JPS61281116A - Contact lens material - Google Patents

Abstract

PURPOSE:The titled material, obtained by copolymerizing a specific organosiloxane with a specific alcohol and fluoroalkyl alcohol ester of methacrylic acid, etc., having improved oxygen permeability and hydrophilicity, usable continuously for a long period and readily handleable. CONSTITUTION:A material obtained by copolymerizing an organosiloxane expressed by formula I [Y1-Y5 are 1-5C alkyl, aromatic group, formula II (R3 is H or 1-5C alkyl; p is an integer 1-5), etc.; X is formula II (R2 is H or CH3); R1 and R1'' are 1-5C alkyl, aromatic group, etc.; R1' is 1-5C alkyl, aromatic group, etc.; l, l', m and m' are integers 0-10; n is an integer 1-10] with a polyhydric alcohol ester of (meth)acrylic acid, itaconic acid, etc., and/or a 1-20F fluoroalcohol ester of (meth)acrylic acid, itaconic acid, etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a contact lens material that has particularly excellent oxygen permeability and hydrophilicity, can be worn continuously for a long time, and is substantially water-free. The present invention relates to contact lens materials that are easy to handle and handle.

[Prior art and its problems]

Conventionally, contact lenses containing polymethyl methacrylate as a main component, for example, have been put to practical use. Polymethyl methacrylate, the main component of this contact lens, has great advantages such as excellent optical properties and durability, but due to the corneal physiology, it cannot be worn continuously for long periods of time due to poor oxygen permeability. There is a big drawback.

Therefore, as a solution to the above-mentioned drawbacks of hard type contact lenses, water-containing contact lenses containing poly-2-hydroxyethyl methacrylate as a main component have been put into practical use, and in addition, soft type contact lenses have been put into practical use. The lens has good hydrophilicity, so the feeling of wearing it is satisfactory to some extent, but the oxygen permeability is not sufficient, so it cannot be worn continuously for a long time. They have the disadvantage that they are more difficult to handle than lenses.

In order to enable continuous wear, contact lenses with high water content, for example, containing N-vinylpyrrolidone as a main component, have been proposed, and these lenses exhibit favorable features in terms of hydrophilicity and oxygen permeability. However, due to its high water content, it has extremely poor mechanical strength, poor durability, and is extremely troublesome to handle.

Contact lenses made of silicone rubber or silicone resin have been proposed as contact lenses that exceed the above-mentioned contact lenses whose main ingredients are polymethyl methacrylate, poly 2-hydroxyethyl methacrylate, or poly N-vinylpyrrolidone. Since it has no hydrophilicity, it not only requires surface treatment to make it hydrophilic, but also the durability of the surface-treated hydrophilic membrane is poor, making it unsatisfactory.

[Disclosure of the invention]

The present inventor has proposed the following formula: [1]
"" Y @ At least one of the groups is two groups, and
The group is selected from the group consisting of H carbonate C=C-R5 ■ aromatic group, and W group, Wa group is Ra-3i-0-, and Ra is C1-C1 alkyl group or aromatic group. , R+' does not represent a group and KR
I'O-R+' or 01~Cs
selected from the group consisting of alkyl groups, aromatic groups, and W groups, L, t'', m, and m' are integers of 0 to 10, and n
is an integer from 1 to 10, and the two groups are -(CH*)s → -(CM, CH, O) p -u,
, -(CR1)q-(OCHICIII)r-()-
CCHI, q is an integer of 2 to 3, r is an integer of 0 to 5, S
is an integer from 1 to 3, and R1 is a hydrogen atom or 01 to .
C1 is an alkyl group, R4 is a hydrogen atom or a methyl group), an organosiloxane represented by a C1 to C1° monohydric or polyhydric alcohol, and an acid selected from the group consisting of methacrylic acid, acrylic acid, and itaconic acid. An ester and/or an ester consisting of a linear or branched fluoroalkyl alcohol having 1 to 20 fluorine atoms and an acid selected from the group consisting of methacrylic acid, acrylic acid, and itaconic acid. Materials made of polymerized copolymers have excellent oxygen permeability and hydrophilicity, and are substantially water-free.Contact lenses made of such materials are easy to handle, have excellent durability, and They found that it is comfortable to wear and can be worn continuously for long periods of time, and that it also has excellent vision correction effects and dimensional stability.

In addition, as the organosiloxane represented by the above general formula [1], for example, IMe Me 1-methacryloxyethoxypropyl-3-(acetoxypropyl)-1,1,3,3-(tetramethyl)disiMe methacryloxy Ethoxypropyl-tris(acetoxyethyldimethylsiloxy)silane, 1,3-bis(methacryloxyethoxypropyl)-1,1,3,3-tetrakis(acetoxyethyldimethylsiloxyfudisiloxane, hetyl-mexycloxyethoxyprobilute) Lis(carboxyethyldimethylsiloxy)silane, 1-methacryloxyethoxypropyl-5-[(methoxyethoxyethoxycarbonyl)ethyl) -1,1,
3,3,5°5-hexamethyldisiloxane, 1-methacryloxyethoxypropyl-3-acetoxypropyl-1,1,3,3-tetramethyldisiloxane, 7′′ C,H.

1-methacryloxyethoxypropyl-5-[(acetoxypropyloxycarbonyl)ethyl)-3,7-diprobyl-1.3,5.7-(tetramethyl)tetracyclosiloxane, CM.

C1(,CHtO-C,0 1-methacryloxyethoxypropyl-1,3,5,7
-(Tetramethyl)-3,5,7-)su(acetoxyethyl)tetracyclosiloxane, Me Me 1-methacryloxyethoxyprobyl-3-(hydroxyethoxyprobyl) -1,1,3,3-( Tetramethyl)disiloxane, 1-acryloxyethoxypropyl-3-(4,7゜1
0,13.16-bentaoshioctadecyl-18-ol)-1,1,3,3-(tetramethyl)disiloxane, 1-methacryloxyethoxyprobyl-3-(12
-Acedoxy 4.7.10-)
-1,1,3,3-(tetraphenyl)disiloxane,
1-acryloxyethoxypropyl-3-(4,7゜1
0,13-tetraoxyhexadecyl) -1,1,3
, 3-(tetrapentyl)disiloxane 1-methacryloxyethoxypropyl-19-(acetoxypropyl)icosamethyldecasiloxane, 1-acryloxyethoxypropyl-3-((3,6-cyoxyoctyl-8- All-1-oxycarbonyl)ethyl]-1,1,3,3-(tetramethyl)disiloxane, 1-methacryloxyethoxypropyl-3-[(hydroxyethyloxycarbonyl)propyl]-1,1,3
,3-(tetramethyl)disiloxane, 1-acryloxyethoxypropyl-5-((1,4゜7-drimethyl-3.6.9-)lioxadecyloxycarbonyl)ethyl) -1,1,3 ,3,5,5-(hexamethyl)
Trisiloxane, 1,3-bis(methacryloxyethoxyprobyl)-1
, 1,3,3-tetrakis(a7toxibu4pyltetramethyldisiloxane)disiloxane, 1-methacryloxyethoxypropyl-9-((acetoxyisopropyloxycarbonyl)ethyl)decamethylpentasiloxane, CMHPS- 4) 1-Methacryloxyethoxypropyl-5-[(dihydroxypropyloxy]propyl) -1,1,3゜3
．． Examples include 5.5-(hexamethyl)trisiloxane.

In addition, examples of esters consisting of C1 to CI· monohydric or polyhydric alcohols and acids selected from the group consisting of methacrylic acid, acrylic acid, and itaconic acid include methyl methacrylate, methyl acrylate, dimethyl itaconate, and itaconic acid. Monomethyl, ethyl methacrylate, ethyl acrylate, diethyl itaconate, monoethyl itaconate, n-7'pyl methacrylate, n-propyl acrylate, di-n-propyl ichconate, monol]-propyl itaconate, inpropyl methacrylate, isopropyl acrylate , diisopropyl itaconate, monoisopropyl itaconate, n-butyl methacrylate,
n-butyl acrylate, di-n-butyl itaconate, mono-n-butyl itaconate, pentyl methacrylate, pentyl acrylate, cypentyl icconate, monopentyl itaconate, neopentyl methacrylate, neopentyl acrylate, dineopentyl itaconate, mononeo itaconate Pentyl, n-hexyl methacrylate, n-hexyl acrylate, di-n-hexyl itaconate, mono-n-hexyl itaconate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclohexyl itaconate, monocyclotetrahexyl itaconate, 2
-ethylhexyl methacrylate, 2-ethylhexyl acrylate, di-2-ethylhexyl itaconate, mono-2-ethylhexyl itaconate, ethylene glycol dimethacrylate, ethylene glycol diacrylate,
Diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, 1,3-butanediol dimethacrylate, 1,3-butanediol dimethacrylate acrylate), 1,4-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1.6-
Hexanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate,
Trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate, ethylene glycol monomethacrylate, ethylene glycol monoacrylate, thiethylene glycol monomethacrylate, diethylene glycol monoacrylate, triethylene glycol monomethacrylate, Triethylene glycol monoacrylate, 2
Examples include -hydroxypropyl methacrylate, 2-hydroxybrobyl acrylate, 2-hydroxybutyl meccrylate, 2-hydroxybutyl acrylate, 2-hydroxystyrene methacrylate, and 2-hydroxystyrene acrylate.

Esters of monohydric alcohol and methacrylic acid or acrylic acid, or diesters of monohydric alcohol and itaconic acid are mainly used to improve the processability and toughness of polymer materials. Monoesters of alcohol and methacrylic acid or acrylic acid, or 1
Monoesters of alcohol and itaconic acid are mainly used to improve the hydrophilicity of polymeric materials. It is also possible to use methacrylic acid, acrylic acid, acrylamide, methacrylamide, N-methylolmethacrylamide, N-vinylpyrrolidone, etc. in place of the above-mentioned esters used to improve hydrophilicity.

In addition, linear or branched fluoroalkyl alcohols having 1 to 20 fluorine atoms = Shigiko and Methacrylate,
Examples of esters consisting of an acid selected from the group consisting of acid, acrylic acid, and itaconic acid include 2.2.2-trifluoroethyl methacrylate), 2,2.2-)trifluoroethyl acrylate, and bisfluoroethyl acrylate. -2,2,2-trifluoroethylitacone* -), 2,2.2-) trifluoroethylitacone), 2,2,3.3-tetrafluoropropyl methacrylate), 2,2.3 -tetrafluoropropyl acrylate, bis-2,2,3,3-tetrafluoroprobylitaco, t, -), 2,2,3.3-
Tetrafluoroprobyl itakone), 2,2,3,
3゜4.4.5.5-octafluoropentyl methacrylate, 2, 2.3.3.4.4.5.5-octafluoropentyl methacrylate, bis-2,2,3,3,
4,4,5,5-octafluoropentyl itaconate, 2.2.3.3.4.4.5.5-octafluoropentyl itaconate, IH.

IH, 2T (, 2H-hebutadecafluorodecyl methacrylate-1, IH, LH, 2H, 2H-hebutadecafluorodecyl acrylate, bis-IH, IH, 2H.

2H-heptadecafluorodecyl icconate, IH9
II (,21,2H-heptadecafluorodecylitacone), LH,ll1-pentadecafluorooctyl methacryle-), IH,LH-pentadecafluorooctyl acryle-), 11(,II(-pentadecafluorooctyl methacryle-)), Fluorooctyl itaconate, bis-I H, I II-pentade fluorooctyl itaco*-), IH, IH-pentafluoropropyl methacrylate), II (, LH-
Pentafluoropropyl acrylate, bis-II (,
IH-pentafluoroprobyl itakone), IH,I
H-pentafluoroprobyl icconate, hexafluoroisopropyl methacrylate, hexafluoroisopropyl acrylate, bishexafluoroisopropyl itaconate, hexafluoroisopropyl itaconate, IH, IH-hebutafluorobutyl methacrylate, LH, IH-hepfluoro butyl acrylate,
BisLH,IH-hebutafluorobutylitacone-1.
etc.

These esters mainly act together with the organosiloxane to improve the oxygen permeability of the polymer material, and also improve the optical transparency.

In addition, a part of the organosiloxane is expressed by the general formula [2] (where As is selected from the group consisting of a C1 to C4 alkyl group, an aromatic group, and a B group, and the B group is (SiO)n-). Yes, As, Al' is C+ ~
Cg is selected from the group consisting of alkyl AI' groups and aromatic groups, n is an integer of 1 to 3, m is a number of 0 or 1, and As is CHs or H
, Al and A4 do not represent a group but represent a bond chain connecting AlA4, or Ar is selected from the group consisting of a Ct -Cs alkyl group and an aromatic group, and A4 is a C3 to C6 alkyl group, an aromatic group. selected from the group consisting of group groups and B groups. ) and/or a monofunctional organosiloxane represented by the general formula [3] (where X, to x6 are selected from the group consisting of an alkyl group of CI"" Cs, an aromatic group, and a Y group, and the Y group is HtC
-CRt 0-COCHxCHsOCHtCILCH*- and (
However, Ra is selected from the group consisting of a group, an aromatic group, and two groups, and Ra is RL-5i-0-, and Ra is an alkyl group or an aromatic group of CI'' Cm, R, / does not represent a group, KR% O
represents a bonding chain R+' or is selected from the group consisting of an alkyl group, an aromatic group and two groups of CI""Cs, 1
．． , m, L', m' are integers from 'o to to, n is 1 to 10
copolymerization may be used instead of the polyfunctional organosiloxane represented by (an integer of ).

In addition, examples of the organosiloxane represented by the above general formula [2] include methacryloxyethoxyprobilpentamethyldisiloxane, acryloxyethoxyprobilpentamethyldisiloxane, methacryloxyethoxyprobilhebutamethyltriditetraxane, acryloxy Ethoxib tetravirheptamethyltrisiloxane, methacryloxyethoxypropyltris(trimethylsiloxy)silane, acryloxyethoxypropylphenyltris(trimethylsiloxy)silane, methacryloxyethoxypropylphenyltetramethyldisiloxane, acryloxyethoxypropylphenyltetra Methyldisiloxane, methacryloxyethoxyprobyltripendyldiethyldisiloxane, acryloxyethoxyprobyltrihenzyldiethyldisiloxane, methacryloxyethoxyprobyl n-pentylhexamethyltrisiloxane, acryloxyethoxyprobyl n-pentylhexa Methyltrisiloxane, methacryloxyethoxyprobildi n-propylpentamethyltrisiloxane, acryloxyethoxyprobildi n-propylpentamethyltrisiloxane, methacryloxyethoxyprobilphenyl octamethyltetrasiloxane, acryloxyethoxyprobilphenyl octamethyltetra Cytetraxane, methacryloxyethoxyprobylisobutyltetramethyldisiloxane, acryloxyethoxyprobylisobutyltetramethyldisiloxane, methacryloxyethoxypropylmethylbis(trimethylsiloxy)silane, acryloxyethoxypropylmethylbis(trimethylsiloxy) Silane, methacryloxyethoxypropyrutris (dimethylcyclohexylsiloxy) Silane, acryloxyethoxypropyrutris (dimethylcyclohexylsiloxy)
Silane, methacryloxyethoxyprobylpentamethyldisiloxybis(trimethylsiloxy)silane, acryloxyethoxyprobylpentamethyldisiloxybis(
trimethylsiloxy) silane, methacryloxyethoxyprobyl to butamethylcyclotetrasiloxane, acryloxyethoxyprobyl to butamethylcyclotetrasiloxane, methacryloxyethoxyprobyltetramethyltriprobylcyclotetrasiloxane, acryloxyethoxyprobyltetramethyltri Examples include brobylcyclotetracyp-xane.

Further, as the organosiloxane represented by the above general formula [3], for example, 1,3-bis(methacryloxyethoxyprobyl)-1,1,3,3-(tetramethyl)disiloxane, 1,5-bis (acryloxyethoxyprobyl) -1,1,3,3,5,5-(hexamethyl)trisiloxane, 1,7-bis(methacryloxyethoxyprobyl) -1,1,7,7-tetrakis(trimethyl) siloxy) -3,3,5,5-(tetramethyl)-
Tetrasiloxane, 1,3-bis(methac130-+jethoxyprovir) -1,1,3,3-? ) 5-kis(bis(trimethylsiloxy)methylsiloxy)disiloxane, 1,3-bis(acryloxyethoxyprobyl-1,1,3,3-(tetraphenyl)disiloxane, 1,5-bis(methacrylate) 1,3,5-(dimethyl)-1,3゜5-(tripropyl)trisiloxane, 1,5-bis(methacryloxyethoxypropyl)-1,3,5゜7 -(Tetramethyl)-3,7-(dipropyl)cyclotetrasiloxane, 1,3,5-tris(acryloxyethoxyprobyl) -1,3,5,7-(tetramethyl)-7-
(propyl)cyclotetrasiloxane, 1,3,5.7
- Tetrakis (methacryloxyethoxyprobil) -
Examples include 1,3,5,7-(tetramethyl)cyclotetrasiloxane, [tris(acryloxyethoxyprobyl)dimethylsiloxytwomethylsilane, etc.].

The ratio of the organosiloxane and ester constituting the copolymer as a material for contact lenses is preferably about 5 to 80 parts by weight to about 95 to 20 parts by weight, but even more preferably. is about 5 to 95 parts by weight of an ester of monohydric alcohol and methacrylic acid or acrylic acid, or a diester of monohydric alcohol and itaconic acid, fluoroalkyl alcohol and methacrylic acid, to 5 to 80 parts by weight of organosiloxane. 50 parts by weight or less of an ester with acrylic acid or itaconic acid (diester is particularly preferred when itaconic acid is used), 60 parts by weight or less of an organosiloxane represented by the general formula (2) or (3), Approximately 0.5 to 15 parts by weight of diesters, triesters, and tetraesters of polyhydric alcohols and methacrylic acid or acrylic acid, monoesters of polyhydric alcohols and methacrylic acid or acrylic acid, and monohydric alcohols and itaconic acid. monoester of fluoroalkyl alcohol and itaconic acid, or a copolymer of about 5 to 10 parts by weight of a hydrophilic monomer such as methacrylic acid instead of these esters. desirable.

Then, dimethyl-2.
2'-azobisisobutyrate, 2.2/-azobis(
4-methoxy-2,4-dimethylvaleronitrile), 2
．． 2'-azobis(2,4-dimethylvaleronitrile)
, 2.2'-azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, methyl ethyl ketone peroxide, isobutyl peroxide, diisopropyl peroxydicarbonate, etc. Polymerization is done by law.

In addition, for example, 1-methacryl-oxyethoxypropyl-3-(
Acetoxypropyl)-1,1,3,3-tetramethyldisiloxane is obtained as follows.

First, using methacrylic acid and allyloxyethanol,
Allyloxyethyl methacrylate ester (boiling point 2BHg-64-65
°C, n: 1.4463) is obtained.

Approximately 1 mole of allyl acetate and 10-5 moles of platinum catalyst were added to a three-loaf flask equipped with a reflux condenser, thermometer, dropping funnel, and stirrer, and after heating to 90°C, 1.1 mole of allyl acetate was added from the dropping funnel. .3. About 1 mole of 3-tetramethyldisiloxane was added dropwise, the reaction was carried out while stirring at 90°C, and then distillation was performed under reduced pressure to obtain 1-acetoxypropyl-1,1°3.3- Tetramethyldisiloxane is obtained.

Next, a reaction mixture obtained by adding 10-5 moles of platinum catalyst to 1 mole of allyloxyethyl methacrylate was heated to 75°C, and the 1-acetoxypropyl-1 obtained above was heated to 75°C.
, 1 mol of 1,3,3-tetramethyldisiloxane was added dropwise, and the reaction was carried out while stirring at 75°C. Thereafter, unreacted allyloxyethyl methacrylate and 1-acetoxypropyl- 1,1,3,3-
Tetramethyldisiloxane was distilled off and 1-methacryloxyethoxypropyl-3-(acetoxypropyl)-
1,1,3,3-(tetramethyl)disiloxane is obtained.

Further, for example, 1-methacryloxyethoxyprobyl-tris(acetoxyethyldimethylsiloxy)silane can be obtained as follows.

First, methacrylic acid allyloxyethyl ester was obtained in the same manner as in the above case, and the "R'tAE cooler"
Approximately 1 mole of the above allyloxyethyl methacrylate and 10 moles of platinum catalyst are added to a three-hole flask equipped with a thermometer, dropping funnel, and stirrer, and the mixture is heated to approximately 75°C, and then 1.1 mole of trichlorosilane is added dropwise. . Then, the reaction is carried out while stirring while maintaining the temperature at 75 to 80°C, and then unreacted allyloxyethyl methacrylate and trichlorosilane are distilled off under reduced pressure to obtain methacryloxyethoxyprobyltrichlorosilane.

Next, a solution of 0.3 mol of the above methacryloxyethoxyprobyl trichlorosilane and 1.8 mol of acetoxyethyldimethylchlorosilane dissolved in 3 mol of isopropyl alcohol was placed in a three-neck flask equipped with a cooler, thermometer, and dropping funnel. , the reaction mixture is kept at a temperature of 0-10°C and 4 mol of distilled water is added to carry out the co-hydrolysis.

Then, the upper organic layer was separated, washed with an aqueous sodium bicarbonate solution and distilled water, desorbed with anhydrous sodium sulfate, decolorized by adding an appropriate amount of activated carbon, and then filtered through a membrane filter (0.2μ). The low boilers are distilled off under reduced pressure to obtain 1-methacryloxypropyl-tris(acetoxyethyldimethylsiloxy)silane.

Also, for example, 1-methacryloxyethoxyprobyl-3-
(Human tetraxyethoxypropyl) -1,1゜3.3-
Tetramethyldisiloxane is obtained as follows.

First, allyloxyethyl methacrylate ester was obtained in the same manner as in the previous case, and approximately 1 mol of allyloxyethoxytrimethylsilane and 10 mol of platinum catalyst were placed in a three-loaf flask equipped with a reflux condenser, a thermometer, a dropping funnel, and a stirrer.
After heating to 90°C, approximately 1 mol of 1.1.3.3-tetramethyldisiloxane was added dropwise from the dropping funnel, and the reaction was carried out with stirring while maintaining the temperature at 90°C. Distillation is performed under reduced pressure to obtain 1-trimethylsiloxyethoxypropyl-1,1,3,3-tetramethyldisiloxane.

Next, a reaction mixture of 1 mole of allyloxyethyl methacrylate and 10-5 moles of platinum catalyst was heated to 75°C. 1 mol of 3,3-tetramethyldisiloxane was added dropwise, the reaction was carried out while stirring at 75°C, and then unreacted allyloxyethyl methacrylate and 1-trimethylsiloxyethoxyprobyl-1 were added under reduced pressure. After distilling off 1,3,3-tetramethyldisiloxane and performing acid hydrolysis in an alcohol solution, the organic layer was separated, washed with an aqueous sodium bicarbonate solution and water, and anhydrous sulfuric acid. After dehydration and decolorization with activated carbon, low-boiling substances are distilled off to obtain 1-methacryloxyethoxyprobyl-3-(hydroxyethoxyprobyl)-1,1,3,3-tetramethyldisiloxane.

Also, for example]-methacryloxyethoxyprovir-5-
(dihydroxypropyloxypropyl)-1,1,3
,35,5-hexamethyltrisiloxane is obtained as follows.

First, as in the above case, methacrylic acid allyloxyethyl ester is obtained by a normal esterification method using methacrylic acid and allyloxyethanol under a sulfuric acid catalyst.

Then, 1 mole of ketal allyl ether obtained by reacting allyl glycidyl ether and acetone in the presence of a boron trifluoride catalyst and 1 mole of 1.1.3°3,5.5-hexamethyltrisiloxane were mixed with platinum. Catalyst 10-5
After reaction at 70 °C in the presence of mol, distillation was carried out under reduced pressure to produce 1-(6,7-6-imprivylidene-4-oxaheptyl)-L 1.3.3.5.5- Hexamethyltrisiloxane is obtained. Next, a reaction mixture of 1 mole of allyloxy methacrylate and 10-5 moles of platinum catalyst was heated to 75°C, and the 1-(6
, 7-6-imbropylidene-4-oxaheptyl)
- 1 mol of 1,1,3,3,5,5-hexamethyltrisiloxane was added dropwise, the reaction was carried out with stirring while maintaining the temperature at 75°C, and then acid hydrolysis was performed and the organic layer was separated.
After washing with an aqueous sodium bicarbonate solution and distilled water, dehydrating with anhydrous sodium sulfate, and decolorizing with activated carbon, low-boiling substances were distilled off under reduced pressure. Propyloxypropyl)-1,1,3,3,5,5-hexamethyltrisiloxane is obtained.

[Examples 1 to 9] 1'/A P S -15 to 80 parts by weight, 7 to 82 parts of methylmeccryle-1 (hereinafter referred to as MMA) as an ester of monohydric alcohol and methacrylic acid, and as a hydrophilic monomer V-65 (trade name, 2.2' −Azobis (
Polymerization initiator for 2,4-dimethylvaleronitrile) 0.
Add the 01 heavy Itt part and make it 16NL in diameter and 10 in height.
After pouring into a cylindrical polypropylene polymerization mold and replacing the upper space with nitrogen, the mixture was kept at 40°C for 20 hours in an oven that had been replaced with nitrogen, and then heated to 70°C and 90°C.
℃ for 10 hours, then 100℃ for 10 hours.
Polymerization is completed by holding for a certain period of time to obtain a colorless, transparent, hard rod-shaped block.

Then, a contact lens is obtained by subjecting this rod-shaped block to normal processing.

The characteristics of the contact lenses thus obtained are shown in Table 1.

Table 1 [Examples 10 to 20] 1 part by weight of PS-245, ester 42 consisting of a monohydric alcohol of CI"C+ shown in Table 2 and an acid selected from the group consisting of methacrylic acid, acrylic acid, and itaconic acid. Heavy duty part, hydrophilic monomer MA8 parts by weight, TGD5 parts by weight, V
Example 1 Using 0.03i parts of -601 (trade name, dimethyl-2,2'-azobisisobutyrate)
A colorless and transparent hard rod-shaped block is obtained in the same manner as above, and this is processed to obtain a contact lens.

The properties of the contact lenses thus obtained are shown in Table 2.

[Examples 21 to 49] 30 to 5 offtil of various organosiloxanes, H as ester consisting of monohydric alcohol and methacrylic acid
A colorless, transparent, hard rod-shaped block was obtained in the same manner as in Example 1 using 1 part of MA27-57 weight J, 1 part of MA weight, 5 parts of TGD, and 1 part of V-650.0, and this was processed to make contact lenses. get.

The characteristics of the contact lenses thus obtained are shown in Table 3.

[Examples 50 to 78] 5 to 80 parts by weight of various organosiloxanes, 95 parts by weight or less of esters of monohydric alcohols and methacrylic acid, acrylic acid, or itaconic acid, Fluo. 95 parts by weight or less of an ester of ayakyl alcohol and methacrylic acid, acrylic acid or itaconic acid, a diester or triester of a polyhydric alcohol and methacrylic acid or acrylic acid as a crosslinking agent,
15 parts by weight or less of tetraesters, monoesters of polyhydric alcohol and methacrylic acid or acrylic acid, monoesters of monohydric alcohol and itaconic acid, monoesters of fluoroalkyl alcohol and itaconic acid as hydrophilic monomers, A colorless, transparent, hard rod-shaped block was obtained in the same manner as in Example 1 using 10 parts by weight or less of methacrylic acid, acrylic acid, or N-viny L-pyrrolidone and 0.01 part of TrL or less of a free radical polymerization initiator. Process to obtain contact lenses.

The characteristics of the contact lenses thus obtained are shown in Table 4.

[Examples 79 to 95] Various organosiloxanes 50 to 60 i i u ,
Esters of monohydric alcohol and methacrylic acid and acrylic acid 351 i! Below, 10 parts by weight or less of an ester of fluoroalkyl alcohol and methacrylic acid or acrylic acid, 15 parts by weight or less of a diester of polyhydric alcohol and methacrylic acid as a crosslinking agent, 10 parts by weight or less of nuccrylic acid as a hydrophilic monomer, V A colorless, transparent, hard rod-shaped block is obtained in the same manner as in Example 1 using -650.01 parts by weight, and this is processed to obtain a contact lens.

The characteristics of the contact lenses thus obtained are shown in Table 5.

Procedural amendment September 3, 1985

Claims (1)

[Claims] General formula▲ Numerical formula, chemical formula, table, etc.▼ (However, Y_1 to Y_6 groups are selected from the group consisting of C_1 to C_5 alkyl groups, aromatic groups, and Z groups, and Y_1 to Y
At least one of the _5 groups is a Z group, the X group is ▲ there are mathematical formulas, chemical formulas, tables, etc.
_1″ is selected from the group consisting of C_1 to C_5 alkyl groups, aromatic groups, and W groups, the W group is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and Ra is C_
1 to C_5 alkyl group or aromatic group, R_1'
does not represent a group but represents a bonded chain of R_1'-O-R_1', or is selected from the group consisting of C_1 to C_5 alkyl groups, aromatic groups, and W groups, l, l', m, m' is an integer from 0 to 10, n is an integer from 1 to 10, and Z
The group is -(CH_2)_3-O-(CH_2CH_2O)p-
R_3, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and p is 1
~5 integer, q is an integer of 2 to 3, r is an integer of 0 to 5, s is 1
is an integer of ~3, R_3 is a hydrogen atom or C_1~C_
an organosiloxane represented by an alkyl group (R_4 is a hydrogen atom or a methyl group), a monohydric or polyhydric alcohol of C_1 to C_1_0, methacrylic acid, acrylic acid,
an ester consisting of an acid selected from the group consisting of itaconic acid and/or a linear or branched fluoroalkyl alcohol having 1 to 20 fluorine atoms and methacrylic acid;
A contact lens material characterized in that it is copolymerized using at least an ester consisting of an acid selected from the group consisting of acrylic acid and itaconic acid.