hexyl peroxy-ethyl fumarate , T
-Hexyl peroxy-isopropyl fumarate, t-
Hexyl peroxy-n-butyl fumarate, t-hexyl peroxy-n-pentyl fumarate, t-hexyl peroxy-n-hexyl fumarate, t-hexyl peroxy-n-octyl fumarate, t-hexyl peroxy-2-ethylhexyl Fumarate, t-hexyl peroxy-lauryl fumarate, t-hexyl peroxy-stearyl fumarate, t-hexyl peroxy-phenyl fumarate, t-cumyl peroxy-methyl fumarate, t-cumyl peroxy-ethyl fumarate, t-cumyl peroxy-isopropyl fumarate,
t-cumyl peroxy-n-butyl fumarate, t-cumyl peroxy-n-pentyl fumarate, t-cumyl peroxy-n-hexyl fumarate, t-cumyl peroxy-n-octyl fumarate, t- Cumyl peroxy-2-ethylhexyl fumarate, t-cumyl peroxy-lauryl fumarate, t-cumyl peroxy-stearyl fumarate, t-cumyl peroxy-phenyl fumarate and the like can be mentioned.

Here, the N-vinyl lactam polymer type polymerization initiator (binary) as a precursor of the first graft copolymer according to the present invention is composed of the above-mentioned components, ie, a predetermined N-vinyl lactam and It is obtained by copolymerizing a monomer mixture comprising a peroxide-containing fumarate represented by Chemical Formula 5, and in the present invention, in addition to these components, an alkyl-fluoroalkyl fumarate and an alkyl-silicon-containing Alkyl fumarate,
Fluoroalkyl-silicon containing alkyl fumarate,
A terpolymer-type polymerization initiator obtained by copolymerization using a fumaric acid diester selected from the group consisting of bis (fluoroalkyl) fumarate and bis (silicon-containing alkyl) fumarate is a second graft copolymer Used as a precursor for

As the above-mentioned alkyl-fluoroalkyl fumarate, for example, those represented by the following formula 7 are used.

[0025]

Embedded image (Wherein, R ₁ is as defined above, and R ₄ is-(C
_{H 2) k -C a H b} F 2a + 1-b [a is 1 to 21 integer, b is 0 or 1, k is an integer of 0 to 3] This shows the)

Specifically, methyl-trifluoroethyl fumarate, ethyl-trifluoroethyl fumarate,
Isopropyl-trifluoroethyl fumarate, octyl-trifluoroethyl fumarate, phenyl-trifluoroethyl fumarate, methyl-hexafluoroisopropyl fumarate, ethyl-hexafluoroisopropyl fumarate, isopropyl-hexafluoroisopropyl fumarate, octyl- Hexafluoroisopropyl fumarate, cyclohexyl-hexafluoroisopropyl fumarate, phenyl-hexafluoroisopropyl fumarate, methyl-octafluoropentyl fumarate, ethyl-octafluoropentyl fumarate, isopropyl-octafluoropentyl fumarate, octyl-octafluoro Pentyl fumarate, cyclohexyl-octafluoropentyl fumarate, phenyl-octafluoro Pliers fumarate, and the like.

As the alkyl-silicon-containing alkyl fumarate, for example, the one represented by the following formula 8 is used.

[0028]

Embedded image (Wherein, R ₁ is the same as described above, and R ₅ is [A ₁ , A ₂ , and A ₃ are each —CH ₃ or —O—Si
(CH ₃ ) ₃ ], 1 is 0 or 1,
m is an integer of 1 to 3, and n is 0 or 1. Where n = 1
When l = 0)

Specific examples of such alkyl-silicon-containing alkyl fumarate include methyl-trimethylsilylpropyl fumarate, ethyl-trimethylsilylpropyl fumarate, isopropyl-trimethylsilylpropyl fumarate, octyl-trimethylsilylpropyl fumarate, and cyclohexyl-trimethylsilylpropyl fumarate. , Phenyl-trimethylsilylpropyl fumarate, methyl-pentamethyldisiloxanylpropyl fumarate, ethyl-pentamethyldisiloxanylpropyl fumarate, isopropyl-pentamethyldisiloxanylpropyl fumarate, octyl-pentamethyldi Siloxanylpropyl fumarate, cyclohexyl-pentamethyldisiloxanylpropyl fumarate, phenyl-pentamethyl Siloxanyl propyl fumarate,
Methyl-methylbis (trimethylsilyloxy) silylpropyl fumarate, ethyl-methylbis (trimethylsilyloxy) silylpropyl fumarate, isopropyl-methylbis (trimethylsilyloxy) silylpropyl fumarate, octyl-methylbis (trimethylsilyloxy) silylpropyl fumarate, cyclohexyl- Methyl bis (trimethylsilyloxy) silylpropyl fumarate, phenyl-methylbis (trimethylsilyloxy) silylpropyl fumarate, methyl-tris (trimethylsilyloxy) silylpropyl fumarate, ethyl-tris (trimethylsilyloxy) silylpropyl fumarate, isopropyl-tris ( Trimethylsilyloxy) silylpropyl fumarate, octyl-tris (trime Lucylyloxy) silylpropyl fumarate, cyclohexyl-tris (trimethylsilyloxy) silylpropyl fumarate, phenyl-tris (trimethylsilyloxy) silylpropyl fumarate, methyl-pentamethyldisiloxanylpropyloxyethyl fumarate, ethyl-pentamethyldi Siloxanylpropyloxyethyl fumarate, isopropyl-
Pentamethyldisiloxanylpropyloxyethyl fumarate, octyl-pentamethyldisiloxanylpropyloxyethyl fumarate, cyclohexyl-pentamethyldisiloxanylpropyloxyethyl fumarate,
Phenyl-pentamethyldisiloxanylpropyloxyethyl fumarate and the like.

Further, as the fluoroalkyl-silicon-containing alkyl fumarate, for example, those represented by the following formula 9 are used.

[0031]

Embedded image (Wherein, R ₄ , R ₅ , m and n are the same as described above)

Specific examples thereof include trifluoroethyl-trimethylsilylpropyl fumarate, hexafluoroisopropyl-trimethylsilylpropyl fumarate, octafluoropentyl-trimethylsilylpropyl fumarate, trifluoroethyl-pentamethyldisiloxanyl propyl fumarate, Hexafluoroisopropyl-pentamethyldisiloxanylpropyl fumarate, octafluoropentyl-pentamethyldisiloxysanylpropyl fumarate, trifluoroethyl-methylbis (trimethylsilyloxy) silylpropyl fumarate, hexafluoroisopropyl-methylbis (trimethylsilyloxy ) Silylpropyl fumarate, octafluoropentyl-methylbis (trimethylsilyloxy) silylpro Rufumareto, trifluoroethyl - tris (trimethylsilyloxy) silyl propyl fumarate, hexafluoroisopropyl - tris (trimethylsilyloxy) silyl propyl fumarate, octafluoropentyl - tris (trimethylsilyloxy) silyl propyl fumarate, trifluoroethyl -
Examples thereof include pentamethyldisiloxanylpropyloxyethyl fumarate, hexafluoroisopropyl-pentamethyldisiloxanylpropyloxyethyl fumarate, and octafluoropentyl-pentamethyldisiloxanylpropyloxyethyl fumarate.

Further, the bis (fluoroalkyl)
As the fumarate, for example, one represented by the following formula 10 is used. Specifically, bis (trifluoroethyl) fumarate, bis (tetrafluoropropyl) fumarate, bis (hexafluoroisopropyl) fumarate, bis (octa) Fluoropentyl) fumarate and the like.

[0034]

Embedded image (Wherein, R ₄ is the same as described above)

The bis (silicon-containing alkyl)
As the fumarate, for example, one represented by the following formula 11 is used.

[0036]

Embedded image (Wherein, R ₅ , m and n are the same as described above)

Specifically, bis (trimethylsilylpropyl) fumarate, bis (pentamethyldisiloxanylpropyl) fumarate, bis (pentamethyldisiloxanylpropyloxyethyl) fumarate, bis (methylbis (trimethylsilyloxy) silylpropyl) Fumarate, bis (tris (trimethylsilyloxy) silylpropyl) fumarate and the like.

Here, as a precursor of the first graft copolymer of the present invention, a binary N-vinyl lactam polymer comprising the N-vinyl lactam and the peroxide-containing fumarate represented by the above formula (5) In producing the type polymerization initiator, 60 to 40 mol% of the latter is copolymerized with respect to 40 to 60 mol% of the former. That is, the peroxide-containing fumarate is poor in homopolymerizability, but has the property that it copolymerizes well with N-vinyllactam, and exhibits the unique property that the resulting copolymer is rich in alternating properties. However, when the amount of N-vinyl lactam is less than 40 mol%, only unreacted peroxide-containing fumarate remains, which is not economical.
If more than 0 mol% is used, in other words if the peroxide-containing fumarate is used in an amount less than 40 mol%, the resulting polymer will be composed of a peroxide-containing fumarate-containing polymer and a homopolymer of N-vinyllactam. This is unfavorable because the mixture is likely to be a mixture, making it difficult to separate and purify the polymer type polymerization initiator.
Therefore, the amount of N-vinyl lactam used is 40 to 60 mol%, and more preferably 50 mol%.

When the first graft copolymer having the binary N-vinyl lactam polymer type polymerization initiator as a precursor is used as a contact lens solution, When a highly hydrophobic substituent is introduced into the backbone polymer, the graft copolymer is strongly adsorbed on the surface of the contact lens, and thus the peroxide-containing fumarate used in the synthesis of the polymer-type polymerization initiator has an R Preferably, ₁ is a linear alkyl group, a branched alkyl group or a cyclic alkyl group having 8 to 18 carbon atoms, or an aromatic group having 6 to 18 carbon atoms.

In the present invention, the tertiary N-vinyllactam polymer type polymerization initiator, which is a precursor of the second graft copolymer, comprises (a) 40 to 60 mol of the N-vinyllactam. And (b) the peroxide-containing fumarate and the predetermined fumaric acid diester in a ratio of 9: 1 to 1: 1.
Combined in a ratio (mol) of 1: 9,
They are produced by copolymerizing them using 40 mol%.

Also in this case, as described above, not only the peroxide-containing fumarate but also the fumaric acid diesters, for example, the fumaric acid diesters represented by the chemical formulas (7) and (8) are poor in homopolymerizability. Have the property that they copolymerize well with N-vinyl lactam, and the resulting copolymer exhibits the unique property of being rich in alternation. When used in amounts less than mole%,
If the unreacted material remains and is not economical, and if more than 60 mol% of N-vinyl lactam is used, the resulting polymer will be a homopolymer of N-vinyl lactam and a polymer containing fumarate and fumaric acid diester containing peroxide. A mixture is apt to be formed, and it becomes difficult to separate and purify the polymer type polymerization initiator, which is not preferable. Therefore, the amount of N-vinyl lactam used is 40 to 60 mol%, and more preferably 50 mol%.

In the ternary polymer type polymerization initiator, the fumaric diester exhibiting hydrophobicity is copolymerized and contained, for the following reasons. That is, as described above, when the first graft copolymer having a binary polymer-type polymerization initiator as a precursor is used as a contact lens solution, in order to improve its hydrophilicity-imparting effect. It is preferable that the graft copolymer contains a substituent exhibiting strong hydrophobicity.Therefore, the peroxide-containing fumarate used in the production of the polymer-type polymerization initiator which is a precursor of the graft copolymer is used. It is preferable to make the carbon number of R ₁ relatively large. However, when the carbon number of R ₁ is increased, the glass transition point of the polymerized polymerization initiator to be synthesized is lowered, and the polymer becomes viscous and tends to be difficult to handle. In the initiator, such an inconvenience is ameliorated. Particularly, in the production of the terpolymer-type polymerization initiator, R _{1 of the} peroxide-containing fumarate used therein is used.
Is a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group or a cyclic alkyl group, or a phenyl group,
By combining the above-mentioned predetermined fumaric acid diester as a copolymerization component, the obtained polymer-type polymerization initiator can be made into a powdery form, and a strong hydrophobic group can be introduced arbitrarily. The production of the graft copolymer is easy, and a graft copolymer having good surface activity can be obtained.

As a result, the fumaric acid diester is used together with the peroxide-containing fumarate in the production of the tertiary N-vinyl lactam polymer type polymerization initiator. If the amount is less than 1: 9 (mol) relative to the fumaric acid diester, the graft copolymer produced from the produced polymer-type polymerization initiator has a low grafting efficiency, which is not preferable. If it is used in an amount of more than 9: 1 (mol) with respect to the acid diester, the amount of the fumaric acid diester inevitably must be reduced, and the fumaric acid diester functions as a hydrophobic site in the polymerization initiator. It is not preferable because the effect of fumaric acid diester is not effectively exhibited. Therefore, the amount of the peroxide-containing fumarate to be used must be a molar ratio of 9: 1 to 1: 9 with respect to the fumaric acid diester, and the total amount of the peroxide-containing fumarate and the fumaric acid diester is required. Is determined to be 60 to 40 mol% in relation to the amount of the N-vinyl lactam used.

Further, in the third graft copolymer according to the present invention, in the polymer type polymerization initiator which is a precursor thereof, 40 to 90 mol% of styrene and peroxide represented by the above formula (5) 60 to 10 of contained fumarate
The resulting polymer (polymerization initiator) will be used by copolymerizing them using mol%.

In such a polymerization initiator, the peroxide-containing fumarate is poor in homopolymerizability, but has the property of copolymerizing well with styrene. However, if less than 40 mol% of styrene is used, it becomes unsatisfactory. Only the fumarate containing the reactive peroxide remains and is not economical, whereas if more than 90 mol% of styrene is used, ie less than 10 mol% of the fumarate containing peroxide, the resulting polymer in the The styrene content increases and the hydrophobicity increases, and the graft copolymer obtained using this polymer-type polymerization initiator is uniformly dissolved in a good solvent of a polymer mainly composed of 2-hydroxyethyl methacrylate. It becomes difficult. Therefore,
The copolymerization ratio of styrene / peroxide-containing fumarate in such a polymer type polymerization initiator is to be 40 to 90 mol% / 60 to 10 mol%.

Further, such a polymer type polymerization initiator includes:
Since a monomer having hydrophobicity such as styrene is used, R _{1 of the} peroxide-containing fumarate to be copolymerized is preferably a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group or a cyclic alkyl group. Or a phenyl group. That is, if the carbon number of R ₁ is large, the obtained polymer type polymerization initiator becomes too strong in hydrophobicity, so that the polymer type polymerization initiator is a monomer of 2-
Hydroxyethyl methacrylate and its polymerization solvent are difficult to dissolve, which is not preferable.

As described above, as the N-vinyllactam-based and styrene-based polymer-type polymerization initiators which are the precursors of the graft copolymer according to the present invention, general radical polymerization initiators are used. It is easily synthesized by a radical polymerization method, and is polymerized using a known polymerization technique such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.

The temperature of the polymerization reaction is suitably in a range where decomposition of the peroxide group in the peroxide-containing fumarate is suppressed, that is, in a range of about 0 ° C. to about 60 ° C. Examples of the radical polymerization initiator that can be used within such a polymerization temperature range include, for example, 2,2′-azobis (4
-Methoxy-2,4 dimethylvaleronitrile), 2,2'-
Azobis (2-cyclopropylpropionitrile), 2,
2'-azobis (2,4-dimethylvaleronitrile), 2,
Examples include azo compounds such as 2'-azobisisobutyronitrile and organic peroxides such as isobutyl peroxide, diisopropylperoxydicarbonate and t-butylperoxypivalate.
More than one species can be selected and used.

The amount of the radical polymerization initiator used is preferably in the range of about 0.01 to 5 parts by weight based on 100 parts by weight of all monomers to be polymerized. Further, the polymerization time is determined according to the polymerization temperature, the type of the radical polymerization initiator, and the like, and about 1 to 72 hours is suitably employed.

The number average molecular weight of the thus obtained polymer type polymerization initiator is preferably in the range of about 100 to 1,000,000, and more preferably in the range of about 1000 to about 1,000,000.
It is ten thousand. By the way, when the number average molecular weight is less than about 1000, the properties of the backbone polymer in the graft copolymer obtained by using the polymer type polymerization initiator tend not to be exhibited. When the average molecular weight is more than about 1,000,000, the molecular weight of the graft copolymer obtained using the polymer type polymerization initiator becomes very large, and therefore, in order to prepare a contact lens solution according to the present invention, This is because when such a graft copolymer is dissolved in a predetermined solvent, its solubility tends to be inferior.

Incidentally, the N-
The vinyl lactam polymer type polymerization initiator adopts a structure in which an N-vinyl lactam unit exhibiting hydrophilicity in a polymer chain and a peroxide-containing fumarate unit or a fumaric acid diester unit having a hydrophobic site are alternately present. Then, when subsequently graft copolymerizing a monomer mixture containing 2-hydroxyethyl methacrylate or 2-hydroxyethyl methacrylate as a main component, such a polymer type polymerization initiator dissolves in the monomer mixture or the polymerization solvent. Easy and uniform polymerization is possible.
Then, the obtained graft copolymer has excellent surface activity due to the presence of a hydrophobic site in the backbone polymer.

The styrene-based polymer type polymerization initiator used in the present invention is hydrophobic in the polymer chain,
In addition, the obtained graft copolymer has excellent hydrophobic-hydrophilic surface activity because it has a benzene ring that favors the adsorption phenomenon. Then, the graft copolymer of the present invention uses 2-hydroxyethyl methacrylate or 2-hydroxyethyl methacrylate by using at least one of N-vinyllactam-based and styrene-based polymer-type polymerization initiators as described above. Although it is obtained by polymerizing (grafting) a monomer mixture containing 80% by weight or more as a main component, in the case of using the monomer mixture as described above at the time of graft polymerization, It is also possible to copolymerize other monomers together with 2-hydroxyethyl methacrylate.

In particular, as a monomer to be copolymerized with 2-hydroxyethyl methacrylate, alkyl (meth) acrylate, siloxanylalkyl (meth) acrylate, fluoroalkyl (meth) acrylate, styrene monomer and vinyl ester are used. In such a case, the adhesion of the obtained polymer to the contact lens surface can be effectively improved.
In addition, such a monomer may be used alone or in combination of two or more, but it is preferable that the total amount thereof is 20% by weight or less in the monomer mixture. . That is, when used in an amount exceeding 20% by weight, the hydrophobicity of the obtained polymer increases, and the hydrophilicity-imparting effect, which is an important effect of the contact lens solution of the present invention, becomes poor. It is not desirable. In addition, "... (meth) acrylate" represents "... methacrylate" or "... acrylate", and the same applies to the following.

Here, as more specific examples of such a monomer, examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate. A) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, phenyl (meth) acrylate, and the like.

The siloxanylalkyl (meth)
Specific examples of the acrylate include trimethylsilylmethyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, pentamethyldisiloxanylmethyl (meth) acrylate, pentamethyldisiloxanylpropyl (meth) acrylate, and methylbis [trimethylsiloxy] Silylpropyl (meth) acrylate,
Tris [trimethylsiloxy] silylpropyl (meth)
Acrylates and methylbis [trimethylsiloxy] silylpropylglycerol (meth) acrylate can be exemplified.

Further, specific examples of the fluoroalkyl (meth) acrylate include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1, 1, 3, 3, 3
-Hexafluoro-2-propyl (meth) acrylate, 2,2,3,3,4,4,5,5-octafluoropentyl (meth) acrylate, 2,2,3,3,4,4,5 5, 6,
6, 7, 7-dodecafluoroheptyl (meth) acrylate and the like can be mentioned.

Further, as the styrene monomer, for example, styrene, para-methylstyrene, tert
-Butylstyrene, pentafluorostyrene, trimethylsilylstyrene, tris (trimethylsiloxy) silylstyrene and the like can be used, and as the vinyl esters, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate and the like are used. Can be done.

By the way, the graft copolymer according to the present invention is prepared by appropriately combining the above-mentioned polymer type polymerization initiator and 2-hydroxyethyl methacrylate or a monomer mixture containing 2-hydroxyethyl methacrylate as a main component. By performing the above, it is easily synthesized. This polymerization is performed by radical polymerization.In general, various methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization are used for radical polymerization. Since the main component, 2-hydroxyethyl methacrylate, itself has a hydroxyethyl group which is susceptible to a radical chain transfer reaction, for example, in a bulk polymerization or the like, a crosslinking reaction proceeds and becomes insoluble in a solvent. Because it is not desirable,
A solution polymerization method containing a chain transfer agent or a solution polymerization method using a solvent which itself has a chain transfer ability is suitably adopted.

As described above, when a chain transfer agent is used in combination, examples of the chain transfer agent include mercaptans such as n-butyl mercaptan, dodecyl mercaptan, and thioglycolic acid; chloroform; carbon tetrachloride; And the like. The amount of these chain transfer agents used is
A range of about 0.05 to 5 parts by weight per 100 parts by weight of the total monomers to be polymerized is preferred.

Further, in order to obtain the graft copolymer according to the present invention, the amount of the polymer type polymerization initiator to be used is set to 10% of the total monomer or the total monomer mixture to be polymerized.
The range of 0.01 to 10 parts by weight relative to 0 parts by weight is preferable. That is, when the amount used is less than 0.01 part by weight, the surface activity of the obtained graft copolymer becomes poor, while when it is more than 10 parts by weight, the obtained graft copolymer becomes This is because the hydrophilicity of the compound becomes poor.

Examples of the solvent to be used in the solution polymerization include alcohols such as methanol, ethanol and ethylene glycol monomethyl ether, and dimethyl sulfoxide. These solvents are preferably used in the range of 50 to 1000 parts by weight based on 100 parts by weight of the total monomers to be polymerized. If the amount is less than 50 parts by weight, the crosslinking reaction tends to proceed during the polymerization and gelation often occurs. In the process of purifying the polymer,
This is because a large amount of precipitation solvent must be used, which is not preferable.

The polymerization reaction is carried out at room temperature to 120 ° C. for a time necessary for the polymerization reaction to be substantially completed.

Here, the polymer type polymerization initiator used for obtaining the graft copolymer according to the present invention contains a large amount of peroxide which is a radical generating group, and the decomposition temperature of the peroxide is relatively high. There is
When graft polymerization of 2-hydroxyethyl methacrylate or a monomer mixture containing 2-hydroxyethyl methacrylate as a main component, the decomposition rate of peroxide is low, so even if those monomers complete polymerization, peroxide is still present. Therefore, the stability of the obtained graft copolymer is remarkably deteriorated. That is, the peroxide remaining in the graft copolymer is gradually decomposed even at room temperature to generate a radical, and the radical acts on, for example, a 2-hydroxyethyl group in the graft copolymer to cause grafting. This causes a phenomenon that the copolymer is crosslinked. Therefore, in order to avoid such a problem, it is preferable to use a tertiary amine or the like having a property of increasing the decomposition rate of peroxide.

Examples of such tertiary amines include triethylamine, N, N-dimethylaniline, dimethylbenzylamine and the like.
It is preferably used in a range of equimolar amount to twice the molar amount of the peroxide contained in the polymer type polymerization initiator used. That is, if the amount used is less than the molar equivalent to the peroxide, the peroxide may remain, while if it is more than twice the molar amount of the peroxide, the polymer solution after the polymerization is severely colored. It becomes. As described above, by using a tertiary amine together during the graft polymerization, the grafting efficiency can be further increased, and the peroxide can be completely decomposed, so that a stable graft copolymer can be obtained. It is.

As described above, after the polymerization reaction is carried out under predetermined conditions by combining the polymer type polymerization initiator and the monomer, the obtained polymerization product is diluted with methanol,
Pour into a poor solvent such as acetone or diethyl ether to precipitate the polymer. Then, the precipitate is collected by filtration and dried under reduced pressure, whereby the intended graft copolymer-containing substance can be obtained.

By the way, when the graft copolymer of the present invention is produced, a linear polymer that is not grafted with free radicals can be produced as a by-product. By doing so, the desired graft copolymer can be obtained.

In the contact lens solution according to the present invention, since the hydrophobic contact lens can be made sufficiently hydrophilic without performing the above-mentioned fractional purification of the graft copolymer, the graft polymerization is carried out. Subsequent formed polymer (hereinafter, referred to as graft copolymer-containing material)
Can be used as it is.

The number average molecular weight of the thus obtained graft copolymer-containing material is preferably in the range of about 1,000 to about 10,000,000, and more preferably in the range of about 2,000 to 100,000. That is, when the number average molecular weight is less than about 1000, the solubility of the graft copolymer-containing material in water tends to increase, and thus the contact lens prepared using the graft copolymer-containing material When using a solution for the graft copolymer content,
Even if it is adsorbed, it is easily detached from the lens by rinsing with tap water, and a sufficient hydrophilicity-imparting effect cannot be obtained.
If the molecular weight is larger than 10,000, the solubility of the graft copolymer-containing material in the solvent becomes poor.

On the other hand, as the solvent to be used in the contact lens solution according to the present invention, a solvent that does not change the specifications (base curve, power, size, etc.) of the contact lens is selected. Generally, water is mainly used as a solvent for the contact lens solution, and the specifications of the contact lens are kept good.In the present invention, however, the graft copolymer-containing material is water. Because they are insoluble, solvents other than water are required. Therefore, the solvent that can be used in the present invention does not change the specifications of the contact lens,
Further, it can dissolve the graft copolymer-containing material.

In the present invention, such a solvent is represented by the following formula 12: HO— (CH ₂ CH ₂ O) _n —R ₃ (wherein R ₃ is hydrogen or a methyl group, n is an integer of 1 to 20), and a solvent composed of 20 to 100% by weight of ethylene glycol compound and 80 to 0% by weight of water is preferably used.

In the above formula (12), when n = 0, water or methanol is used. However, water cannot dissolve the graft copolymer-containing material, and methanol changes the contact lens specification. On the other hand, if n is larger than 20, the molecular weight of the compound increases, and the viscosity of the solution increases, which makes it difficult to handle.

Then, the contact lens solution according to the present invention is mainly prepared from the solvent and the graft copolymer-containing material. The higher the concentration of the polymer in the dissolved solution in the solvent),
When rinsing with water, the polymer precipitates quickly and causes a problem that polymer particles are deposited on the contact lens surface. On the other hand, when the concentration is less than 0.01% by weight, the polymer has a contact lens surface. The concentration is desirably 0.01 to 1.5% by weight, and more preferably 0.1 to 1% by weight, since the amount of adsorption to water decreases and the effect of hydrophilicity becomes poor. 0.0% by weight.

The contact lens solution according to the present invention prepared as described above may be added with a surfactant, a viscous base, an isotonic agent, a preservative, etc., if necessary. No problem. By combining these components,
In addition to the function as a hydrophilizing agent, a function as a cleaning agent, a preservative, a cleaning preservative, or the like can be provided.

The method of using the contact lens solution according to the present invention prepared as described above includes immersing the contact lens in the contact lens solution, or spraying or applying the solution to the contact lens surface. After that, it is sufficient to sufficiently rinse with tap water, and by such a simple operation, the hydrophilic grafter copolymer containing 2-hydroxyethyl methacrylate contained in the solution as a main component is applied to the contact lens surface. By being adsorbed, good hydrophilicity can be imparted to the contact lens.

Further, since the hydrophilic graft copolymer is insoluble in water, it is strongly adsorbed to the contact lens surface. Adsorbed on
Hydrophilicity can be imparted. Therefore, it is possible to effectively prevent lipid stains from adhering to the surface of the contact lens, control the phenomenon of clouding of the contact lens, and enable long-time wearing.

[0076]

EXAMPLES Hereinafter, some examples of the present invention will be described to clarify the present invention more specifically. However, the present invention imposes some restrictions by the description of such examples. It goes without saying that you don't receive anything. In addition, the present invention, in addition to the following examples, in addition to the above specific description, various modifications based on the knowledge of those skilled in the art, unless departing from the spirit of the present invention,
It should be understood that modifications, improvements and the like can be made.

First, in the following Production Examples 1 to 5, the polymer type polymerization initiators used for synthesizing the graft copolymer according to the present invention were all prepared by a solution polymerization method.

Production Example 1 N-vinyl-2-pyrrolidone (hereinafter abbreviated as NVP): 0.31 g (0.0028 mol), t-butylperoxy-lauryl fumarate (hereinafter abbreviated as LF-PO) : 1.00 g (0.0028 mol), 2, 2'-
Azobis (2,4-dimethylvaleronitrile (hereinafter referred to as V-
65): 0.002 g (8.05 × 10 ⁻⁶ mol) and 2 cc of tetrahydrofuran (hereinafter abbreviated as THF) were placed in a 50 ml glass ampule, and the ampoule was purged with nitrogen gas. After that, the tube was sealed and polymerized at 40 ° C. for 18 hours. After the completion of the polymerization, the polymer solution was diluted with 30 cc of diethyl ether and transferred to a separating funnel. Then, 3 times with distilled water
After washing twice, the ether layer was separated, dried over anhydrous magnesium sulfate, and filtered, and the ether was distilled off under reduced pressure. The obtained residue was a very viscous polymer, and the yield was 1.23 g and the yield was 93.9%. Its Fourier transform infrared absorption spectrum (IR)
Is shown in FIG.

As is apparent from the results of the IR spectrum, the absorption peak (1629) derived from the vinyl group of NVP was obtained.
cm ^-1) and LF-PO absorption peak derived from vinyl group (1643cm ^-1) has disappeared, the progress of the polymerization are shown. The characteristic absorption band in the IR spectrum is
= N = O (ν = 1690-1700 cm ⁻¹ ) in NVP,
= C = O of lauryl ester in LF-PO (v = 17
25-1735 cm ^-1 ), = C = O of t-butyl peroxyester in LF-PO (v = 1770-1780 cm)
^-1 ). Therefore, it was confirmed that the obtained polymer was the intended polymer type polymerization initiator.

Production Example 2 NVP: 0.73 g (0.0066 mol), t-butylperoxy-ethyl fumarate (hereinafter abbreviated as EF-PO): 0.85 g (0.0039 mol), bis (octa) (Fluoropentyl) fumarate (hereinafter abbreviated as DF ₈ F): 1.43 g (0.0026 mol), V-6
5: 0.33 g (1.33 × 10 ⁻⁴ mol) and THF:
1.82 g was placed in a 50 ml glass ampoule, the inside of the ampoule was replaced with nitrogen gas, and the tube was sealed.
Polymerization was performed at 18 ° C. for 18 hours. After the end of such polymerization,
The obtained polymerization product, i.e., a polymer solution was poured into a large amount of n-hexane to precipitate the polymer, and the obtained polymer was separated by filtration and dried to obtain a desired polymer type polymerization initiator. Was. The yield was 2.64 g, and the yield was 87.7%. Fourier transform IR of this polymer
The spectrum is shown in FIG.

The characteristic absorption band in the IR spectrum is as follows: = N = O (ν = 1690-1700 c
m ^-1 ), = C = O (ν) of ethyl ester in EF-PO
= 1730-1740 cm ⁻¹ ), ＣC ＝ O of t-butyl peroxyester in EF-PO and ＣC ＝ O of octafluoropentyl ester in DF ₈ F (ν = 176)
5 to 1780 cm ⁻¹ ) and —CF ₂ — (ν = 1140 to 1200 cm ⁻¹ ) in the octafluoropentyl group.

Production Examples 3 to 5 Production Examples 2 to 5 were prepared using the monomer mixtures shown in Table 1 below.
After polymerization in the same manner as described above, treatment and purification were performed to obtain a polymer type polymerization initiator. The IR spectrum of each of the obtained polymerization initiators was measured. As a result, it was confirmed that the used monomers were introduced into the polymer.

[0083]

[Table 1]

Examples 1-4 Synthesis of Graft Copolymer Synthesized Using Polymeric Polymerization Initiator and Evaluation of Its Performance Polymeric polymerization initiator (hereinafter referred to as NF) obtained in Production Example 1
-PO <L>), the polymer type polymerization initiator obtained in Production Example 2 (hereinafter abbreviated as NF ₈ F-PO <E> 523), and the polymer type polymerization initiator obtained in Production Example 3 (Hereinafter abbreviated as NS ₂ F-PO <E> 532) and the polymerized polymerization initiator (hereinafter referred to as SF-F) obtained in Production Example 5.
Using PO <E> 82, a graft polymerization of 2-hydroxyethyl methacrylate (hereinafter, abbreviated as 2-HEMA) was respectively performed.

That is, the composition for polymerization shown in Table 2 below was put into a 50 ml glass ampule, the inside of the ampoule was replaced with nitrogen gas, the tube was sealed, and the tube was kept at 80 ° C. for 18 hours and further at 115 ° C. Heating was carried out for 2 hours to complete the polymerization. After the completion of the polymerization, each of the polymer solutions was diluted with methanol, poured into a large amount of diethyl ether to precipitate the polymer, and the polymer was separated by filtration and dried to obtain a desired graft copolymer. The content was obtained.

[0086]

[Table 2]

The obtained polymers were dissolved in ethylene glycol at concentrations of 0.05%, 0.1%, 0.5% and 1.0%, respectively, and the surface tension was measured. The result is shown in FIG.

Comparative Examples 1-4 Synthesis of random copolymers of 2-HEMA and hydrophobic monomers and comparison of their performance The hydrophobic groups present in each of the polymer-type polymerization initiators used in Examples 1-4, ie, NF- PO <L> for lauryl group, NF ₈ F-PO <E> 523 for octafluoropentyl group, NS ₂ F-PO <E> 532 for pentamethyldisiloxanyl group, SF-PO In the case of <E> 82, focusing on the phenyl group, the polymer containing the grafted poly2-HEMA synthesized using each polymer type polymerization initiator and the similar hydrophobic group contained in each are equimolar amounts. , Prepared to contain randomly
The performance of the random copolymer of HEMA was compared.

That is, each of the polymerization compositions shown in Table 3 was placed in a 50 ml glass ampoule,
After replacing the inside of the ampoule with nitrogen gas, the tube was sealed, and poured into a large amount of diethyl ether to precipitate a polymer, which was separated by filtration and dried to obtain a desired random copolymer.

[0090]

[Table 3]

The obtained polymers were dissolved in ethylene glycol so as to have concentrations of 0.05%, 0.1%, 0.5% and 1.0%, respectively.
Surface tension was measured in the same manner as described above. The results are also shown in FIG.

As is apparent from FIG.
The polymers containing grafted poly 2-HEMA synthesized in Comparative Examples 1 to 4 are the same as the random poly 2-HEMAs containing hydrophobic groups obtained in Comparative Examples 1 to 4 in equimolar amounts. It was confirmed that it had a better surface tension lowering ability than that of

Examples 5 to 7 Polymer type polymerization initiator (hereinafter referred to as SF) obtained in Production Example 4
-PO <E> 55), SF-PO <E> 82, and NF ₈ F-PO <E> 523, for graft polymerization of 2-HEMA or a monomer mixture containing 2-HEMA as a main component. Done.

That is, using the polymerization compositions shown in Table 4 below, polymerization was carried out in the same manner as in Examples 1 to 4, respectively, to obtain the intended graft copolymer-containing material.

[0095]

[Table 4]

Examples 8 to 21 Each of the polymers obtained in Examples 1 to 7 was dissolved in each of the solvents shown in Table 5 below to prepare solutions for contact lenses.

[0097]

[Table 5]

Then, tris (trimethylsiloxy) silylpropyl methacrylate and 1,1,1,3,3,3-
A hard contact lens storage case in which a high oxygen permeable hard contact lens made of a copolymer containing hexafluoro-2-propyl methacrylate as a main component is inserted into a holder for storing a hard contact lens and filled with a solution for each contact lens. After dipping the holder together with the holder for 5 seconds, the holder was taken out and rinsed sufficiently with tap water to perform a hydrophilic treatment on the contact lens. Thereafter, water droplets on the surface of each lens were blown off by an air compressor, and the contact angle was measured by a droplet method using a goniometer-type contact angle measuring device G-1 manufactured by Elma Optical Co., Ltd. The results are shown in Table 5.

Comparative Examples 5 to 7 The same hydrophilic treatment as described above was carried out using a polyvinyl alcohol aqueous solution and a poly N-vinylpyrrolidone aqueous solution which have been conventionally used to impart a hydrophilic effect. After that, the contact angle of the lens was measured, and the results are shown in Table 5 as Comparative Examples 5 and 6. Further, Comparative Example 7
Shows the results of measuring the contact angle of a contact lens which was not subjected to any hydrophilic treatment.

As is apparent from the above results, when the predetermined hydrophilic treatment was performed using the contact lens solution according to the present invention, a remarkable decrease in the contact angle was observed in a very short time. Thereby, it was found that the surface of the hydrophobic contact lens can be easily and satisfactorily made hydrophilic.

[Brief description of the drawings]

FIG. 1 shows the Fourier transform infrared absorption spectrum (I) of the polymer type polymerization initiator used in the present invention obtained in Production Example 1.
FIG.

FIG. 2 shows the Fourier transform infrared absorption spectrum (I) of the polymer type polymerization initiator used in the present invention obtained in Production Example 2.
FIG.

FIG. 3 is a graph showing the results obtained by measuring the surface tensions of solutions obtained by dissolving the polymers obtained in Examples 1 to 4 and Comparative Examples 1 to 4 in ethylene glycol.

Continued on the front page (58) Fields surveyed (Int. Cl. ⁷ , DB name) C08F 265/04 C08F 4/34 C08F 271/02 G02C 7/04 CA (STN) REGISTRY (STN)

Claims (8)

(57) [Claims] 1. 40 to 60 mol% of N-vinyl lactam
And 2-hydroxyethyl methacrylate or 2-hydroxyethyl methacrylate using a polymer-type polymerization initiator obtained by copolymerizing at least one kind of peroxide-containing fumarate represented by the following formula 1 with 60 to 40 mol%. Copolymer obtained by polymerizing a monomer mixture containing at least 80% by weight of Embedded image (However, R ₁ is a linear alkyl group having 18 or less carbon atoms,
Branched alkyl or cyclic alkyl group, or a carbon atoms indicated from 6 to 18 aromatic radical,, R ₂ is 13 carbon atoms
The following linear alkyl groups, branched alkyl groups or cyclic alkyl groups, or phenyl groups are shown) 2. The graft copolymer according to claim 1, wherein the N-vinyl lactam is N-vinyl-2-pyrrolidone. 3. 40 to 60 mol% of N-vinyl lactam
And at least one peroxide-containing fumarate represented by the following formula (2) and an alkyl-fluoroalkyl fumarate, an alkyl-silicon-containing alkyl fumarate,
Fluoroalkyl-silicon containing alkyl fumarate,
Bis (fluoroalkyl) fumarate and at least one fumaric acid diester selected from the group consisting of bis (silicon-containing alkyl) fumarate are combined in a molar ratio of 9: 1 to 1: 9.
80% by weight of 2-hydroxyethyl methacrylate or 2-hydroxyethyl methacrylate using a polymer type polymerization initiator obtained by copolymerizing 40% by mole of
A graft copolymer obtained by polymerizing the monomer mixture containing the above. Embedded image (However, R ₁ is a linear alkyl group having 18 or less carbon atoms,
Branched alkyl or cyclic alkyl group, or a carbon atoms indicated from 6 to 18 aromatic radical,, R ₂ is 13 carbon atoms
The following linear alkyl groups, branched alkyl groups or cyclic alkyl groups, or phenyl groups are shown) 4. The graft copolymer according to claim 3, wherein the N-vinyl lactam is N-vinyl-2-pyrrolidone. 5. A polymerized polymerization initiator obtained by copolymerizing 40 to 90 mol% of styrene and at least one of 60 to 10 mol% of a peroxide-containing fumarate represented by the following chemical formula (3). , 2-hydroxyethyl methacrylate, or a graft copolymer obtained by polymerizing a monomer mixture containing 80% by weight or more of 2-hydroxyethyl methacrylate. Embedded image (However, R ₁ is a linear alkyl group having 18 or less carbon atoms,
Branched alkyl or cyclic alkyl group, or a carbon atoms indicated from 6 to 18 aromatic radical,, R ₂ is 13 carbon atoms
The following linear alkyl groups, branched alkyl groups or cyclic alkyl groups, or phenyl groups are shown) 6. At least one kind of polymer selected from the graft copolymers according to claim 1, 3 and 5,
A solution for contact lenses, which is dissolved in a solvent that dissolves the polymer. 7. The solvent for dissolving the polymer is as follows: HO— (CH ₂ CH ₂ O) _n —R ₃ (Formula 4) (where R ₃ is a hydrogen or methyl group, and n is 1 to ₃ ) The solution for contact lenses according to claim 6, which is composed of 20 to 100% by weight of an ethylene glycol compound represented by the following formula (indicating an integer of 20): and 80 to 0% by weight of water. 8. The contact lens solution according to claim 6, wherein the surface of the contact lens is wetted with the solution, and then the surface is contacted with a poor solvent for the polymer dissolved in the solution. A method for hydrophilizing a contact lens, comprising the steps of: