WO1993014153A1 - Contact lens manufacturing method - Google Patents

Abstract

In graft-polymerizing the surface of a contact lens, a suitable amount of reducing agent is added to the polymerization system so as to decompose at a low temperature the peroxide which is introduced to the surface of the contact lens base material by an electric discharge process and to produce radicals. When a fluorine-containing base material is used as the contact lens base material, the processing time can be reduced, so that a change in color of the base material is prevented during the processing. Oxygen dissolved in the polymerization system is removed by reducing the pressure in the polymerization system and applying ultrasonic waves thereto. Alternatively after adding diammonium cerium (IV) nitrate to the polymerization system, the surface graft polymerization is carried out under normal pressure.

Description

 Akira Φ

 Contact lens manufacturing method

 Technical field

 The present invention relates to a manufacturing method for maintaining the wettability of a surface permanently and obtaining a hard contact lens with an excellent wearing feeling. Background branch art

 In order to reduce the foreign body sensation when wearing a contact lens and improve the wearing sensation, it is important to improve the familiarity between the cornea and the lens. Optimization of the design surface, such as the size and shape of the lens, is also an important factor. In addition to the force, the chemical cornea (living tissue) on the contact lens surface and Affinity is indispensable for obtaining a contact lens with excellent wearability. A typical example of a surface treatment method intended to permanently add corneal affinity to the contact lens surface is to use an acrylic surface on the lens surface. By graft polymerizing hydrophilic monomers such as silica, it is possible to improve functions such as wettability (including water retention) and slidability of the lens surface. Furthermore, in order to maintain the wettability over a long period of time, a method of improving the abrasion resistance of the graphite chain by cross-linking with Ν′-methyl benzene acrylamide or the like has been proposed. is there.

There are two major points in performing the surface graph reaction efficiently. Firstly, a radical is formed on the surface of the target substrate to serve as a polymerization initiation point. Secondly, a polymerization inhibitor which inhibits the graphitization reaction is exposed to the environment (solution ) (This causes the growth of the graphite chain from the polymerization start point). The first point and the second point do not have optimal conditions independently of each other, but do not find the optimal conditions in the combination of both. I have to do it. Furthermore, surface graph polymerization reaction conditions vary depending on the target substrate, and this point must be taken into account. So far, each of the two points mentioned has its own means. What is the difference between these two points when the hydrophilic monomer is graphed on the surface of the contact lens substrate under a certain force? Briefly describe what has been done with technology.

 First, the method of producing radicals on the surface of the contact lens substrate, which is the first point, is the first step in order to produce radicals. It is necessary to introduce peroxide into the lens surface by discharge treatment or the like. Radicals are first formed on the surface of the substrate by chemically decomposing them.However, conventionally, decomposition of peroxide requires 60 ° C to 9 ° C. Thermal decomposition was performed at a high temperature of 0 ° C. Next, the second point, removal of the polymerization inhibition factor, is described. In general, the most important of the polymerization inhibiting factors in a solution system is the dissolved oxygen present in the solution. Therefore, if the dissolved oxygen is removed by any method, the intended graphene polymerization reaction can be started. Conventionally, as a method of sufficiently removing dissolved oxygen, a vessel containing a monomer solution is evacuated, and then struck from the outside, and then the inside of the vessel is filled with an inert gas such as nitrogen. And then re-evacuated—it was done by repeating the series of steps several times.

 However, the above-described prior art has the following serious drawbacks.

 The first point is the decomposition of peroxide (radical formation) on the lens substrate surface by heating, which is 60 as described above in the prior art. C-90. C was needed. However, since the degradation point of the lens base forest, which is mainly made of acrylic resin, is exactly the same as this temperature range, the lens base material It had the drawback that the shape was greatly changed and the optical characteristics were inferior (change in lens power, change in transmittance in the visible region, etc.).

On the other hand, the second point, the method of removing dissolved oxygen (polymerization inhibition factor) necessary to cause the growth reaction of the graphite chain from the polymerization initiation point, is described. , The aforementioned prior art, i.e. with solution After evacuating the container and hitting it from the outside, the inside of the container is replaced with an inert gas such as nitrogen, and the process of evacuating again is repeated several times. With such a method, the process is too complicated for mass production. In addition, because process control is difficult, the dissolved oxygen in the solution cannot be removed uniformly, and slight unevenness in the amount of residual oxygen may cause fluctuations in the graphitization polymerization conditions and the state of the graphitic surface. It had the disadvantage of causing non-uniformity and, consequently, variation in contact lens wearing sensation.

 Furthermore, as pointed out earlier, the method of connecting these two points under optimal conditions has been considered up to now, including the target base material. There is no such example.

 The object of the present invention is to solve the various problems described above. In other words, for radical formation (first point), peroxide decomposition reaction is possible at a temperature sufficiently lower than the softening point of the contact lens base material. The purpose is to provide a method for manufacturing contact lenses. Regarding the removal of dissolved oxygen (second point), a method that simplifies the operation of removing dissolved oxygen during surface-graft polymerization, facilitates process control, and has excellent mass productivity. Alternatively, it is possible to provide a method for producing a contact lens that enables high-yield surface-graft polymerization treatment in a simple and mass-production manner without requiring this operation. aimed to. Another object of the present invention is to take into account the process consistency between the first and second points, including the target substrate, and to connect them under optimal conditions. To provide a manufacturing method. Disclosure of the invention

The process for producing a contact lens according to the present invention is directed to a contact lens using a polymer of an ester compound of acrylic acid or methacrylic acid as a main raw material. A lens substrate or a copolymer of an ester compound of acrylic acid or methyl acrylate and an ester compound of fumaric acid A contact lens substrate made mainly of polymer is used as a base material. (A) (B) immersing the substrate in a hydrophilic monomer solution, (c) immersing the substrate in a hydrophilic monomer solution, and (c) adding a reducing substance. d) a step of subjecting a hydrophilic monomer to graphitic polymerization under normal pressure or decompression pressure on the surface of the base material. Further, the method for producing a contact lens according to the present invention is characterized in that the reducing substance is ammonium diammonium nitrate (W) or the reducing substance is ammonium ferrous sulfate. (Mole salt). Further, the method for producing a contact lens according to the present invention is characterized in that the initiation of the graph polymerization is caused by heating. Further, in the method for producing a contact lens of the present invention, the hydrophilic monomer may be acrylamide or N, N'-methylbenzenebisacrylamide. And. Further, the method for producing a contact lens of the present invention comprises a siloxane or a siloxane substituted ester of methacrylic acid represented by the following general formula:

X X O R

I I II I

R ¹ [Si— 0] «Si (CHa) nO-CC = CH ₂

 I i

 Y Y

However, R = CH ₃ or is H;

 X = C i-C s alkyl, cyclohexyl, phenyl or Z Y = C 1-C s alkyl, cyclohexyl, phenyl or Z

Z = R ² [Si-0] Ρ

R ³ R ¹ = C 1 C 6

R ² = CT c 6

R ³ = C.

R ⁴ = C, e 6, hex, or hex m or m = 1-3

 n = 1 to 5

 P = 1 to 3

), A fluoroalkyl substituted product of acrylic acid or methacrylic acid having not more than 20 fluorine atoms represented by the following general formula (

A O R

I II I

Rr— C -0— C-C = CH ₂

 H

However, R = CH ₃ or is H;

 A = H, cyclohexyl, phenyl or Rr;

 R r = Polyfluoroalkyl group or Penfluoroalkyl group

), A poly (fluoroalkyl) siloxy substituted ester of acrylic acid or methacrylic acid represented by the following general formula (

C (CH ₃ ) m OR

 I I II I

[Rr-CHa-CHa-Si-O] n-Si- (CH ₂ ) i -0-CC = CH ₂

I But R = CH 3 or H;

R _f = Fluoroalkyl of Ci to Co S; m = 0, 1 or 2;

 n = 1-3;

 ), Acryl (methacryl) oxyalkyl silanol represented by the following general formula (

XOR

I II I

H [O-Si] _m (CH ₂ ) _n OCC = CH ₂

 Y

Where R = C H 3 or H;

 X, Y = alkyl of C i ~ C s; phenyl or Z

R ¹

 I

Z = R ^a [Si-O] P

 I

R ³ m = 1 to 3;

 n = 1 to 5 Ϊ

 P = 1 to 3;

R ¹ = C! To C hex or phenyl:

R ² = C 1-C cyclohexyl or phenyl;

R ³ = C 1-C cyclohexyl or phenyl;

), A polyacryl (metacryl) represented by the following general formula: XXOR

 I I II I

• 0 [Si (0-Si) _m (CH ₂ ) nO-CC = CH ₂ ]

 I I

Ύ Y but R = CH ₃ or H;

 m = 03;

 n 5;

 XC, ~ C6 alkyl, cyclohexyl, cell or ZYC l ~ Cs alkyl, cyclohexyl, file or Z

R '

Z = R ² [Si-O]

R ³

P 3;

R ¹ = Alkyl, cyclohexyl or phenyl of C1 to Cs

R ² = Alkyl, cyclohexyl or phenyl of C1 to Cs

R ³ = C1-C6 alkyl, cyclohexyl or phenyl

), A fluorine-containing siloxanyl metal create represented by the following general formula (

C ₃ F7-0 (CF-CF ₂ -0) k-CF-CN (CH ₂ ) n [Si-0] _m -Si- (CH ₂ ), -0-CC = CH ₂

 II I I I

0 H CH ₃ CH3 1 = 1 to 3;

 m = 1 to 10;

 n = 1-3;

 k-1 to 3;

 ), A fluorine-containing acrylic acid or methyl acrylate ester monomer represented by the following general formula (

0 R ¹

 . II I

Ef-0-CH2-CH-0-CC = CH ₂

R ² -C-0-CHa

 II

 0

R r = a C 1 to C 30 fluoroalkyl group which may contain an oxygen atom having at least three fluorine atoms bonded thereto;

R ¹ = CH 3 or H;

R ² = an alkyl group which may contain a hydrogen atom or an oxygen atom of C i to C ₃ B;

), A fluorine-containing acrylic acid or methacrylic acid ester monomer represented by the following general formula:

0 R '

 II I

_{^{R 2 - 0 - CH 2 -}} CH - CH 2 -0 - C- C = CHs

R r = a C 1 -C 3 B fluoroazole group which may contain an oxygen atom to which at least three fluorine atoms are bonded; hi Q— Q— or

II II 3 ¾

 1 1 i

 II

Mountain mountain o o ~ r Θ

 id 1 1 Ω

 J— J C J— J I Ma

 II? M I

Ω Ο

 〇 Ω =

 9¼ = o

 〇 〇

 9+ 1 Θ

M Q Q

 9+ Ok j

 W

 t

 1.1

 Ω

K W

it 鹏 1 1 vl

 〇 屮

〇

 ¾: »$ JDef tf: l C 7;:.

12 = ~

CHH = C = H, F or an alkyl group;

 D = F or a fluoroalkyl S of C i -C 3 e which may contain an oxygen atom bonded to at least one fluorine atom;

 n = 0, 1 or 2;

), A copolymer prepared from a copolymer of acrylic acid or an ester compound of methacrylic acid, which is a copolymer containing at least one of them. (A) a step of subjecting the surface of the substrate to discharge treatment under normal pressure or reduced pressure; and (b) a step of subjecting the substrate to acrylamide and Ν, A step of immersing in a mixed monomer-solution containing Ν'-methylenebisacrylamide as a main component, and (c) adding diammonium cerium nitrate (17) And (d) a step of subjecting the mixed monomer to a graphene polymerization under a normal pressure on the surface of the base material. It is characterized in that the amount of added lithium (IV) is 0.0 1 g or more and 1 g or less per 1 g of the mixed monomer. That. Further, the method for producing a contact lens according to the present invention comprises at least an alkylmethacrylate, an alkylmethacrylate, a fluoroalkylmethacrylate and a siloxymethacrylate. Sani Ruff Malate (

H 0

 I II

 A-0-C-C = C-C-0-A '

 II I

0 A In the formula, A and A 'are C! ~ Is A alkyl group or a C ₅ selected Ri by group et al. Or D based on ing, D is the structural formula

B X

C _k F _2fc- (CHa),-[Si-0] _m -Si- (C¾) „-BY It has a base. In the formula, X and Y are selected from the group consisting of an alkyl group and a Z group of c C s, and z is a general formula

 B

B- [Si-0] _m-

I

Ri also One Motodea the B, B denotes an A Ruki Le group of C ₁ ~ C s. k, 1, m, and n indicate 0 or a positive integer. (A) a copolymer lens base material made from a polymer of ester compound of methacrylic acid and fumaric acid, which is a copolymer with (B) a step of subjecting the surface of the base material to discharge treatment under normal pressure or reduced pressure; and A step of immersing the mixture in a mixed monomer solution containing ^luamide as a main component; (c) a step of adding diammonium nitrate (17); and (d) the base material. A process for producing a contact lens, comprising a step of subjecting the mixed monomer to graphitic polymerization under normal pressure on the surface, wherein diammonium nitrate (IV) is added. It is characterized in that the amount is greater than or equal to 0.1 lg and less than or equal to 1 lg per 1 g of the mixed monomer. The method for producing a contact lens of the present invention is a siloxane-substituted ester of acrylic acid or methacrylic acid represented by the following general formula. Le (

X X O R

I I II I

R ⁴ [Si-0] _m Si (CHe) nO-CC = CH ₂

 Y Y

However, R = C Η 3 or Η;

X = Ci to C6 alkyl, cyclohexyl, phenyl or Z; Y = C1 to C6 alkyl, cyclohexyl, phenyl Le or Z; R '

ZHI = R ² [S i -O] P-R ³

R ¹ = alkyl, cyclohexyl or phenyl of C i to C s

R ² = Ci to C6 alkyl, cyclohexyl or phenyl

R ³ = Alkyl, cyclohexyl or phenyl of Ci to Cs

R ⁴ = alkyl of C t to C s, cyclohexyl or phenyl m = 1 to 3;

 11 = 1 to o;

 P = 1 to 3;

), A fluoroalkyl substituted product of acrylic acid or methacrylic acid having not more than 20 fluorine atoms represented by the following general formula (

However, R = C H 3 or H;

A = H, cyclohexyl, phenyl or R _r ;

 R r = Polyfluoroalkyl group or Bentafluorophenyl group

), A poly (fluoroalkyl) siloxy substituted ester of acrylic acid or methacrylic acid represented by the following general formula (

CH ₃ but R = CH ₃ or H;

 R (= fluoroalkyl group of Ci to Cd;

 1 =:! To 4;

 m = 0, 1 or 2;

 n = 1 to 3;

), An acryl (metaacryl) oxyalkylsilane represented by the following general formula (

XOR

I II I

H [0-Si] _m (CH ₂ ) nO-CC = CH ₂

 Ύ

However, R = C Η 3 or Η;

 X, Υ = alkyl of C i-C s; phenyl or Z

R ¹

Z = R ² [Si— 0] P

 I

R ³ m = 1 ~ ^3;

 n = 1 to o;

P = 1 to 3; R ¹ = Al to C i to C 6, cyclohexyl or phenyl

R ² = Alkyl, cyclohexyl or phenyl of C1 to Cs

R ³ = Alkyl, cyclohexyl or phenyl of C 1 to C s

), Polyacrylic (methacrylic) represented by the following general formula:

X X 0 R

 I I II I

— 0 [Si (0-Si) _ra (CH ₂ ) nO-CC = CH ₂ ] z

 Υ Υ

Where R = C H 3 or H;

 m = 03;

 n. 5;

 X Ci to C6 Alkyl, Cyclohexyl, Fel or Z Y Ci to Cs Alkyl, Cyclohexyl, Fel or Z

Z = R ² [Si-O]

R ³

P = 3;

A Le key Le of R ¹ = C 1~ C 6, shea click b to key sheet le or the full e d ^{le: R 2 = C 1 ~ C} s of A Ruki Le, key sheet Le or the sheet click b Or fenir

R ³ = Alkyl, cyclohexyl or phenyl of C1 to Cs ), A fluorine-containing siloxanyl methacrylate represented by the following general formula (

CF ₃ CF ₃ CH ₃ CH ₃ 0 CH3

 I I I I II I

C3F7-0 (CF-CF ₂ -0) K-CF-CN (CH ₂ ) n [Si-0] m-Si- (CH ₂ ), -0-CC = CH ₂

 II I I I

0 H CH ₃ CH3

1 = :! ~ 3;

 m = 1 to 10;

 n = 1-3;

 k = 1 to 3;

), A fluorine-containing acrylic acid or methacrylic acid ester monomer represented by the following general formula (

0 R ¹

 II I

Rr-0-CH ₂ -CH-0-CC = CH ₂

R ² -C-0-CH ₂

 II

 o

R f = a C 1 -C 3 B fluoroalkyl group which may contain an oxygen atom having at least three fluorine atoms bonded thereto;

R ¹ = CH 3 or H;

R ² = an alkyl group which may contain a fluorine atom or an oxygen atom of C i to C _3B ;

), A fluorine-containing acrylic acid or methyl acrylate ester-based monomer represented by the following general formula: 〇 R '

R ² -0-CH ₂ -CH-CH ₂ -0-CC = CH ₂

 Rr-C-0

 II

 o

R _f = a C 1 -C 3 B fluoroalkyl group which may contain an oxygen atom having at least three fluorine atoms bonded thereto;

R ¹ = CH 3 or H;

 An alkyl group of R S C! ^ C so which may contain a fluorine atom or an oxygen atom;

), A fluorine-containing crylate or dimethacrylate-like monomer represented by the following kill formula (

CFs 0 OR ¹

 I II II I

(CF ₂ -0-CF) «CO (CHa-CHa-O). C_C = CH ₂

(CF ₂ ), CFs 0 OR ²

 I I II II 1

(CFa-O-CF) nCO (CH 2 -CH 2 -0). C-I C = CH2

RR ² = CH 3 or H;

 1 = 2-4;

 P, q = 1 or 2;

m and n are each an integer whose sum is in the range of 1 to 20:) and a fluorine-containing cyclic olefin represented by the following general formula (

A = H, F or alkyl group

 B = H, F or alkyl group

 C = H, F or alkyl group

 D = F or a C 1 to C 30 fluoroalkyl group which may contain an oxygen atom bonded to at least one fluorine atom; n 0, or Is 2;

), A polymer containing at least one of acrylic acid or an ester compound of methacrylic acid, which is a copolymer containing at least one of these, is used as a raw material. (A) a step of subjecting the surface of the metal substrate to a discharge treatment under normal pressure or reduced pressure, and (b) an acrylic resin substrate for the contact lens substrate. Immersion in a mixed monomer solution containing Nd and N, N'-methylene bisacrylamide as main components; and (c) ammonium ferrous sulfate ( (D) a step of subjecting the mixed monomer to a graphene polymerization under reduced pressure on the surface of the base material. Addition of ammonium ferrous sulfate (mole salt) is more than 0.02 g and less than 0.6 g per 1 g of mixed monomer. It characterized the door. In addition, the production method of contact lenses of the present invention is to use at least an alkyl acrylate and an alkyl malate. Malate and siroxaelf malate ( H 0

 I II

 A-0-C-C = C-C-0-A '

 li I

 A and A 'in the formula are selected from the group consisting of an alkyl group or a D group of CtCs, and D is a structural formula

B X

_{C k F 2 -. (CHa} ) -. [Si-0] n -Si- (C¾) "-. Ru group Der having BY formula wherein X Contact and Υ is C, ~ C 5 of A Ruki Le group And Z are selected from the group consisting of

B

A group having B- [Si-0] -B, where B represents an alkyl group of Ct to C5, and k, 1, m, and n represent 0 or a positive integer.) A contact lens substrate made from a polymer of an ester compound of methacrylic acid and fumaric acid, which is a copolymer of (a) the surface of the substrate; (B) discharging said base material with acrylamide and Ν, Ν'-methylbisacrylamide as main components. (C) adding ammonium ferrous sulfate (mole salt); and (d) adding the mixed monomer solution to the substrate surface under reduced pressure. In the method for producing contact lenses, which comprises a step of graph-polymerizing a mer, the addition of ammonium ferrous sulfate (male salt) is carried out in a mixed monomer. g It is characterized by being not less than 0.02 g and not more than 0.06 g You. Further, the method for producing a contact lens of the present invention includes a siloxane-substituted acrylate or methacrylate represented by the following general formula. STELL (

X X O R I I II I

R '[Si-0] _m Si (CH ₂ ) nO-CC = CH ₂

 I I

Y Y

However, R = CH ₃ or H;

 X = C i to C 6 alkyl, cyclohexyl, phenyl or Z; Y = C, to C 6 alkyl, cyclohexyl, Phenyl or Z;

Z = R ² [Si-0]

R ³

R ¹ C1 to C6 alkyl, cyclohexyl or phenyl

R ² C1-C6 alkyl, cyclohexyl or phenyl

R ³ C 1 A Le key Le of ~ C 6, shea the key sheet was le or to click B full et D Le

R ⁴ C 1 -C 6 alkyl, cyclohexyl or phenyl m = 1-3;

 η = 1 to O J

 P = 1 to 3;

), The fluoroalkyl of acrylic acid or methacrylic acid having not more than 20 fluorine atoms represented by the following general formula: Substitution ( AOR

 i II I

Rr-C-0-CC = CH ₂

 H

Where R = C H 3 or H;

 A = H, cyclohexyl, phenyl or Rf;

 R r = Polyfluoroalkyl group or pen fluorophenyl group

), A poly (fluoroalkyl) siloxy substituted ester of acrylic acid or methacrylic acid represented by the following general formula (

 CHs but R = C H 3 or H;

 R f = Ci to C <i, a fluoroalkyl group;

 1 = 1 to 4;

 m = 0 1 or 2;

 n = 1 to 3;

), Acryl (metaacryl) represented by the following general formula:

X O R I II I

H [0-Si] ₀ (CHs) nO-CC = CH ₂

Y However, R = CH ₃ or H;

 X, Y = C! ~ C s alkyl; phenyl or Z

R '

 I

R ² [Si-0]

 I

R ³

m = 1-3;

 n = 1 to 5;

 P = 1-3;

R ¹ = Al to C i to C 6

R ² = ci to CS Alkyl, through mouth hexil or f

R ³ = c1 to C6 alkyl, hexahedral or x

), Polyacrylic acid (methacrylic acid) represented by the following general formula:

X X O R I I II I

One 0 [Si (0-Si) _m (CH ₂ ) nO-CC = CH ₂ ]

 I I

 γ Y

However, R = CH ₃ or H;

 m = 03;

 n 5;

XC1 to C6 alkyl, cyclohexyl, and ま YC1 to C6 alkyl, cyclohexyl, and C Is Ζ R '

Z = R ² [Si-0]

R ³

p = 1-3;

R ¹ = Alkyl, cyclohexyl or phenyl of C i to C s

R ² = C i -C 6 alkyl, cyclohexyl or phenyl

R ³ = Alkyl, cyclohexyl or phenyl of C i to C s

), A fluorine-containing siloxanyl methacrylate represented by the following general formula (

CF ₃ CF ₃ CH ₃ CHs 0 CH3

C3F7-0 (CF-CF ₂ -0) _k -CF-CN (CHa) n [Si-0] «-Si- (CH2) .- 0-CC = CH2

 II I I I

 0 H CHs CH3

3;

 m = 1 0 (

 n = 3;

 k = 3;

), A fluorine-containing acrylic acid or methacrylic acid ester monomer represented by the following general formula (

0 R ¹

 II I

Rr-0-CH ₂ -CH-0-CC = CH ₂

R ² -C-0-CH ₂

 II

o R r = a C-Ca fluoroalkyl group which may contain an acid-line atom to which at least three fluorine atoms are attached;

R ¹ = CH or H;

_{^{R 2 = C, ~ C 3}} a of full Tsu is hydrogen atom or it may also contain an oxygen atom Rere A Ruki Le group;

), A fluorine-containing acrylic acid or methacrylic acid ester monomer represented by the following general formula:

0 R ¹

 II I

_{^{R 2 - 0 - CH 2 -}} CH - CH2-0 - C one C = CH ₂

 Rr-C-0

 II

O

R f = a C 1 -C 3 B fluoroalkyl group which may contain an oxygen atom having at least three fluorine atoms bonded thereto;

R ¹ = CH ₃ or H;

R ² = C, an alkyl group which may contain a fluorine atom or an oxygen atom of ~ C _{3 B} ;

), A fluorine-containing crylacrylate or dimethacrylate-related monomer represented by the following general formula (

CH ₂

CH ₂ HR ² = CH or H;

 1 = 2-4;

 p, q = 1 or 2;

 m and n are each an integer whose sum is in the range of 20;

) And a fluorine-containing cyclic olefin represented by the following general formula (

A = H, F or alkyl group:

 B = H.F or alkyl group

 C = H. F or alkyl group:

 D = F or a fluoroalkyl group of C which may contain an oxygen atom to which at least one fluorine atom is bonded;

II = 0, or 2;

), A polymer of an ester compound of acrylic acid or methacrylic acid, which is a copolymer containing at least one of these, is used as a raw material. (A) discharging the surface of the contact lens substrate under normal pressure or reduced pressure, and (b) grafting a hydrophilic monomer onto the lens surface. A method for producing a contact lens, comprising a step of polymerizing, wherein ultrasonic waves are applied to the hydrophilic monomer solution in the step (b) under vacuum. . In addition, the contact lens of the present invention The manufacturing method of the present invention is characterized in that the output of the ultrasonic wave is 10 watts or more and the application time is 10 seconds or more and 10 minutes or less.

The effects described above of the present invention ⁵ and the following effects can be obtained by these methods of the present invention.

 The addition of a reducing agent (such as Mohr's salt or cerium salt) to the polymerization system should lower the reaction temperature due to its catalysis and reduce the thermal load on the substrate. Can be done. However, in the method of the present invention in which a reducing agent is added, particularly in a system using a mol salt, the concentration of the components in the system is lower than in a conventional polymerization reaction by heating. Highly accurate control of the homogeneity (including the concentration of the reducing agent) and the amount of dissolved oxygen is required. That is, if these arrangements are not properly balanced, the length of the graphite chain becomes excessively long, causing the viscosity of the solution in the system to increase (gelling) or conversely to polymerize. The reaction may not take place. In the former case, this corresponds to the case where the amount of dissolved oxygen in the system is extremely low or the monomer concentration is higher than the optimal condition.However, the graphite layer on the substrate surface becomes cloudy, This causes a decrease in the transmittance of the visible region. The latter case (corresponding to the case where the amount of dissolved oxygen is high) means, of course, that the surface cannot be modified. As shown in the present invention, when a method of maintaining a vacuum in the system while applying ultrasonic waves when removing dissolved oxygen is employed, the following effects are obtained, and the concentration of the components in the system is reduced. This makes it possible to control the homogeneity (including the degree of reduction of the reducing agent) with high accuracy regarding the amount of dissolved oxygen.

When ultrasonic waves are applied to the polymerization system, the wave energy is first converted into the vibration energy of the molecules in the system. Via this oscillating energy, the applied energy is converted to thermal energy, resulting in a local temperature rise. At this time, the boiling point is uniquely determined by the degree of vacuum (pressure) in the system. However, if the temperature at a local area indicates the boiling point, deoxygenation due to boiling will occur. You. Since the probability that deoxygenation locally occurs is proportional to the amount of dissolved oxygen at that moment, the dissolved oxygen decreases exponentially and nonlinearly with the ultrasonic application time. When the exponent is The constant is a force determined by the size of the system, the output of the ultrasonic application device, etc., and this value is experimentally determined from the time change of the dissolved oxygen storage. On the other hand, the concentration of the components in the system increases almost in proportion to time while the vacuum is maintained. This is because the solvent evaporates at an almost constant rate. This compression rate is determined by the size of the system, the capacity of the exhaust pump used in the vacuum system, and the like.

 By the above actions, the amount of dissolved oxygen and the concentration of components in the system can be controlled with high accuracy by only time management by optimizing the equipment parameters.

 It should be noted that removal of dissolved oxygen by application of ultrasonic waves has an advantage that, even if it is applied to a conventional graphite polymerization process by heating, it can be avoided from the complexity of the operation. Further, in the present invention, cerium salt is also used as a reducing agent. However, cerium salt has a function of accelerating the graphitization reaction even in the presence of dissolved oxygen, which is very simple. The goal can be achieved in a simple process.

 Explaining the properties of the contact lens base material, the fumarate-based base material and the fluorine-containing base material used in the present invention are made of metal acrylate (silicone). Base material） Siloxanyl methacrylate (non-fluorine) base material has higher peroxygen generation efficiency by discharge treatment than base material Since it is high, a high-density polymerization initiation point can be introduced. In particular, a fluorine-containing base material has the highest peroxide generation efficiency. The higher the density of the polymerization starting point, the shorter the reaction time required for the surface-graft polymerization treatment. Therefore, the fumarate-based base material and the fluorine-containing base material used in the present invention are not used. Have the following advantages.

In the present invention, it was possible to lower the polymerization reaction temperature by adding a reducing agent. However, when this reducing thorn is oxidized during the polymerization reaction, a discoloration reaction occurs (for example, Mohr's salt). In this case, the color changes from transparent to yellow), and if the polymerization reaction takes a long time, the original contact lens substrate also changes color. However, in the fumarate-based substrate and the fluorine-containing substrate used in the present invention, the polymerization reaction time was short for the reasons described above. As a result, there is almost no discoloration of the g material. The fluorine-containing base material having the shortest reaction time has the advantage that there is no discoloration due to surface graph polymerization. BEST MODE FOR CARRYING OUT THE INVENTION

 In order to explain the present invention in detail, this will be described in the following examples.

 (Example 1)

 Dissolve 5 g of N, N'-methylenebisacrylamide and 35 g of acrylamide, which are crosslinking agents, in distilled water to make 100 ml, A monomer aqueous solution was prepared.

 The graphitization treatment was performed as follows. y—Metacryloxypro build tris (trimethylsiloxy) silane 48 wt%, 2,2,2-trifluoroethyl meta Crylate 19 wt%, 1,3-bis (y-methacryloxypropyl) -1,1,3,3—tetraxyl (trimethylsiloxy) B) 8% by weight of disiloxane, 7% by weight of bis (trimethylsiloxy) -y-methacryloxyprovir silanol, 10% by weight of methacrylic acid %, Methyl methacrylate lwt%, ethyl glycol methacrylate 7 wt%, 2,2'-azobis (2,4-iso Petrolonitrile) (However, as a polymerization initiator) 0.25 wt% of a contact lens substrate consisting of a copolymer is used as a normal contact lens. We prepared it as a close-up type.

The lens substrate is placed in a discharge device (6 cm between electrodes, voltage between electrodes is 270 volts, frequency is 60 Hz), and the discharge is performed in an argon atmosphere of 0.04 torr. Glow discharge treatment was performed for 2 seconds. After the discharge-treated lens substrate was exposed to the air, it was placed in a test tube having a diameter of 18 mm, and 3 ml of the above-mentioned aqueous solution of the monomer was added. 0.1 g of sodium cerium (IV) was added, and the mixture was dissolved by sufficiently stirring. After sealing the upper part of the test tube with a silicon stopper, place it in a thermostat at 50 ° C. 60 minutes ίΙΠSurface graph reaction was performed. After the reaction is completed, remove the lens from the test tube and immerse it in pure water at 50 ° C for 20 hours to remove the homopolymer that adhered to the surface. did. Polyacrylamide, a hydrophilic polymer (Ν, Ν'-methyl as a cross-linking agent), is applied to the contact lens surface obtained by the above operation. (Including acrylamide) was evaluated by evaluating the water wettability of the lens surface. The contact angle of pure water was measured using a static contact angle meter (Kyowa Interface Science, CII-D type). The contact angle was 18 degrees. This value is obtained by the conventional production method, that is, the method of removing dissolved oxygen in a reaction system under a vacuum and then heating the reaction system to about 80 ° C to perform surface graphitization. The value was the same as the contact angle of the lens surface. On the other hand, for comparison, when the pure water contact angle of a lens substrate without surface graphing was measured, the contact angle was 90 degrees.

 According to the present invention, diammonium nitrate is used as a reducing agent.

(17) Tsu by the and this addition of the peroxide was introduced to the co-pointer click preparative lenses substrate surface discharge treatment to decompose at low temperatures will have a 5 0 ^e C, that Do the polymerization initiation points Radial could be generated. Furthermore, the method of the present invention to which diammonium nitrate (IV) is added allows the hydrophilicity of the contact lens surface by the graphite without removing dissolved oxygen. It became clear that the conversion process was possible.

 (Example 2)

 Dissolve 5 g of N, N'-methyl acrylamide and 35 g of acrylamide in distilled water to make 100 ml. A mar aqueous solution was prepared.

The graphitization treatment was performed as follows. y-Methacriloxiv mouth build tris (trimethylsiloxy) silane 48 wt%, 2,2,2-trifluorochloromethacrylate -19 wt%, 1,3-bis (y-methacryloxyprovir)-1,1,3,3-tetrax (trimethylsiloxy) disiloxane 8 wt%, bis (trimethylsiloxy) 1 y — methacryloxyprovir silanol 7 wt%, methacrylic acid 10 wt%, methyl methacrylate lwt%, ethylene glycol Call dimethacrylate 7 wt%, 2,2'-azobis (2,4-isobutyronitrile) (but as polymerization initiator) 0.2 10 contact lens base materials of 5 wt% copolymer were prepared in a normal contact lens type.

 A space made of spacers with a thickness of 1.5 mm was provided between the electrodes of a corona discharge treatment device with a distance of 3.5 cm between electrodes, a voltage of 15 kilovolts between electrodes, and a frequency of 60 Hz. Then, the lens substrates were placed one by one, and discharge treatment was performed. The discharge treatment was performed on each side and on both sides for 40 seconds. Next, each of the lens substrates subjected to the discharge treatment was placed one by one in a test tube having a diameter of 18 mm, and the above-mentioned monomer aqueous solution was added thereto in an amount of 3 ml each. A predetermined amount (Table 1) of ammonium serum (IV) was added, and the mixture was dissolved by sufficiently mixing. After sealing the top of the test tube with a silicon stopper, a surface graphing reaction was performed for 60 minutes in a thermostat kept at 50 ° C. At the end of the reaction, remove the lens from the test tube and transfer it to 50. By immersing in pure water of C for 20 hours, homopolymers and the like adhering to the surface were removed. Polyacrylamide (N, N'-methyl bisacrylamide as a crosslinking agent) is applied to the contact lens surface obtained by the above operation. ) Was determined using the Ninhydrin method. Polyacrylamide (including N, N'-methylenebisacrylamide as a cross-linking agent) graphitized on the surface is hydrolyzed with hydrochloric acid, and neutralized. Add hydrin. The amount of polyacrylamide (including 架橋, Ν'-methyl bisacrylamide as a cross-linking agent) is determined from the coloration at that time.

For 10 lenses (samples 1 to 10) that had been subjected to the graphitic polymerization treatment, the polymer was graphed on the lens surface by the ninhydrin reaction. Acrylamide (including Ν, IT-methyl bisacrylamide as a cross-linking agent) was placed in place, and the surface state was observed with an optical microscope. Was. Conclusion The results are shown in Table 1. From Table 1, it is found that Samples 1 and 2, that is, the amount of diammonium selenium nitrate (IV) added was higher than that of monomer (Ν, Ν'-methylene bisacrylamide). Acrylic amide) If less than 0.01 g per 1 g, polyacrylamide (Μ, Ν'-method as a cross-linking agent) (Including acrylamide) are not graphed. On the other hand, the addition amount of diammonium nitrate (IV) is monomer (Ν, Ν'-methyl bisacrylamide and acrylamide). If the weight is more than 1 g (Samples 9 and 10), the lens surface may become cloudy due to excessive graphite, making it unsuitable for processing conditions. found. Samples 3 to 8, that is, the amount of diammonium cerium nitrate (17) added to the monomer (Ν, Ν'-methylene bisacrylamide and acrylamide) ) Good surface graph treatment was possible for those with a value of 0 lg or more and lg or less per lg.

table 1

* Amount per g of monomer (g) (Example 3)

 Dissolve 5 g of N, -methyl acrylamide and 35 g of acrylamide, which are crosslinking agents, in distilled water to make 100 ml. -An aqueous solution was prepared.

 Graph polymerization was carried out as follows. Contact lenses consisting of copolymers of alkyl wolframate, siloxane wolframate, fluoroalkyl acrylate and methyl methacrylate The substrate was prepared in the form of a normal contact lens.

 The lens substrate was placed in a discharge device (6 cm between electrodes, voltage between electrodes: 270 volts, frequency: 60 Hz), and glowed for 5 seconds in an argon atmosphere of 0.04 torr. One discharge treatment was performed. After the discharge-treated lens substrate was exposed to the air, it was placed in a test tube having a diameter of 18 mm, and 3 ml of the above-mentioned aqueous monomer solution was added. Then, diammonium nitrate cell was added.

0.1 g was added and the mixture was dissolved by sufficiently stirring. After sealing the upper part of the test tube with a silicon stopper, the surface graphing reaction was performed for 60 minutes in a thermostat kept at 50 ° C. After the reaction, remove the lens from the test tube and immerse it in pure water at 50 ° C for 20 hours to remove the homopolymer adhered to the surface. Was. A hydrophilic polymer, polyacrylamide (N, N'-methyl bismuth as a cross-linking agent) is applied to the surface of the contact lens obtained by the above operation. (Including acrylamide) was evaluated by evaluating the water wettability of the lens surface. As a result of measuring the contact angle of pure water using a static contact angle meter (Kyowa Interface Science, CA—!) Type, the contact angle was 18 degrees. This value is the contact value obtained by the conventional production method, that is, the method of removing dissolved oxygen in a vacuum and heating to about 80 ° C to perform surface graphitization. The value was the same as the contact angle on the lens surface. On the other hand, for comparison, when the pure water contact angle of the lens substrate without the surface graph was measured, the contact angle was 90 degrees.

According to the present invention, diammonium nitrate is used as a reducing agent. By adding (N), the peroxide introduced on the surface of the contact lens substrate by the discharge treatment is decomposed at a low temperature of 50 ° C, and the polymerization initiation point Could be generated. Furthermore, the method of the present invention to which diammonium selenium nitrate (IV) is added enables the graphene to be formed on the contact lens surface without removing dissolved oxygen. It has been clarified that hydrophilization treatment can be performed by using the method.

 (Example 4)

 Dissolve 5 g of N, N'-methylenebisacrylamide and 35 g of acrylamide, which are crosslinking agents, in distilled water to make 100 ml. A monomer aqueous solution was prepared.

 Graph polymerization was carried out as follows. Consists of copolymers of alkyl maleate, siloxane malate, fluoroalkyl maleate and methyl methacrylate 10 contact lens substrates were prepared in the usual contact lens type.

A space made of a 1.5 mm thick spacer was provided between the electrodes of a corona discharge treatment device with a distance between electrodes of 3.5 cm, a voltage of 15 electrodes, and a frequency of 60 Hz. Then, the lens substrates were placed one by one, and a discharge treatment was performed. The discharge treatment was performed on each side and on both sides for 40 seconds. Next, these lens substrates subjected to the discharge treatment are placed one by one in a test tube having a diameter of 18 mm. After adding 3 ml of each of the above-described monomer aqueous solutions, diammonium nitrate is added.ゥ Musselium (IV) was added in a predetermined amount (Table 1), and dissolved by sufficiently stirring. After sealing the top of the test tube with a silicon stopper, 50. The surface graph reaction was carried out in a thermostat kept at C for 60 minutes. After the reaction is completed, remove the lens from the test tube and immerse it in pure water at 50 ° C for 20 hours to remove the homopolymer adhered to the surface. did. Polyacrylamide (N, IT-methyl bisacrylamide as a crosslinking agent) is applied to the surface of the contact lens obtained by the above operation. ) Was determined using the Ninhydrin method. Graphite acrylamide on the surface (used as a cross-linking agent) (Including N, N'-methylene bisacrylamide) with hydrochloric acid, neutralize and add ninhydrin. The coloration at that time determines the amount of polyacrylamide (including ビ ス, Ν'-methyleneacrylamide as a cross-linking agent).

For 10 lenses (samples 1 to 10) on which the graphene polymerization treatment was performed, polyacrylic was grafted on the lens surface by a ninhydrin reaction. Luamide (including ア, Ν'-methylenebisacrylamide as a cross-linking agent) was quantified, and the surface state was observed with an optical microscope. Table 2 shows the results. From Table 2, it is found that Samples 1 and 2, that is, the amount of diammonium selenium nitrate (IV) added to the monomer (Ν, Ν'-methyl acrylamide and acrylic) If the amount is less than 0.01 g per g, polyacrylamide (Ν, Ν'-methylene as a cross-linking agent) is applied to the lens substrate surface. (Including acrylamide) is not graphed. On the other hand, the amount of diammonium cerium nitrate (IV) added to the monomer (Ν, Ιί'-methyl bisacrylamide and acrylamide) It was found that when the amount was larger than lg (samples 9 and 10), the lens surface became turbid due to excessive graphite and was unsuitable as a treatment condition. Samples 3 to 8, ie, the amount of diammonium nitrate (IV) added, the monomer (Ν, N'-methylethylene acrylamide and acrylic) Amide) 0.0 1 g or more and 1 g or less per 1 g could be treated with a good surface graph.

Table 2

* Amount per g of monomer (g) (Example 5)

 The graph polymerization was performed as follows. y — Metacryloxy Pro Build Tris (Trimethylsiloxy) Silane 48 wt%, 2,2,2—Trifluoroethyl Meta Relate 19 wt%, 1,3-bis (y-methyl oxyprobiol) -1,1,3,3—tetrax (trimethylsilicone mouth) Siloxane 8 wt%, bis (trimethylsiloxy) bisphenol 11 wt% Acid 10 wt. Chilmethacrylate 1 wt%, ethylene glycol dimethacrylate 7 wt%, 2,2'-azobis (2,4-isobutyroni) A contact lens base material consisting of 0.25 wt% copolymer (trill) (as a polymerization initiator) was prepared. Place the lens base material in the discharge device (6 cm between electrodes, voltage between electrodes 270 τίΓ, frequency 60 Hz), and place it in an argon atmosphere of 0.04 = Torr. Glow discharge treatment was performed for 2 seconds. The discharge-treated lens substrate was exposed to the air, and then placed in a test tube.

 7 g of acrylamide and 1 g of Ν, Ν'-methylene acrylamide were dissolved in 12 g of pure water to obtain a monomer aqueous solution. The aqueous ammonia solution was dispensed into a 2.5 ml test tube, and 0.0361 g of ammonium ferrous sulfate (mole salt) was added thereto, stirred, and dissolved. The discharge-treated lens was placed in the container, and after nitrogen gas replacement, the tube was sealed under reduced pressure. The test tube was placed in a thermostat at 45 for 15 minutes, and the monomer was graft-polymerized on the lens surface. In this way, six samples (sample Nos. 1 to 6) subjected to the same operation were prepared.

In addition, for comparison with the conventional method, six samples were prepared using a monomer aqueous solution without addition of ammonium ferrous sulfate (Mohr salt) (Comparative Examples 1 to 6). The polymerization temperature 8 0 ^e C when this is set to the polymerization time 1 5 minutes, discharge conditions are ferrous A Nmoni © arm sulfate (model Lumpur salt) addition of the sample (specimen N o. 1 ~ Operation similar to 6) was performed.

Measure the curvature of the lens after the graph processing and record it in advance The change ffi of the curvature and of the lens before processing was determined. In addition, the contact angle was measured by the droplet method in order to evaluate the water droplets on the lens surface. Table 3 shows these results. Table 3

Sample Curvature change Contact angle

 N o.% Θ / 2 d e g

1 0 1 3

 2 1 1 5

 3 1 1 8

 4 1 1 8

 5 1 1 6

 6 1 1 5 Comparative example

 1 6 2 1

 2 8 2 0

 3 8 1 3

 4 9 1 5

 5 5 2 1

6 8 1 5 As is clear from Table 3, the change in the curvature of the lens was 5% or more in all cases of the conventional thermal polymerization method. On the other hand, all of the samples according to the method of the present invention to which low-temperature treatment was performed by adding ammonium ferrous sulfate (mole salt) remained at 1% or less. However, when the lens surface was evaluated for the water swelling property by the contact angle, it was not inferior to the conventional thermal polymerization method. It became clear that foot processing was possible.

 (Example 6)

 y — methacryloxyprovir-1 tris (trimethylsiloxy) silane 48 wt%, 1,1-dihydrono, 1-fluorobutyl methyl acrylate 19 wt%, 1,3-bis (y-methacryloxypropyl) -1,1,3,3—tetraxyl (trimethylsiloxy) disiloxane 7 wt%, (Trimethylsiloxy) 1 y-methyl chloroxyprovir silanol 8 wt%, methacrylic acid llwt%, ethylene glycol dimethacrylate 7 wt%, 2,2'-azobis (2,4-isobutyltritol) (but as a polymerization initiator) 0.25 wt% of a contact made of a copolymer A lens substrate was prepared. Distance between electrodes 3.5 cm. Space between the electrodes of a corona discharge treatment device with a voltage between electrodes of 15 kilovolts and a frequency of 60 Hz was provided with a 1.5 mm thick spacer. (C) The lens substrate was placed here, and discharge treatment was performed. In addition, discharge treatment was performed for 40 seconds on each side and both sides.

35 g of acrylamide and 5 g of N, N'-methylbisacrylamide were dissolved in 40 g of pure water to obtain a monomer aqueous solution. In addition, 1.568 g of ferrous ammonium sulfate hexahydrate (Mohl salt) was dissolved in 10 g of pure water to obtain an aqueous Mohr salt solution. 2.4 ml of the aqueous monomer solution, 0.3 ml of Mohr's salt solution, and 0.3 ml of pure water were placed in a test tube and stirred. The discharge-treated lens was placed in it, replaced with nitrogen gas, and sealed with a decompression tube. A test tube in a constant temperature bath of 3 5 ^e C every 5-6 0 minutes, and graph door IE if the mono-mer lenses surface. Thus, exactly the same Six samples (samples N 0.1 to 6) subjected to the operation were prepared.

 In addition, for comparison with the conventional method, six samples were prepared using a monomer aqueous solution without addition of ammonium ferrous sulfate (mole salt) (Comparative Example 1). ~ 6). At this time, the polymerization temperature was set at 80 ° C, and the polymerization time was set at 20 minutes. The discharge conditions, etc., were the samples (sample Nos. 1 to 6) to which ammonium ferrous sulfate (male salt) was added. ) Was performed in exactly the same way.

The curvature of the lens after the graph processing was measured continuously, and the amount of change from the curvature of the lens before processing, which was recorded in advance, was determined. The contact angle was measured by the droplet method in order to evaluate the water wettability of the lens surface. Table 4 shows these results.

Table 4

Sample Curvature change Contact angle

N o.% Θ / 2 deg

1 0 1

2 0 1 5

3 1 1 9

4 1 1 8

5 1 1 7

6 0 1 5 Comparative example

 1 8 2 2

2 6 2 3

3 8 1 3

4 9 1 9

5 7 1 3

6 6 1 7

As is evident from Table 4, the change in the curvature of the lens was 5% or more in all cases of the conventional thermal method. On the other hand, all of the samples obtained by the method of the present invention to which low-temperature treatment was performed by adding ammonium ferrous sulfate (mole salt) remained at 1% or less. However, when the water wettability of the lens surface was evaluated by the contact angle, there was no inferiority to the conventional thermal polymerization method, and the method of the present invention was excellent. It became clear that surface graphitization was possible.

 In the examples of the present invention, acrylamide is used as a hydrophilic monomer, and N'-methylene bisacrylamide is used as a crosslinking agent. However, other hydrophilic monomers are not limited to those described above. 2 — Hydroxylmethyl It was confirmed that the same results could be obtained by using N-vinyl alcohol, polyethylene glycol, dimethyl acrylamide, etc. Was. Further, as a crosslinking agent, glyceryl acrylate, trimethylol phenolic triacrylate, such as acrylates, and ethylene glycol. Call Glyme Crate, Diet Glycol Glyme Cry Grate, Trie Grace Gly Cole Gyme Crate, 1,3-Bu Similar results were obtained using meta-create systems such as Geo-Jimme-Create. (Example 7)

Graph polymerization was carried out as follows. y — Metacryloxy Pro Build Tris (Trimethylsiloxy) Silane 48 wt%, 2,2,2-Trifluoroethyl Rate 19 wt%, 1,3-bis (y-methacryloxyprovir) -1,1,3,3—tetrax (trimethylsilicone mouth) Roxane 8 wt%, bis (trimethylsiloxy) -γ-methacryloxypropylsilanol 7 wt%, methacrylic acid 10 wt%, Chilemethacrylate 1 wt%, ethylene glycol dimethacrylate 7 wt%, 2,2'-azobis (2,4-isobutyronite A contact lens base material consisting of 0.25 wt% of a copolymer (provided as a polymerization initiator) was prepared. Discharge device (6 cm between electrodes, The lens substrate is set at the electrode and pressure of 270 volts and the frequency is 60 hertz (S), and treated in a 0.04 ton argon atmosphere for 5 seconds. Did. The discharge-treated lens substrate was exposed to the air.

 The monomer aqueous solution was adjusted as follows. First, 35 g of acrylamide and 5 g of Ν, N'-methylbenzeneacrylamide were weighed and dissolved in 40 g of water. It was decided. Further, 1.568 g (0.04 mol) of ammonium sulfate hexahydrate hexahydrate was weighed and dissolved in 10 g of water to obtain a solution B.

 2.4 ml of solution A and 0.15 ml of solution B were dispensed into test tubes, and 0.45 ml of water was added thereto to prepare a polymerization solution. At this time, the composition of the aqueous polymerization solution was about 1.05 g of acrylamide, about 0.15 g of N, N'-methylenebisacrylamide and sulfuric acid. Ferrous ammonium (mol salt) Approx. 0.025 g. In other words, the amount of Mohr salt added was 0.0 with respect to 1 wt% of the amount of monomer in the polymerization system (total of acrylamide and N, N'-methylene bisacrylamide). It is 2 wt%. The discharge-treated lens was placed in a monomer aqueous solution in a test tube, and after nitrogen gas replacement, the tube was sealed under reduced pressure. The test tube was placed in a thermostat at 35 ° C for 20 minutes, and the monomer was subjected to graph-polymerization on the lens surface. In this way, two samples (sample N 0.1, 2) were prepared under these conditions.

2.4 ml of solution A and 0.3 ml of solution B were dispensed into test tubes, and 0.3 ml of water was added thereto to prepare a polymerization solution. At this time, the composition of the polymerization aqueous solution was about 1.05 g of acrylamide, about 0.15 g of N, N'-methylene acrylamide, and about 0.15 g of water. 1.8 g and ferrous sulfate ammonium (mole salt) about 0.05 g. In other words, the addition of Mohr's salt is 0.1% based on the polymerized monomer amount (total of acrylamide and N, N * -methylene bisacrylamide). 0 4 wt%. The discharge-treated lens was placed in a monomer aqueous solution in a test tube, and after nitrogen gas replacement, the tube was closed under pressure. The test tube was placed in a thermostat at 35 ° C for 20 minutes, and the monomer was subjected to graph-polymerization on the lens surface. Thus, the book Under the conditions, two samples (sample Nos. 3, 4) were prepared.

2.4 ml of the solution A and 0.45 ml of the solution B were dispensed into test tubes, and 0.15 ml of water was added thereto to prepare a polymerization solution. At this time, the composition of the aqueous polymerization solution is about 1.05 g of acrylamide, and about 0.15 g of N, N'-methyleneacrylamide. And ferrous sulfate ammonium (mol salt) weighs about 0.075 g. That is, 1 mol% of the monomer of the polymerization system (the sum of acrylamide and N, N, -methylbisacrylamide) is equivalent to 1 mol% of the mol salt. The amount of addition is 0.06 wt%. The discharge-treated lens was placed in a monomer aqueous solution in a test tube, and after nitrogen gas replacement, the tube was sealed under reduced pressure. Place 2 0 minutes the tubes in a constant temperature bath of 3 5 ^e C, and graph preparative polymerization of mono Ma over to lenses surface. Thus, two samples (Sample Nos. 5 and 6) were prepared under these conditions.

 For comparison, in addition to the above, four graph polymerization samples were prepared using polymerization solutions in which the ratio of solution B to water was changed (Comparative Examples 1 to 4). The discharge conditions and polymerization temperature at this time were exactly the same as those for the above samples (Sample Nos. 1 to 6).

Subsequently, the opacity of the lens surface after the graphite treatment was observed with an optical microscope. In addition, in order to confirm the completion of the graph- ter polymerization treatment, the water wettability of the contact lens surface was evaluated by the contact angle by a liquid method. Table 5 shows these results.

Table 5

* With white rinse: χ, Without white ：: 〇

As is clear from Table 5, the samples N 0.1 to 6 did not have any surface white dots. The contact angle was 50 ° or less, indicating that the graphitization proceeded without hindrance.

 On the other hand, the contact angle was sufficiently reduced in the case where the mole salt was not added (Comparative Example 2), and the graphitization treatment was completed. However, surface turbidity occurs, making it unsuitable for surface treatment. In addition, those with a large amount of mol salt added (Comparative Examples 3 and 4) had a high contact angle, which indicates that the graphitization did not proceed. It should be noted that, as in Comparative Example 1, the polymerization was not progressed without any addition of the mol salt.

 In Examples of the present invention, acrylamide is used as a hydrophilic monomer, and N, N'-methylenebisacrylamide is used as a crosslinking agent. Explained by way of example, but not limited to, other hydrophilic monomers such as 2 — hydroxymethacrylate, Bolivia alcohol It was confirmed that similar results could be obtained using N-vinylviridone, polyethylene oxide, dimethylacrylamide, and the like. Further, as a crosslinking agent, glycerine acrylate, trimethylol bronitol acrylates such as triacrylate, and ethylene glycol. Chill rate Chill rate, diethyl glycol, Chill rate, Triethylen glycol, Chill rate, 1,3-butanediol Similar results were obtained using a metacrete system such as Create. (Example 8)

y —Metacryloprosiprovir tris (trimethylsiloxy) silane 48 wt%, 1,1-dihydrono, 1-fluorobutyrol Crylate 19 wt%, 1,3-bis (y-methyl chlorosiloxane)-1,1,3,3-tetrax (trimethylsiloxy) Xi) 7% by weight of disiloxane, bis (trimethylsiloxy) 1%, 8% by weight of acryloxypropyl silanol, Acid 11 wt%, ethylene glycol dimethyl acrylate 7 wt%, 2,2'-azobis (2,4-isobutyl nitrile) A contact lens substrate consisting of 0.25 wt% of a copolymer (as a polymerization initiator) was prepared. ^ Pole interrogation distance 3.5 cm, interpole voltage 15 kilopoles, frequency of 60 Hz Corona discharge treatment device 7Ε space between poles 1.5 mm thick spacer Was provided, and the lens substrate was placed thereon, and a discharge treatment was performed. In addition, discharge treatment was performed for 40 seconds on each side and both sides.

 The aqueous monomer solution was prepared as follows. First, 35 g of acrylamide and 5 g of N, N'-methyleneacrylamide were weighed and dissolved in 40 g of water. did. In addition, 1.568 g (0.04 mol) of ferrous ammonium sulfate hexahydrate was weighed out, dissolved in 10 g of water, and used as solution B.

 2.4 ml of solution A and 0.15 ml of solution B were dispensed into test tubes, and 0.45 ml of water was added thereto to prepare a polymerization solution. At this time, the composition of the polymerization aqueous solution was about 1.05 of acrylamide, about 0.15 g of N, N'-methyl acrylamide, and of ferrous sulfate. Mon (mol salt) Approx. 0.025 g. In other words, the amount of Mohr salt added is 0% per lwt% of the monomeric amount of the polymerization system (total of acrylic acid and N, N'-methylene bisacrylamide). 0 2 wt%. The discharge-treated lens was placed in a monomer aqueous solution in a test tube, and after nitrogen gas replacement, the tube was closed under pressure. The test tube was placed in a thermostat at 35 for about 10 minutes, and the monomer was subjected to graph polymerization on the lens surface. In this way, two samples (Sample Nos. 1 and 2) were prepared under these conditions.

A 2.4 ml portion of Solution A and 0.3 ml of Solution B were dispensed into a test tube, and 0.3 ml of water was added thereto to obtain a polymerization solution. At this time, the composition of the aqueous polymerization solution was about 1.05 g of acrylamide, about 0.15 g of N, N'-methylbenzeneglycramide, and water. Approximately 1.8 g and ferrous sulfate ammonium (male salt) approximately 0.05 g. That is, the polymerization system monomer (total of acrylamide and N, N'-methylene acrylamide) lwt%, Added S becomes 0.04 wt% Yes. The treated lens was placed in a monomer aqueous solution in a test tube, and after nitrogen gas replacement, the tube was sealed under reduced pressure. The test tube was placed in a thermostat at 35 ° C for about 10 minutes, and the monomer was subjected to graph-polymerization on the lens surface. In this way, two samples (samples N 0.3 and 4) were prepared under these conditions.

 2.4 ml of solution A and 0.45 ml of solution B were dispensed into test tubes, and 0.15 ml of water was added thereto to prepare a polymerization solution. At this time, the composition of the aqueous polymerization solution is about 1.05 g of acrylamide, and about 0.15 g of N, N'-methylene acrylamide. And ferrous sulfate ammonium (mol salt) Approx. 0.075 g. In other words, the amount of the monomer in the polymerization system (the sum of the acrylamide and the N, N'-methyl acrylamide) is 1 wt%, and the The amount of salt added is 0.06 wt%. The discharge-treated lens was placed in a monomer aqueous solution in a test tube, and after nitrogen gas replacement, the tube was closed under pressure. The test tube was placed in a thermostat at 35 ° C for about 10 minutes, and the monomer was graph-polymerized on the lens surface. In this way, two samples (Sample Nos. 5, 6) were prepared under these conditions.

 For comparison, in addition to the above, four graph polymerization samples were prepared using a polymerization solution in which the ratio of solution B to water was changed (Comparative Examples 1 to 4). The discharge conditions and polymerization temperature at this time were completely the same as those of the above samples (Sample Nos. 1 to 6).

Subsequently, the opacity of the lens surface after the graphite treatment was observed with an optical microscope. In addition, in order to confirm the completion of the graph- ter polymerization treatment, the water wettability of the contact lens surface was evaluated by the contact angle using a liquid method. Table 6 shows these results. Table 6

* With cloudiness: X, Without cloudiness: 〇

As is clear from Table 6, the samples N 0.1 to 6 did not have any surface white dots. The contact angle was 50 ° or less, which indicates that the graphitization proceeded without hindrance.

 On the other hand, the contact angle was sufficiently reduced in the case where the amount of added mol salt was small (Comparative Example 2), and the graphitization treatment was completed. However, surface turbidity occurs, making it unsuitable for surface treatment. In addition, those with a large amount of mol salt added (Comparative Examples 3 and 4) had a high contact angle, which indicates that the graphitization did not proceed. It should be noted that, as in Comparative Example 1, the polymerization is not progressing without any addition of mol salt!].

 In the examples of the present invention, acrylamide is used as a hydrophilic monomer, and Ιί, fT-methylene bisacrylamide is used as a crosslinking agent. However, the present invention is not limited to this example. Other hydrophilic monomers such as 2 — hydrocyanic acid acrylate, polyvinyl alcohol, etc. It was confirmed that similar results could be obtained using lysone, N-vinyl alcohol, polyethylene oxide, dimethyl acrylamide, and the like. In addition, cross-linking agents such as glycerin diacrylate, trimethylol prono, triacrylate, and other types of ethyl acetate, and ethylene glycol Cold refill, diethylene glycol Refill, trimethyl recall, dimethacrylate, 1,3-butanediol dimethyl Similar results were obtained using a meta-relate system such as tac-relate. (Example 9)

 Acrylamide was weighed in an amount of 1 Og, dissolved in distilled water to make 100 ml, and an aqueous monomer solution was prepared.

The graph polymerization was carried out as follows. y-Metacryloxy Pro Build Tris (Trimethylsiloxy) Silane 48 wt%, 2,2,2 -Trifluoroethyl Tactylate 19 wt%, 1,3-bis (y-methacryloxyprobiol)-1,1,3,3-tetrax (trimethylsilicone) Mouth mouth) disiloxane 8 wt%, bis (trimethylsiloxy) one y -Methyl cryoxylobyryl lanole 7 wt%, methacrylic acid 1 O wt%, methyl methacrylate lwt%, ethylene glycol Methacrylate 7 wt%, 2,2'-azobis (2,4-isobutyronitrile) (but as polymerization initiator) 0.25 wt% A contact lens substrate made of a polymer was prepared.

The lens substrate was placed in a discharge device (6 cm between electrodes, voltage between electrodes S: 270 volts, frequency: 60 Hz), and was placed in an argon atmosphere of 0.04 tons. Glow discharge treatment was performed for 2 seconds. After the discharge-treated lens substrate is exposed to the air, it is put into a test tube, and the above-mentioned aqueous solution of acrylamide monomer is added. Connected to vacuum system. Subsequently, the test tube was immersed in the water filled with the ultrasonic vibration tank. In this state, the inside of the tube was evacuated for 1 minute by a rotary pump, and then ultrasonic waves were applied at a predetermined output. After one minute, the test tube was vacuum sealed tube, the Re this to 4 0 ^e thermostatic bath of C immersed for 15 minutes, was tried graph preparative polymerization onto lenses substrate surface. The output of the applied ultrasonic wave is as shown in Table 7, and Table 7 similarly shows whether surface graph polymerization was possible under each applied condition.

As is evident from Table 7, surface graph polymerization was possible when the output of the applied ultrasonic wave was 10 watts or more. On the other hand, if the applied output was less than 10 ヮ, the dissolved oxygen in the monomer solution could not be sufficiently degassed, and the surface graphitization could not be performed.

Table Ί

Apart from the above example, the conventional method that does not use ultrasonic waves during polymerization, that is, the removal of dissolved oxygen is performed by drawing a vacuum into the vessel containing the monomer solution and then removing it from the outside. The process was repeated five times by repeatedly tapping and then replacing the inside of the vessel with nitrogen gas, and then evacuating again. Then, despite the same operation performed on 10 lens substrates, three of them did not undergo surface graphitization, and seven had excessively surface graphitization polymerization reactions. Nevertheless, in any case, the conventional method could not control the components of the system and the dissolved oxygen S, and could not obtain a good product. (Example 10)

 y—Metacryloxypropyl tris (trimethylsiloxy) silane 48 wt%, 1,1-dihydrono, 1-fluorobutyral Luminous create 19 wt%, 1,3-bis (y-methacryloxy brobiyl) -1,1,3,3—tetrax (Methyl siloxane) 7% by weight of disiloxane, bis (trimethyl siloxane) 1 y—Metacryloxypropyl silanol 8 wt% %, Methacrylic acid 11 wt%, ethylene glycol dimethacrylate 7 wt%, 1,1-azovis (2,4-isobutyl nitrate) A contact lens base material consisting of 0.25 wt% copolymer was prepared.

 A space made of a 1.5 mm thick spacer was provided between the electrodes of a corona discharge treatment device with a 3.5 cm interelectrode distance, an interelectrode voltage of 15 kilovolts, and a frequency of 60 Hz. The above-mentioned lens base material was installed in the apparatus, and discharge treatment was performed. The discharge treatment was performed for 40 seconds on each side and each side. Next, the lens substrate subjected to the discharge treatment was placed in a test tube, and thereafter the same treatment as in Example 9 was performed. Table 8 shows the results.

As in the case of Example 9, when the output of the applied ultrasonic wave was equal to or more than 10 ヮ, surface graph polymerization was possible. On the other hand, when the applied output was less than 10 ヮ, the dissolved oxygen in the monomer solution could not be sufficiently degassed, and the surface graphitization could not be performed.

Table 8

Apart from the examples performed above, the conventional method that does not use ultrasonic waves during polymerization, that is, the removal of dissolved oxygen is performed by drawing the container containing the monomer solution to a vacuum and then removing it from the outside. The process was repeated five times by repeatedly tapping, then replacing the inside of the vessel with nitrogen gas, and applying vacuum again. Then, despite the same operation performed on 10 lens substrates, four of them did not undergo surface grafting, and six had excessively surface graft polymerization reactions. In any case, the conventional method could not control the concentration of the system components and the amount of dissolved oxygen, and could not obtain a good product. (Example 11)

 Acrylic amide was weighed in an amount of 10 g, dissolved in distilled water to make 100 ml, and an aqueous monomer solution was prepared.

 Graph polymerization was carried out as follows. y-me-clear violent beauty (trimethylen mouth opening) silane 48 vt%, 2,2,2-trifluoroethyl Evening rate 19 wt%, 1,3-bis (γ-methacryloxyprobiol) -1,1,3,3-tetrax (trimethylsilicone) Mouth Kishi) Gishi α xan 8 wt%, bis (trimethylsiloxy)-y-methacryloxyprobisilanol 7 wt%, Methacrylic acid 10 wt Methyl methacrylate lwt%, ethylene glycol dimethacrylate 7 wt%, 2,2'-azobis (2,4-isobutyronitrile) (However, as a polymerization initiator) Prepare a contact lens base material consisting of 0.25 wt% copolymer. Was.

 Place the lens substrate in a discharge device (6 cm between electrodes, voltage between electrodes 27,0 volts, frequency 60 Hz), and place it in an argon atmosphere of 0.04 torr for 5 seconds. Glow discharge treatment was performed. After the discharge-treated lens substrate is exposed to the air, it is put into a test tube, the above-mentioned aqueous solution of acrylamide monomer is added, then Mohr salt is added, and the lens is connected to a vacuum system. Was. After the bow, the test tube was immersed in the water filled with the ultrasonic vibration tank. In this state, the inside of the tube was evacuated for 1 minute with a rotary pump, and then ultrasonic waves were applied. After the lapse of a predetermined time, the application of the ultrasonic wave was stopped, and the test tube was vacuum-sealed. It was immersed in a C thermostat for 15 minutes to attempt graph polymerization on the lens substrate surface. The output and applied time of the applied ultrasonic wave are as shown in Table 9 and Table 10.

 As is evident from Table 9, surface graph polymerization was possible when the ultrasonic wave application time was 10 seconds or longer. It was found that when the application time was less than 10 seconds, the dissolved oxygen in the monomer solution could not be sufficiently removed, and the polymerization did not occur.

-According to Table 10, if the ultrasonic application time is longer than 10 minutes, the monomer One solution was shrunk, and it became clear that cloudiness occurred on part or all of the resulting graphitized surface. When the application time was 10 minutes or less, the condition of the graph-treated surface was good.

Table 9

〇 Surface graphing possible X Surface graphing not possible

Table 10

 良好 Good surface graph condition

 X Bad surface condition (cloudy)

Apart from the above example, the conventional method that does not use ultrasonic waves during polymerization, that is, the removal of dissolved oxygen, requires that the container containing the monomer solution be evacuated and then removed from the outside. The process was repeated five times by repeatedly tapping and then replacing the inside of the container with nitrogen gas, and then evacuating again. Then, although the same operation was performed on 10 lens substrates, three of them did not undergo surface graphitization, and seven had excessive surface graphitization polymerization reactions. In any case, the conventional method could not control the concentration of the system components and the dissolved oxygen fi and could not obtain a good product. (Example 12)

y—Medium Cryoxypropyl tris (trimethylsiloxy) silane 4 8 wt% _N 1,1 -dihydrofluorofluorobutyl Tactylate 19 wt%, 1,3-vis (y-methacryloxypropyl propyl) -1,1,3,3—tetrax (trime 7% by weight of bisiloxane) disiloxane, bis (trimethylsiloxy) y-methyl siloxane 8 wt%, methacrylic acid 11 wt%, ethylene glycol methacrylate 7 wt%, 2,2'-azobis (2,4-isobutyl A contact lens base made of 0.25 wt% copolymer was prepared.

 A space made of a 1.5 mm thick spacer was provided between the electrodes of a corona discharge treatment device with a distance between electrodes of 3.5 cm, a voltage of 15 electrodes, and a frequency of 60 Hz. The above-mentioned lens base material was placed on this, and discharge treatment was performed. In addition, discharge treatment was performed for 40 seconds each on one side and both sides. Next, the lens substrate subjected to the discharge treatment was placed in a test tube, and thereafter the same treatment as in Example 11 was performed. The results are shown in Table 11 and Table 12.

As in Example 11, if the ultrasonic wave application time was less than 10 seconds, the dissolved oxygen in the monomer solution could not be sufficiently degassed, and surface graph polymerization could not be performed. In addition, it was found that when the application time was longer than 10 minutes, white turbidity occurred on the surface after the surface graphing treatment. From the results shown in Tables 11 and 12, it was found that a good surface graph was obtained only when the application time was 10 seconds or more and 10 minutes or less.

Output 1 0 1 0 0 5 0 0 Time ヮ ヮ ヮ ヮ 時間

8 seconds X X X

10 seconds 〇 〇 〇

60 seconds 〇 〇 〇

3 0 0 seconds 〇 〇 〇

〇 Surface graphing possible X Surface graphing not possible

Table 1 2

良好 Good surface graph condition

 X Bad surface condition (cloudy)

Apart from the examples performed above, the conventional method that does not use ultrasonic waves during polymerization, that is, the removal of dissolved oxygen is performed by drawing the container containing the monomer solution to a vacuum and then removing it from the outside. We hit it, then replaced the inside of the vessel with nitrogen gas, and evacuated it again, repeating the first-speed process five times. Then, despite the same operation performed on 10 lens substrates, 4 sheets did not undergo surface graphitization, and 6 sheets had excessive surface graphat polymerization reaction. In any case, the conventional method could not control the concentration of the system components and the amount of dissolved oxygen, and could not obtain a good product. (Sowase 1 3)

 3 ml of pure water was placed in a test tube with an inner diameter of 18 mm, and this was connected to a refreshing air system. Ultrasonic waves were applied to the test tube while the inside of the system was evacuated with an exhaust pump with an exhaust capacity of 60 1 miη. The temporal change in the amount of dissolved oxygen in pure water was monitored with a dissolved oxygen meter. The dissolved oxygen storage I (t) after time t minutes is

I (t) = I (0) e X p (-a x t)

The time constant a = 5 when P = 100 watt and the a = 8 when P = 200 watt for the ultrasonic output P. (Example 14)

 A test tube with an inner diameter of 18 mm was filled with 3 ml of pure water and connected to a vacuum system. While exhausting the inside of the system with an exhaust pump with an exhaust capacity of 600 min, the test tube was hit from the outside, and then the inside of the container was replaced with nitrogen gas and the vacuum was drawn again. The process was repeated five times. The temporal change in the amount of dissolved oxygen during that time was monitored with a dissolved oxygen meter. When this experiment was repeated 10 times, the time variation of the dissolved oxygen amount was different from the 10 times, and the time was used as a variable, as obtained in Example 13. Was not obtained.

 (Example 15)

 3 ml of a 10% aqueous solution of acrylamide was placed in a test tube having an inner diameter of 18 mm, and this was connected to a vacuum system. Exhaust capacity 60 I The output of 10 O watt ultrasonic waves to the test tube while evacuating the inside of the system with an exhaust pump of Zmin, when the degree of acrylamide in the aqueous solution is longer The changes were examined. After time t minutes (t <5), the acrylamide concentration C (t) is

 C (t) = C (0) (1-0.06 X t) (%)

 Where C (0) = 10

It changed according to.

 (Example 16)

A 3 rnl 10% aqueous solution of acrylamide was placed in an 18 mm test tube, which was connected to a vacuum system. Exhaust capacity 60 1 Z min While exhausting the system with a pump, hit the test tube from the outside, then replace the inside of the container with nitrogen gas, and then evacuate again. Returned. During this period, the temporal change in the degree of acrylamide filling in the aqueous solution was examined. When this experiment was repeated 10 times, the change in the acrylamide concentration with time was different from the 10 times, and the time was as obtained in Example 15. A function with as a variable was not obtained.

 (Example 17)

 y-methacryloxyprobiol-tris (trimethylsiloxy) silane 48 wt%, 1, 1-dihydrono, 1-fluorobutyrume Evening rate 19 wt%, 1,3-bis (y-methacryloxyprobiol) -1,1,3,3—tetrax (trimethyl) (Siloxy) 7% by weight of disiloxane, bis (trimethylsiloxy) 1 y-methyl chlorooxypropyl silanol 8% by weight, metal 11% by weight of lylic acid, 7% by weight of ethylene glycol dimethacrylate, 2,2'-azobis (2,4-isobutyl ditolyl)

A fluorine-containing contact lens substrate consisting of 0.25 wt% of a copolymer (as a polymerization initiator) was prepared. A space made of a 1.5 mm thick spacer was provided between the electrodes of a corona discharge treatment device with a 3.5 cm distance between electrodes, a voltage of 15 kilovolts between electrodes, and a frequency of 60 Hz. The lens base material was placed there, and the discharge treatment was performed. The discharge treatment was performed on each side and each side for 40 seconds.

35 g of acrylamide and 5 g of N, N'-methylethylene acrylamide were dissolved in 40 g of pure water to obtain a monomer aqueous solution. In addition, 1.568 g of ferrous ammonium sulfate hexahydrate (Mohl salt) was dissolved in 1 Og of pure water to obtain an aqueous Mohr salt solution. 2.4 ml of a monomer aqueous solution, 0.3 ml of a mol salt aqueous solution, and 0.3 ml of pure water were placed in a test tube and stirred. The discharge-treated lens was placed in the tube, and the tube was sealed under reduced pressure. The test tube was placed in a thermostat at 35 ° C, and the shortest time for the monomer to undergo graph polymerization on the lens surface was examined. The polymerization time was 7 minutes. Similarly, a fumarate-based base material, siloxane Tcraterate (without fluorine), base material, and methacrylate (without silicon and fluorine) system a 2 each

0 minutes, 50 minutes, and 60 minutes.

 When the transmittance at a wavelength of 500 II m was measured before the discharge treatment and immediately after the surface graft polymerization treatment was performed for each of the shortest polymerization times, the results shown in Table 13 were obtained. As is clear from the above, the transmittance of the fluorine-containing base material and the fumarate-type base material hardly changes before and after the surface graphitization treatment. In particular, in the case of a fluorine-containing base material, the transmittance did not change at all. On the other hand, the discoloration of siloxanil methacrylate (free of fluorine) and methacrylate (free of silicon and fluorine) substrates are markedly discolored. Is received.

 From the above, the superiority of the fluorine-containing base material that can be polymerized in a short time is clear. In addition, with regard to the fumarate-based base material, a favorable effect was found, which was inferior to that of the fluorine-containing base material, but hardly discolored.

Base material Before discharge treatment After Kraft polymerization treatment

Transmittance (500nm) Transmittance (500nm) Fluorine-containing 92 2% 92% Fumarate 92% 90% Sioxaxanil methacrylate 92 2% 16% G 9 2% 6 8% Clinical availability

 As described above, the contact lens manufacturing method of the present invention maintains the surface wettability permanently and obtains a hard contact lens that is excellent in a feeling of wearing. It is suitable for the manufacturing method to perform.

 Further, in the above-described embodiment, the force has been mainly described in connection with the case where a fluorine-based metal acrylate-made transparent lens base material is used. Other hard contact lenses, such as lens bases made from fumarate-based copolymers, or silicone rubbers Similar results have been obtained for all soft contact lenses. In addition, polystyrene film, polypropylene, polyvinyl chloride, polychloride vinylidene, acetate, polyester, polyvinyl Similar results were obtained for surface treatments of rualcohol, polyethylene, polycarbonate, and various other polymeric materials.

 In addition, it can be applied to medical products such as various packaging materials, agricultural water retention materials, and artificial organs using the above-mentioned materials.

Claims

The scope of the claims

1. A contact lens base material made from a polymer of an ester compound of acrylic acid or methacrylic acid, or acrylic acid or Is a contact lens base material mainly composed of a polymer that is a copolymer of an ester compound of methacrylic acid and an ester compound of fumaric acid. (A) discharging the base forest surface under normal pressure or reduced pressure, (b) immersing the base material in a hydrophilic monomer solution, and (c) reducing A step of adding a hydrophilic substance, and (d) a step of subjecting the surface of the base material to graph-polymerization of a hydrophilic monomer under normal pressure or reduced pressure. The method of manufacturing the lens.

 2. The method for producing a contact lens according to claim 1, wherein said reductant is diammonium cerium nitrate.

 3. The method for producing a contact lens according to claim 1, wherein the reducing substance is ammonium ferrous sulfate (Mole salt).

 4. The method for producing a contact lens according to any one of claims 1, 2 and 3, wherein the initiation of the graphitization is by heating.

 5. The method according to claim 21, wherein the hydrophilic monomer is acrylamide or N, N'-methylenebisacrylamide. A method for producing a contact lens as described in paragraphs 1, 2, 3, and 4.

 6. Siloxy-substituted ester of acrylic acid or metaacrylic acid represented by the following general formula (

X X 0 R

 I I II I

R ⁴ [Si-O] »Si (CH ₂ ) _n OCC = CH ₂

YY However, R = CH or H;

 X = C1 to C alkyl, cyclohexyl, phenyl or ZY = C to C alkyl, cyclohexyl, phenyl Or Z

R '

 I

Z = R ² [S i-0]

R ³

R ¹ = Alkyl, cyclohexyl or phenyl of C to Cs

2 = C to C alkyl, cyclohexyl or phenyl R ³ = C, to Cs alkyl, cyclohexyl or phenyl et two le R = C ~ a Le key Le of C _6, shea click b to key sheet le or the full e d le m = 1 - 3;

 n = 1 to Ό

 P = 1-3;

), The fluoroalkyl substitution of acrylic acid or methacrylic acid having no more than 20 fluorine atoms represented by the following general formula: Body (

AOR

H However, R = CH 3 or H;

A = H, silicone, phenyl or R _f ;

R _f = Polyfluoroalkyl or Benzofluorophenyl

), A poly (fluoroalkyl) siloxy substituted ester of acrylic acid or methacrylic acid represented by the following general formula (

However, R = CH 3 or H;

 R r = a fluoroalkyl group of C i to C <i; m = 0, 1 or 2;

 n = 1-3;

), Acrylic (metaacryl) represented by the following general formula:

XOR

H [0-Si] m (CHa) nO-C-C = CH2

 Y

However, R = C Η 3 or Η;

X, Υ = alkyl of C, up to Cs; phenyl or Z; R ¹

 I

Z = R ² [S i -〇]

R ³

m = 1 to 3;

 n = 1-5;

 P = 1 to 3;

R ¹ = C-C s alkyl, silicone, or phenyl

R ² = C-C alkyl, silicone, or phenyl

R ³ = C! -C Alkyl, Cyclic Hexil or File

), A polyacrylic (methacrylic) represented by the following general formula:

X X O R

I I II I

-0 [Si (0-Si) _m (CH ₂ ) nO-CC = CH ₂ ]

 Υ Ύ

However, R = C Η ₃ or H;

 m = 03;

 n 5;

XC to C alkyl, cyclohexyl, filler or ZYC to C alkyl, cyclohexyl, filler or Z 〇

² HD H

Λ (ί <6f: saliva r. ^ C <^ ^ ^-^-(ΰψ., (

: Ε ι =

 'ε I = u ο τ I = πι ■ ε τ = τ

I I I II

¾3 = 0-0-0- ¹ (¾))-TS- [CHS] ^u ( ² HD) N-0-JO- ^¾ (0-¾3-i3) 0- ^A d ^E D

H-Two ^ ^ ¾ ΐί: $ ¾α ^ 51-09 ^, (

Λί-^ L t -J. ^ ΛΙ η ^ ^, ί ω ω ^s 0 ~ ¹ 0 = _ε "a ί-L -J. ^ (^ Η ^ /, * ³ o ~ ¹ s = ₂ " a

^ Α 4 ^, Φ Ίί 0 ⁹ O ~ ¹ 0 =! H

■ ε = d

-89- fr03lO / Z6df / JLDd eSIfl / £ 6 OM

H ', R ² = CH or H;

 1 = 2-4;

 p, q = 1 or 2;

 m and n are each integers whose sum is in the range of 20;

) And a fluorine-containing cyclic olefin represented by the following general formula (

A = H, F or alkyl group

 B = F or alkyl group

 C = H, F or alkyl group

 D = F or a C t to C 3a fluoroalkyl group which may contain an oxygen atom to which at least one fluorine atom is bonded; n = 0, 1 or 2;

), A copolymer made from a copolymer of acrylic acid or an ester compound of methacrylic acid, which is a copolymer containing at least one of them. (A) a step of subjecting the surface of the substrate to a discharge treatment under normal pressure or reduced pressure; and (b) a step of discharging the substrate with an acrylamide and Κ, Ν'- A step of dipping in a mixed monomer solution containing methylene bisacrylamide as a main component; and (c) a step of adding ammonium diammonium cerium (W). (D) On the surface of the S material, the mixture In the method for producing contact lenses, which comprises the step of graphing the normalizer 21, the addition of diammonium cerium nitrate (IV) a A contact lens manufacturing method characterized in that the weight is 0.01 g or more and 1 g or less per 1 g of the combined monomer.

 7. At least Alkyl Metal Creat and Alkyl Malate 'Fluoro Alkyl Malate and Shiroki Sanil Malate (

H 0

 I II

 A-0-C-C = C-C-0-A '

 〇 In Formula H, A and A 'are selected from the group consisting of C i to C 5 alkyl or D groups, and D is a structural formula

B X

 CicFs 1-(C¾) ι-[Si-0] »-Si- (CH2) π-Β Wherein X and Υ are selected from the group consisting of C 1 -C 5 alkyl and Ζ groups, and Ζ is a structural formula

Β

 B- [Si-0],

It is a group having B, and B represents an alkyl group of Ct to Cs. k, 1, m, and n are 0 or a positive integer. In contact lens S material made from copolymers of methacrylic acid and fumaric acid, which are copolymers of a) The surface of the Ω material under normal pressure or reduced pressure (B) a mixed monomer containing said base material as main components of acrylamide and Ν, Ν'-methyl bisacrylamide. A step of immersing in the solution; (c) a step of adding diammonium cerium nitrate (IV); and (d) a step of applying the mixed monomer to the surface of the base under normal pressure. In the method for producing contact lenses, which comprises a step of photopolymerization, the addition of diammonium cerium nitrate (IV) is carried out in a mixed monomer. 0 A method for producing a contact lens, which is not less than 1 g and not more than 1 g.

 8. Siloxy-substituted ester of acrylic acid or methacrylic acid represented by the following general formula (

X X O R

R ^A [Si-O] »Si (CH ₂ ) nO-CC = CH ₂

 Y Y

However, R = CH ₃ or H;

 X = Ci to C6 alkyl, cyclohexyl, phenyl or Z Y = C1 to C6 alkyl, cyclohexyl, phenyl or Z

R ¹

Z = R ^a [Si-O]

R ³

R ¹ = C! Alkyl, cyclohexyl or phenyl of ~ Cs

R ² = Alkyl, cyclohexyl or phenyl of Cι to Cs

R ³ = Alkyl, cyclohexyl or phenyl of C i to C s

R ^Λ = alkyl, cyclohexyl or phenyl of C 1 to C s 餺 y 87 ¾ ^

74 b ^ ぃ

 (fl

Sub ^ T ^ ), An acrylic (methacrylic) oxyalkyl silanol represented by the following general formula (

X O R I II I

H [〇1 Si]. (CHa) _n 〇1 C-1 C = CH ₂

 Y

However, R = C Η 3 or Η;

 X, Υ = alkyl of C t ~ C s; phenyl or Z;

R ¹

 I

Z = R ² [Si-0]

R ³ m = 1 ~ ^3;

 11 = 1 to 5;

 P = 1 to 3;

R ¹ two C ·, - C s of A Ruki Le, Shi click the key sill or to Π full X two le;

R ² -C t--C 8 alkyl, cyclohexyl or fluorinated X 2 alkyl;

R ³ = C! -C6 alkyl, silicon hexyl or vinyl;

), Polyacrylic (methacrylic) represented by the following general formula:

X X O R

I I II I

1 0 [Si (0-Si) _m (CH ₂ ) _n 〇1 C-1 C = CH ₂ ] z

Υ Υ However, R = CH 3 or H;

 m = 0-3;

 n = 1-5;

 X = Ci to C6 alkyl, cyclohexyl, fell or ZY = C1 to C6 alkyl, cyclohexyl, feh Le or Z

R '

Z = R ² [S i-0]

R ³

P = 1-3;

R ¹ = Alkyl, cyclohexyl or phenyl of C1 to C6

R ² = C1-C6 alkyl, cyclohexyl or phenyl

R ³ = Ct to C6 alkyl, cyclohexyl or phenyl

), Fluorine-containing siloxane methacrylate represented by the following general formula:

CFa CF ₃ CH ₃ C 0 CH3

 I I I I II I

Ca FT -0 (CF-CF ₂ -0) _k -CF-CN (CH2) n [Si-0] _m -Si- (C¾) i -0-CC = CH ₂

 II I I I

0 H CH ₃ CH3 1 = 1 to 3;

 m = 1 to 10;

 n = 1-3;

 k = 1-3;

), A fluorine-containing acrylic acid or methyl acrylate ester monomer represented by the following general formula (

0 R ¹

 II I

Rr-0-CH ₂ -CH-0-CC = CH ₂

R ² -C-0-CH ₂

 II

 0

R f = a C 1 -C 3 B fluoroalkyl group which may contain an oxygen atom having at least three fluorine atoms bonded thereto;

R ¹ = CH 3 or H;

 An alkyl group of R s ^ C! C sa which may contain a fluorine atom or an oxygen atom;

), A fluorine-containing acrylic acid or methyl acrylate ester monomer represented by the following general formula:

0 R ¹

 II I

R ² -0-CH ₂ -CH-CHa-0-CC = CH ₂

 Rr-C-0

 II

0 R r = a fluoroalkyl group of C1 to C3B which may contain an acid to which at least three fluorine atoms are bound;

R ¹ = CH ₃ or H;

^{_{R 2 = C 1 ~ C 3}} a was in full Tsu atom or is good also contain oxygen atoms les, A Le key Le group;

), A fluorine-containing jellyrate or dimethacrylate-related monomer represented by the following general formula (

CF ₃ 〇 OR ¹

 I II II I

(CF ₂ -0-CF) mCO (CH ₂ — CH ₂ —〇). C-I C = CH∑

 I

(CF ₂ ). CF ₃ 〇 OR ²

 I I II II I

_{(CF 2 -0-CF) nCO} (CH 2 - CH 2 - 0). C-I C = CH _∑

RR ² = CH ₃ or H;

 1 = 2-4;

 P, q = 1 or 2;

 m and n are integers whose sum is in the range of 20

) And a fluorine-containing cyclic olefin represented by the following general formula (

A = H, F or alkyl S;

 Β = Η,: F or alkyl group;

 C = H.F or an alkyl group;

 D = F or at least one fluorine atom may contain an oxygen atom bonded to C; a fluoroalkyl group of ~ Csa; n = 0, 1 or Or 2;

), A polymer of an ester compound of acrylic acid or methacrylic acid, which is a copolymer containing at least one of them, is used as a raw material. (A) a step of subjecting the surface of the base material to a discharge treatment under normal pressure or reduced pressure, and (b) a step of preparing the base material with an acrylamide. A step of immersing in a mixed monomer solution containing H, N'-methylene bisacrylamide as a main component; and (c) ammonium ferrous sulfate (a mol salt). (D) a step of subjecting the mixed monomer to a graphene polymerization under reduced pressure on the surface of the base material, the method comprising the steps of: It is characterized in that the amount of addition of ferrous ammonium (mol salt) is 0.02 g or more and 0.06 g or less per lg of the mixed monomer. Co-te-click door lenses manufacturing method of that.

 9. At least Alkyl methacrylate, Alkyl malate 'Fluoro alkyl malate and Siloxanil malate (

H 0

 I II

 A-0-C-C = C-C-0-A,

 II I

0 H In the formula, A and A 'are selected from the group consisting of an alkyl group or a D group of C, to C5, and D is a structural formula BX CKF ₂ have, - (C¾) i - [ Si-0] m -Si- (C¾) "-. BY also One Motodea Ru the formula in the X your good beauty Y is C, of ~ C ₅ A Ruki And Z are selected from the group consisting of

B

B- [Si-0] _m-

I

 It is a group with B, and B is C! ~ C 5 represents an alkyl group. k, 1, m and n indicate 0 or a positive integer. A contact lens base material which is a polymer of an ester compound of methacrylic acid and fumaric acid, which is a copolymer with (B) subjecting the base material to acrylamide and Ν, Ν'-methyl bisacrylamide (C) adding ammonium ferrous sulfate (mole salt); and (d) applying a reduced pressure to the surface of the base material. In the process of producing a composite lens, which comprises the step of subjecting the mixed monomer to a graphitization polymerization in step (a), wherein ferrous sulfate ammonium (mol salt) is added. The contact lens is characterized in that the amount is 0.02 g or more and 0.06 g or less per lg of mixed monomer. Production method.

 10. A siloxane substituted ester of acrylic acid or methacrylic acid represented by the following general formula (

X X O R

I I II I

R ⁴ [Si-O] .Si (CH nO-CC = CH ₂

YY However, R = CH 3 or H; '

X = C t~ C ₆ of A Ruki Le, shea click b to key sheet le, full et two Le or is of ZY = C 1~ C s A Ruki Le, key sheet Le to shea click b, full et sulfonyl Or Z

R,

Z = R ^z [S i-0]

R ³

R ¹ = C 1~ C 6 of A Ruki Le, shea click b to key sheet le or the full e d le R ² = C 1~ C 6 of A Ruki Le, the key sill or to the sheet click b off Enil R ³ = Alkyl, cyclohexyl or C1 to Cs alkyl or phenyl R ⁴ = Alkyl, cyclohexyl of C1 to Cs Or phenyl m = 1-3;

 n = 1 to 5;

 P = 1 to 3;

), The fluoroalkyl substituted product of acrylic acid or methacrylic acid having not more than 20 fluorine atoms represented by the following general formula (

A O R I II I

Rr -C -0-C- C = CH≥

H However, R = CH 3 or H;

A = H, cyclohexyl, phenyl or _Rf ;

 R r = Polyfluoroalkyl or Benzofluorophenyl

), A poly (fluoroalkyl) siloxane substituted ester of acrylic acid or methacrylic acid represented by the following general formula (

 CHs but R = C H 3 or H;

 R r = Ci-C 4 fluoroalkyl group;

 J = J to Δ *

 m = 0, 1 or 2;

 n =:! ~ 3;

), An acrylic (metaacryl) oxyalkylsilane represented by the following general formula (

X O R I II I

H [0-Si] _n (CH ₂ ) nO-CC = CH ₂

 Y

However, R = C Η 3 or Η;

X, Υ = alkyl from C i to C 6; phenyl or Z; R '

Z = R ² [Si-0]

R ³

m = 1 to 3;

 n = 1 to 5

 P = 1 to 3;

R ¹ = Alkyl of CI ~ C s

R ² = Al to C l to CS

R ³ = Alkyl to CI to C6

), Poly (acrylamide) represented by the following general formula:

X X O R I I II I

One 0 CSi (0-Si) _n (CH ₂ ) nO-CC = CH ₂ ]

 Y Y

Where R = CH ₃ or H

 m = 0 to 3;

 n = 1 to o;

X = C1-Cs alkyl, cyclohexyl, fel or ZY = C1-Cs alkyl, cyclohexyl, fel or Z

R _f = a C 1 -C 3 B fluoroazole group which may contain an acid cable atom with at least three bonded hydrogen atoms;

R ¹ = CH 3 or H;

 An alkyl group which may contain a fluorine atom or an oxygen atom of R S C t C sa;

), A fluorine-containing acrylic acid or methacrylic acid ester monomer represented by the following general formula:

0 R ¹

 II I

R ^a -0-CH ₂ -CH-CH ₂ -0-CC = CH ₂

R _f = a C 1 to C a fluoroalkyl group which may contain an oxygen atom having at least three fluorine atoms bonded thereto;

R ^l = CH ₃ or H;

R ² = an alkyl group of C t to C ₃ e which may contain a fluorine atom or an oxygen atom;

), A fluorine-containing diacrylate or dimethacrylate-like monomer represented by the following general formula (

(CFa-O-

(CF ₂ ), CFa 0 OR ²

 I I II II I

(CF2-0-CF) nCO (CH ₂ — CH ₂ — O). (_C = CH ₂ RR ² = CH ₃ or H;

 1 = 2-4;

 P, q = 1 or 2;

 m and n are integers whose sum is in the range of 20

) And a fluorine-containing cyclic olefin represented by the following general formula (

A = H, F or alkyl group

 B = H, F or alkyl group

 C = H, F or alkyl group

 D = F or a C1 to C3a fluoroalkyl group which may contain an oxygen atom to which at least one fluorine atom is bonded; n = 0 , Or 2;

), A polymer of an ester compound of acrylic acid or methacrylic acid, which is a copolymer containing at least one of them, was used as a raw material. In the contact lens base material, (a) a step of subjecting the surface of the base material to discharge treatment under normal pressure or reduced pressure; and (b) a step of coating a hydrophilic monomer on the surface of the base material. In the method for producing a contact lens comprising a step of photopolymerization, an ultrasonic wave is applied under vacuum to the hydrophilic monomer solution in the step (b). And a method for manufacturing a contact lens.

10. The contact according to claim 10, wherein the output of the ultrasonic wave is 10 watts or more, and the application time of the motor is 10 seconds or more and 10 minutes or less. The method of manufacturing the lens.

Amended claims

 [March 29, 1993 (29.03.93) Accepted by the International Bureau; Claims 11-11 originally filed were replaced with amended claims 1-11. (Page 29)]

1. Esters of acrylic acid or methacrylic acid, or esters with some of them substituted, or acrylic acid or methacrylic acid Discharge occurs on the surface of a contact lens substrate formed using at least one of the copolymers of the ester of acrylate and the ester of fumarate. Performing a process;

 Forming a state where the contact lens substrate is immersed in a hydrophilic monomer solution to which a reducing substance has been added;

 A step of subjecting the contact lens substrate surface to graphitic polymerization, the method for producing a contact lens.

 2. The method for producing a contact lens according to claim 1, wherein the reducing substance is diammonium nitrate [IV].

 3. The method for producing a contact lens according to claim 1, wherein the reducing substance is ammonium ferrous sulfate (mole salt). .

 4. The method for producing a contact lens according to claim 1, wherein the initiation of the graph polymerization is caused by heating.

 5. The hydrophilic monomer is acrylamide, or 2—hydroxy shetylmetacrylate, or polybutyl alcohol, or N—bulpyrolium. Don't or polyethylene oxide, or dimethyl acrylamide, or N, N'-methylene bisacrynoleamide The method for producing a contact lens according to claim 1, wherein the contact lens is any one type.

6. Methyl methacrylate, or a siloxy-substituted ester of acrylic acid or methacrylic acid represented by the following general formula [ XX 〇 R 4 [S i 〇] inS i [CH 2) n 〇 C-C = CH 2

Y Y

However, R = C H3 or H;

 X = C1-C6 alkyl, cyclohexyl, phenyl or ZY = C1-C6 alkyl, cyclohexyl, phenyl or Z

R 1

Z = R2 [S i — 0] P—

R 3

H1 = alkyl of C1 to C6, cyclohexinole or phenyl R2 = alkyl of C1 to C6, cyclohexyl or phenyl R3 = C1 to C6 Alkyl, cyclohexyl or phenyl R 4 = C1-C6 alkyl, cyclohexyl or phenyl

m = 1 to 3

n = 1 to 5

p = 1 to 3 Or, a fluoroalkyl or methacrylic acid having not more than 20 fluorine atoms represented by the following general formula: Substitution

A 〇 R

 II

 Rf- C-0-C-C = C H 2

H

Where R = C H 3 or H:

 A = H, cyclohexyl, phenyl or Rf:

 R f = polyfluoroalkyl or pentafluorophenyl

) Or a poly (fluoroalkylalkyloxy) substituted ester of acrylic acid or methacrylic acid represented by the following general formula:

CH3 (CH3) m 0 R

 II I

 [Rf-CH2-CH2-Si-0] n-Si- (CH2) 1-0-C -C = CH2

CH3 but R = CH3 or H;

Rf = Cl to C4 phenolic group: / 14153

 90

1 = 1 to 4;

 m = 0, 1 or 2

 n = 1-3;

:) or an acrylic (metaacryl) oxyalkylsilanol represented by the following general formula:

X 0 R

 H [0—S i] m (C H2) nO-C-C = C H2

 Y, but R = C Η 3 or H;

 X, Y = Alkyl from C1 to C6: phenyl or Z

R 1

 Z = R2: S i — 0] P

R 3 / 14153 91

m = 1 to 3

 n = 1 to 5

 P = 1 to 3

 R 1 = alkyl of C 1 to C 6. Cyclohexinole or phenyl

 R 2 = alkyl of C 1 to C 6. Cyclohexinole or phenyl

 R3 = alkyl of C1-C6. Cyclohexyl or phenyl

)> Alternatively, a polyacryl (methacryl) oxyalkylpolysiloxane represented by the following general formula:

X X 0 R

 II

 0 [S i (0— S i) m (C H 2) n0-C-C = C H 2] 2

Y Y

However, R = C Η 3 or H:

 m = 0 to 3

 n = 1 to 5:

X = alkyl from C1 to C6; cyclohexyl, phenol or ZY = alkyl from C1 to C6. Cyclohexyl, phenol or Z / 14153 9

R 1

Z = R 2 [S i — 〇] P

R 3

P = 1 to 3;

 R1 = alkyl of C1-C6. Cyclohexyl or phenyl

 R2 = alkyl of C1 to C6. Cyclohexyl or F: Cnil

 R3 = Alkyl of C1 to C6. Cyclohexyl or phenyl

) Or a fluorine-containing siloxanyl methacrylate represented by the following general formula (

CF3 CF3 CH3 CH3 0 CH3

C3F7-0 (CF-CF2-0) k-CF-C-N (CH2) n [Si-0] m-Si- (CH2) l-0-C-C = CH2

 II I I I

 0 H CH3 CH3

1 = 1 to 3:

 m = 1 to 10

 n = 1-3;

 k = 1-3;

:) or a fluorine-containing acrylic acid or a compound represented by the following general formula: / 14153

Methacrylic acid ester monomer [

〇 R 1

Rf- 0-C H2-C H-0-C-C = C H2

R2- C-0-C H2

0

R f = a C 1 -C 30 phenolic alkyl group which may contain an oxygen atom having at least three fluorine atoms bonded thereto;

 R1 = C H3 or H:

 R2 = Alkyl group which may contain a fluorine atom or an oxygen atom of C1 to C30:

:) or a fluorine-containing acrylic acid or methacrylic acid ester monomer represented by the following general formula (

0 R 1

 II I

 R2— 0-C H2-C H-C H 2-0-C-C = C H2 R f- C-0

〇

Ri == contains oxygen atoms with at least three fluorine atoms bonded 14153 94

A C I -C 30 fluoroalkyl group;

 R1 = C H3 or H:

 R2 = an alkyl group which may contain a C 1 to C 30 fluorine atom or oxygen atom;

) ^ Or. Fluorine-containing or dimethacrylate-like monomer represented by the following general formula (

C F 3 0 0 R 1

 I II II i

 CC P2-0-C F) mC 0 [C H2— C H2 —〇) C-C = C H2

C C F 2) 1 C F 3 0 0 R 2

 I I II II I

CC F 2-0-C P) nC O (C H 2-C H 2-0) qC-C = C H 2

R1, R2 = C H3 or H:

 1 = 2 to 4: '

 P, q = l or 2:

 m and n are each an integer whose sum is in the range of 1 to 20: or a fluorine-containing cyclic ore represented by the following general formula:

C

A = H, F or alkyl group:

 B = H, F or an alkyl group;

 C = H, F or alkyl group:

 D = P or a C1-C30 fluoroalkyl group which may contain an oxygen atom to which at least one fluorine atom is bonded: n = 0 or 2;

), Or alkyl fumarate, or fluoroalkyl fumarate, or siloxaerf fumarate represented by the following general formula (

H 0

 II

 A-0 -C -C = C -C -0 -A '

 II I

 0 H

In the formula, A and A ′ are selected from the group consisting of CI to C5 alkyl groups or D groups, and D is a structural formula [ BX

CkF2k + l- (CH2) 1-[S i -0] m-S i-(CH2) n-

It is a group with B Y. Wherein X and Y are selected from the group consisting of C1-C5 alkyl groups and Z groups, and Z is a structural formula

B

B -CSi-0] m-

It is a group having B, and B represents a C1-C5 alkyl group.

 k, 1, m, and n represent 0 or a positive integer.

), Formed from a polymer of acrylic acid or an ester compound of methacrylic acid, which is a copolymer containing at least one of them. Subjecting the contact lens base material to a discharge treatment, and adding diammonium nitrate (W) to the contact lens base material. A step of forming a state of being immersed in a hydrophilic monomer solution; and a step of subjecting the contact lens substrate surface to graphitic polymerization, wherein the diammonium nitrate cell is used. Characterized in that the addition amount of the polymer [W] is from 0.01 g to 1 g per 1 g of the hydrophilic monomer. / 14153 97

The method of manufacturing the lens.

 7. The method according to claim 1, wherein the hydrophilic monomer is a mixed monomer having acrylamide and N, N'-methylbenzeneacrylamide. A method for producing a contact lens according to item 6.

 8. Methyl methacrylate, or a siloxy-substituted ester of acrylic acid or methacryloleic acid represented by the following general formula (

X X 0 R

 II

 R 4 [S 0] mS i (C H 2) nO— C-C-C H 2

Y Υ

Where R = C H3 or H:

 X = C1-C6 alkyl, cyclohexyl, phenyl or Z Y = C1-C6 alkyl, cyclohexyl, phenyl or Z

R 1

Z = R 2 [S i —〇] P

R 3

R1 = C1-C6 alkyl, cyclohexyl or phenyl R2 = C 1 to C 6 alkyl, silk mouth hexyl or phenyl

 R 3 = Alkyl, C 1-C 6 Alkyl, hexyl or phenyl

 R 4 = alkyl of C 1 to C 6, cyclohexyl or phenyl m-1 to 3;

 n = 1 to 5;

 P = 1-3;

Alternatively, a fluoroalkyl-substituted form of acrylic acid or methacrylic acid having not more than 20 fluorine atoms represented by the following general formula (:

A O R I II I

 Rf— C-1 0— C-1 C = C H2

H

Where R = C H3 or H:

 A = H, cyclohexyl, phenyl or R f:

 R f = Fluoroalkyl or Benzofluorophenyl

Alternatively, polyacryloyl-substituted esters of acrylic acid or methacrylic acid represented by the following general formula: CH3 (CH3) m 0 R

 II I

 [R f-CH2-CH2-Si-0] n-Si- (CH2) 1-0-C -C = CH2

CH3

Where R = C H 3 or H:

 Rf = Fluoroalkyl group of Cl to C4

 1 = 1 to 4;

 m = 0, 1 or 2:

 n = 1 to 3:

Alternatively, an acrylic (methacrylic) compound represented by the following general formula:

X O R I II I

 H [0-S i] m C C H 2) nO — C-C = C H 2

Y

Where R = C H 3 or H:

X, Y = alkyl of C1-C6: phenyl or Z; / 14153 10 0

R 1

Z = R 2 [S i — 0] P

R 3

m = 1 to -3:

 n = 1 to 5;

 P = 1-3;

 R1 = alkyl from C1 to C6; cyclohexylene or phenyl R2 = alkyl from C1 to C6; cyclohexyl or phenyl R3 = from C1 to C6 Alkyl cyclohexyl, phenyl, or polyacryl (methacryl) oxyalkylpolysiloxane represented by the following general formula:

X X O R I I I! 1

One 0 [S i (0— S i) m (C H2) nO— C one C = C H2] 2

Y Y But R = C H 3 or H

 m = 0-3;

 n = 1 to 5;

X = alkyl from C1 to C6; cyclohexyl, phenyl or ZY = alkyl from C1 to C6. Cyclohexyl, phenyl or Z / 14153

R 1

Z = R 2 [S 0] P

R 3

P = 1-3;

 f

 ϋ

 R 1 = alkyl, cyclohexyl or phenyl of C 1 to C 6 R2 = alkyl, cyclohexyl or phenyl of C 1 to 'C 6 R3 = C 1 to C 6 alkyl, cyclohexyl or phenyl

)> Alternatively, a fluorine-containing siloxanyl methacrylate represented by the following general formula (

CF3 CF3 CH3 CH3 0 CH3

I I I I II I

 C3F7-0 (CF-CF2-0) k-CF-C-N (CH2) n [Si-0] m-Si- (CH2) l-0-C-C = CH2

 II I I I

 0 H CH3 CH3

1 == 1-3

 m = 1 to: L 0

 n = 1 to 3:

k = 1 to 3: or a fluorine-containing acrylic acid or a compound represented by the following general formula: Methacrylic acid ester monomer (

〇 R 1

 II I

 Rf- 0-C H2-C H-0-C-C = C H2

R2- C-0-C H2

 II

 0

Rf = a C1-C30 fluoroalkyl group which may contain an oxygen atom having at least three fluorine atoms bonded thereto:

 R1 = C H3 or H:

 R2 = C 1 to C 30 may contain a fluorine atom or an oxygen atom;

:) or a fluorine-containing acrylic acid or methacrylic acid ester monomer represented by the following general formula (

0 R 1

 "II I

 R2-0-C H2-C H-C H2-0 — C-C = C H2 R f- C-0

0 R f = C 1 to C 30 phenol or oleanol group which may contain an oxygen atom having at least three fluorine atoms bonded thereto:

 R 1 = C H 3 or H:

 R2 = It may contain a fluorine atom or an oxygen atom of C1 to C30;

) Or a fluorine containing cryllate or dimethacrylate clear monomer represented by the following general formula (:

C P 3 0 0 R 1

 I II II I

 (C P 2-0-C P) mC O (C H 2-C H 2-0) pC-C = C H 2

(C F 2) 1 C F 3 〇 0 R 2

(C P 2-0-C P) nC 0 [C H 2-C H 2-0] qC-C = C H 2

R1, R2 = CH3 or H:

 1 = 2-4;

 P, q = 1 or 2;

m and n each represent an integer whose sum is in the range of 1 to 20:) or a fluorine-containing cyclic olefin represented by the following general formula [ 3/14153

 104

A = H, F or alkyl group:

 B = H, F or alkyl group:

 C = H, F or alkyl group:

 D = F or at least one fluorine atom bonded to and optionally containing an oxygen atom C1-C30 fluoroalkyl group: n = 0, 1 or 2:

), Or anore kirf malate, or phenolic oleo kirf malate, or siloxanil fumarate represented by the following general formula (

H 〇

 I!

 A-0 -C -C = C-C 〇 one A '

 II I

〇 H Wherein A and A ′ are selected from the group consisting of C 1 to C 5 alkyl groups or D groups, and D is a structural formula

B X

I I

 CkF2k + l- (CH2) 1-[S i -0] m-S i-(CH2) n-

It is a group with B Y. Wherein X and Y are selected from the group consisting of C1-C5 alkyl and Z groups, and Z is a structural formula

B

B-[Si-0] m-

It is a group having B, and B represents a C1-C5 alkyl group.

 k, 1, m and n each represent 0 or a positive integer. ), Using a polymer of an ester compound of acrylic acid or methacrylic acid, which is a copolymer containing at least one of them. Performing a discharge treatment on the surface of the formed contact lens substrate;

 Forming a state in which the contact lens substrate is immersed in a hydrophilic monomer solution to which ammonium ferrous sulfate (mole salt) is added;

And a step of subjecting the contact lens substrate surface to graphitic polymerization. / 14153

 10 6

The amount of the ferrous ammonium sulfate (mol salt) to be added is 0.02 g or more and 0.06 g or less per lg of the hydrophilic monomer. Manufacturing method for contact lenses.

 9. The method according to claim 1, wherein the hydrophilic monomer is a mixed monomer having acryloamide and N, N'-methyl benzoyl amide. A method for producing a contact lens according to item 8.

 10. Methyl methacrylate, or a siloxy-substituted ester of acrylic acid or methacrylic acid represented by the following general formula:

X X 0 R

R4 [S 0] mS i [C H 2] ηθ— C-C = C H 2

Y Y

Where R = C H 3 or H:

 X = C1-C6 alkyl, cyclohexyl, phenyl or Z Y = C1-C6 alkyl, cyclohexyl, phenyl or Z

R 1

Z = R 2 [S i-0] P-

R 3 / 14153

10 7

R 1 = Alkyl cyclohexyl or phenyl of C1 to C6 R2 = Alkyl cyclohexyl or phenyl of C1 to C6

 R3 = C 1-C 6 phenolic cyclohexene or phenyl R4 = C 1-C6 phenolic phenyl.Cylinder mouth hexyl or phenyl m = 1-3 ；

 n = 1-5;

 P = 1--3;

) Or a fluoroalkyl of acrylate or methacrylate having no more than 20 fluorine atoms represented by the following general formula: Substitution (

A 0 R

Rf— C-1 0— C-1 C = C H 2

H

However, R = C H 3 or H:

 A = H, Cyclohexyl, Fennole or Rf:

 R f = polyolefin radical or pentafluorophenyl radical

) Or a poly (fluoroalkyl) siloxane ester of acrylic acid or methacrylic acid represented by the following general formula [ CH3 (CH3) m 0 R

[R f-CH2-CH2-Si-0] n-Si- (CH2) l-O-C-C = CH2

CH3

Where R = C H 3 or H:

 Rf = C1-C4 fluoroalkyl group;

 1 = 1 to 4:

 m = 0, 1 or 2:

 n = 1-3;

:) or an acrylic (metaacryl) represented by the following general formula:

X 0 R

H [0 — S i] in (C H2) ηθ — C-C = C H 2

Y

However, R = C Η 3 or H:

X, Y = C 1 to C 6 キ キ: Final or Z 14153 t 09

R 1

Z = R 2 [S i-0] P

R 3

m = 1-3;

 n = 1 to 5:

 P = 1-3;

 R 1 = alkyl from C 1 to C 6. Cyclohexyl or phenyl R2 = alkyl from C 1 to C 6. Cyclohexyl or phenyl

 R3 = C1-C6 alkyl. Cyclohexyl or phenyl

Alternatively, a polyacryl (methacryl) oxyalkylpolysiloxane represented by the following general formula:

X X O R

I I II I

One 0 [S i (0— S i) m (C H 2) nO— C one C = C H2] 2

Y Y

 Where R = C H 3 or H:

 m = 0 to 3:

 n = 1 to 5;

X = C 1 to C 6 phenol, cyclohexyl, phenyl or ZY = C 1 to C 6 phenol, cyclohexyl, phenyl or Z R 1

Z = R2 [S i — 0] P

R3

P = 1-3;

 R 1 = alkyl, cyclohexyl or phenyl of C 1 to C 6; R 2 = alkyl, cyclohexyl or phenyl of C 1 to C 6: R 3 = C 1 -C 6 alkyl, cyclohexyl or phenyl:

:) or a fluorine-containing siloxanyl methacrylate represented by the following general formula (

CF3 CF3 CH3 CH3 0 CH3

C3F7-0 (CF-CF2-0) k-CF-C-N (CH2) n [Si-0] m-Si- (CH2) l-0-C-C = CH2

 II I I I

 0 H CH3 CH3

1 = 1-3;

 m = 1 to 10;

 n = 1 to 3:

 k = 1-3;

:) or a fluorine-containing acrylic acid or a compound represented by the following general formula: Methacrylic acid ester monomer (

0 R 1

 II I

 Rf— 0— C H2— C H-0— C-C C = C H2

R2- C-0-C H2

 II

 0

Rf = a C1-C30 fluoroalkyl group which may contain an oxygen atom having at least three fluorine atoms bonded thereto:

 R1 = C H3 or H:

 R2 = alkyl group which may contain a C 1 to C 30 fluorine atom or oxygen atom:

) Or a fluorine-containing acrylic acid or methacrylic acid ester monomer represented by the following general formula (

0 R 1

 II I

 R2-0-C H2-C H-C H2-0-C-C = C H2

R f- C-0

 II

〇 t 12

Rf = C 1 -C 30 fluoroalkyl group which may contain an oxygen atom having at least three fluorine atoms bonded thereto:

 R1 = C H3 or H:

 R 2 = an alkyl group which may contain a fluorine atom or an oxygen atom of C 1 to C 30:

), Or a fluorine-containing crylate or dimetacrerate-based monomer represented by the following general formula:

C F 3 0 0 R 1

CC P2-0-C F) mC 0 (C H2-C H2-0) pC-C = C H2

C C P 2) 1 C F 3 0 0 R 2

 [I II II I

 (C P 2-0-C F) nC 0 (C H 2-C H 2-0) qC-C = C H 2

R1, R2 = CH3 or H:

 1 = 2-4;

 P, q = l or 2:

m> n is an integer whose total number is in the range of 1 to 20;) or a group represented by the following general formula: 93/14153

 ¾ 13

A = H, F or alkyl group:

 B-H, F or alkyl group:

 C = H, F or alkyl group:

 DF or a C 1 -C 30 fluoroalkyl group which may contain an oxygen atom to which at least one fluorine atom is bonded: n = 0 or 2;

), Or alkyl fumarate, or fluoroalkyl fumarate, or siloxanyl fumarate represented by the following general formula (

H 0

 II

 A-0 -C -C = C -C -0 -A '

 II I

〇 H In the formula, A and A ′ are selected from the group consisting of C 1 to C 5 alkyl groups or D groups, and D is a structural formula (

B X

CkF2k + ^ (CH2-[Si-0] m-Si- (CH2) n-

It is a group with B Y. Wherein X and Y are selected from the group consisting of C 1 to C 5 alkyl groups and Z groups;

B

B -CSi-0] m-

It is a group having B, and B represents an alkyl group of C1 to C5.

 k, 1, m, and n indicate 0 or a positive integer. :), formed from a polymer of acrylic acid or an ester compound of methacrylic acid, which is a copolymer containing at least one of them. Using the contact lens substrate

 (A) performing a discharge treatment on the contact lens surface;

 (B) a step of immersing the contact lens substrate in a hydrophilic monomer solution to which a reducing substance has been added,

[C) a graphene polymerized on the surface of the contact lens substrate; Yes,

A method for producing a contact lens, wherein ultrasonic waves are applied to the hydrophilic monomer solution under vacuum during the step (b).

A statement based on Article 19 of the koto Claims shall be corrected in order to further clarify the features of the present invention by making the expression and structure of the claims appropriate based on the embodiment. Go

The details are as follows. Claim 1 replaces claim 1 at the time of filing

In addition, the characteristics of the contact lens manufacturing method of the present invention are further clarified.

Was. Claim 2 is the same as claim 2 at the time of filing.

is there. Claim 3 is the same as claim 3 at the time of filing.

is there. Claim 4 is replaced with Claim 4 at the time of filing

In addition, the characteristics of the method for manufacturing a contact lens of the present invention are further clarified.

Was. Claim 5 replaces claim 5 at the time of filing

In addition, the hydrophilic monomer, which is one of the features of the present invention, has been further clarified.

Was. Claim 6 is a combination of claims 6 and 7 at the time of filing.

In addition, the characteristics of the contact lens manufacturing method of the present invention are further clarified.

did. Claim 7 replaces claim 5 at the time of filing

In addition, the hydrophilic monomer, which is one of the features of the present invention, is further clarified.

Was. Claim 8 includes both claims 8 and 9 at the time of filing.

In addition, the characteristics of the contact lens manufacturing method of the present invention are further clarified.

did. Claim 9 clarifies the hydrophilic monomer, which is one of the features of the present invention, differently from claim 5 at the time of filing. Claim 10 has replaced the claim 10 at the time of filing, and has further clarified the features of the contact lens manufacturing method of the present invention. Paragraph 11 of the claim at the time of filing was deleted.