JPH0515724B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to contact lens materials, and in particular to contact lens materials that have excellent oxygen permeability and hydrophilicity, can be worn continuously for long periods of time, are substantially water-free, and are easy to handle. It's about lenses. [Prior art and its problems] Conventionally, for example, contact lenses containing polymethyl methacrylate as a main component have been put to practical use. Although polymethyl methacrylate, the main component of contact lenses, has great advantages such as excellent optical properties and durability,
Due to its poor oxygen permeability, it has a major drawback in that it cannot be worn continuously for long periods of time due to corneal physiology. 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 soft type contact lenses such as these have been put into practical use. Lenses have good hydrophilicity, which makes them comfortable to wear to some extent, but they do not have sufficient oxygen permeability, so they cannot be worn continuously for long periods of time.Furthermore, they are water-containing, so hard contact lenses are recommended. It has the disadvantage that it is more troublesome to handle than . In addition, 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 have 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. And the above polymethyl methacrylate, poly 2-hydroxyethyl methacrylate or poly N
-Contact lenses made of silicone rubber or silicone resin have been proposed as contact lenses that go beyond contact lenses containing vinylpyrrolidone as the main component, but these materials are not hydrophilic and require surface treatment to make them hydrophilic. Not only that, but the durability of the surface-treated hydrophilic membrane is poor and is not fully satisfactory. [Disclosure of the Invention] By the way, contact using methyldi(trimethylsiloxy)silylpropylglycerol methacrylate represented by the following general formula () and methyldi(trimethylsiloxy)silylpropylglycerol ethyl methacrylate represented by the following general formula () It has been proposed to construct a lens (Japanese Patent Laid-Open No. 54-55455). However, although materials using this proposed organosiloxane had good water wettability, they often appeared cloudy and had poor optical properties, making them undesirable as contact lens materials. . As a result of intensive research into this cause, methyldi(trimethylosiloxy) represented by the above general formula () was found.
Silylpropylglycerol methacrylate and methyldi(trimethylsiloxy)silylpropylglycerol ethyl methacrylate represented by the above general formula () have -OH groups, making purification by distillation difficult (because the boiling point increases due to the association of -OH groups). It was thought that impurities such as oligomers were easily mixed in, which caused the cloudiness. In addition, the material in which the proposed organosiloxane is used is relatively soft, making it difficult to mechanically process, and it also has the problem of poor processability into contact lenses. As a result of intensive research into this problem, we found methyldi(trimethylsiloxy)silylpropylglycerol methacrylate represented by the above general formula () and methyldi(trimethylsiloxy)silylpropyl represented by the above general formula (). In glycerol _ethyl methacrylate, the moiety between the methacryloxy group and the organosiloxane group is _-CH2CH (OH)CH2 _- O _{- CH2CH2CH2}
- and -CH ₂ CH ₂ -O0-CH ₂ CH(OH)CH ₂ -O
It was thought that because it had a long chain -CH ₂ CH ₂ CH ₂ -, it became relatively soft. Furthermore, it has been proposed (Japanese Patent Application Laid-Open No. 132725/1983) to construct a contact lens using a siloxanyl alkyl ester monomer represented by the following general formula (). However, materials using this proposed siloxanyl alkyl ester monomer have poor water wettability because they do not contain hydrophilic groups, and are not preferred as contact lens materials.
For this reason, copolymers with hydrophilic monomers have to be used, but if the amount of hydrophilic monomers is increased to improve water wettability, copolymers tend to become cloudy due to poor copolymerizability. There is a limit to its water wettability, and it is not desirable as a contact lens material. The present invention was achieved as a result of further research based on such knowledge, and the object of the present invention is to provide a material that has excellent optical transparency, oxygen permeability, and hydrophilicity, and has substantially It is essentially water-free, and furthermore, it is easy to mechanically process, and the resulting contact lenses are easy to handle, have excellent durability, and are comfortable to wear, allowing for long-term continuous wear. Our goal is to provide contact lenses. The purpose of this invention is to obtain the general formula (However, R ₃ is a C ₁ to C ₆ alkyl group, an aromatic group,
selected from the group consisting of X group, where X group is

[Formula], R ₂ and R ₂ ' are selected from the group consisting of C ₁ to C ₆ alkyl groups and aromatic groups, and n is 1
is an integer of ~3, m is a number of 0 or 1,
R ₅ is CH ₃ or H, R ₁ and R ₄ do not represent a group but represent a bonding chain connecting R ₁ - R ₄ , or R ₁ is C ₁ to C ₆
selected from the group consisting of alkyl groups, aromatic groups,
R ₄ is selected from the group consisting of a C ₁ to C ₆ alkyl group, an aromatic group, and an X group. ), an ester consisting of an organosiloxane represented by _C1 to _C10 monohydric or polyhydric alcohol, and an acid selected from the group consisting of methacrylic acid, acrylic acid, and itaconic acid, and/or 1 to 20 fluorine atoms. From a copolymer copolymerized using at least a linear or branched fluoroalkyl alcohol having atoms, a fluoroalkylbenzyl alcohol, and an ester of an acid selected from the group consisting of methacrylic acid, acrylic acid, and itaconic acid. This is achieved with a contact lens material. That is, the material of the present invention has excellent optical transparency, oxygen permeability, and hydrophilicity, is substantially water-free, and is relatively hard, so it is easy to mechanically process. The contact lenses obtained are easy to handle, have excellent durability, are comfortable to wear, can be worn continuously for long periods of time, are dimensionally stable, and have excellent vision correction effects. It was hot. The organosiloxane represented by the above general formula includes, for example, methacryloxyethoxypropylpentamethyldisiloxane, acryloxyethoxypropylpentamethyldisiloxane, methacryloxyethoxypropylheptamethyltrisiloxane, acryloxyethoxypropylheptamethyltrisiloxane, methacryloxyethoxypropyltris(trimethylsiloxy)silane,
Acryloxyethoxypropyltris(trimethylsiloxy)silane, methacryloxyethoxypropylphenyltetramethyldisiloxane, acryloxyethoxypropylphenyltetramethyldisiloxane, methacryloxyethoxypropyltribenzyldiethyldisiloxane, acryloxyethoxypropyltribenzyldiethyl Dicycloxane, methacryloxyethoxypropyl n-
Pentylhexamethyltrisiloxane, acryloxyethoxypropyl n-pentylhexamethyltrisiloxane, methacryloxyethoxypropyl di-n-propylpentamethyltriquiloxane,
Acryloxyethoxypropyl di-n-propylpentamethyltrisiloxane, methacryloxyethoxypropyl phenyl octamethyltetrasiloxane, acryloxyethoxypropylphenyl octamethyltetrasiloxane, methacryloxyethoxypropylisobutyltetramethyldisiloxane, acryloxyethoxypropylisobutyl Tetramethyldisiloxane, methacryloxyethoxypropylmethylbis(trimethylsiloxy)
Silane, acryloxyethoxypropylmethylbis(trimethylsiloxy)silane, methacryloxyethoxypropyltris(dimethylcyclohexylsiloxy)silane, acryloxyethoxypropyltris(dimethylcyclohexylsiloxy)silane, methacryloxyethoxypropylpentamethyldisiloxybis(trimethylsiloxy) ) Silane, acryloxyethoxypropylpentamethyldisiloxybis(trimethylsiloxy)
Examples include silane, methacryloxyethoxypropylheptamethylcyclotetrasiloxane, acryloxyethoxypropylheptamethylcyclotetrasiloxane, methacryloxyethoxypropyltetramethyltripropylcyclotetrasiloxane, acryloxyethoxypropyltetramethyltripropylcyclotetrasiloxane, and the like. In addition, examples of esters consisting of a _C1 to _C10 monohydric or polyhydric alcohol and an acid selected from the group consisting of methacrylic acid, acrylic acid, and itaconic acid include methyl methacrylate, methyl acrylate,
Dimethyl itaconate, monomethyl itaconate, ethyl methacrylate, ethyl acrylate, diethyl itaconate, monoethyl itaconate, n-propyl methacrylate, n-propyl acrylate, di-n-propyl itaconate, mono-n-propyl itaconate, isopropyl 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, dibepyl itaconate, monopentyl itaconate, Neopentyl methacrylate, neopentyl acrylate, dineopentyl itaconate,
Mononeopentyl itaconate, n-hexyl methacrylate, n-hexyl acrylate, di-n-hexyl itaconate, mono-n-hexyl itaconate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclohexyl itaconate, monocyclohexyl 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 diacrylate, 1,4-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,6-hexane Diol diacrylate, neopentyl glycol dimethacrylate,
Neopentyl glycol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate, ethylene glycol monomethacrylate, ethylene glycol monoacrylate, diethylene glycol monomethacrylate, diethylene glycol monoacrylate, triethylene glycol monoacrylate methacrylate, triethylene glycol monoacrylate,
These include 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxystyrene methacrylate, and 2-hydroxystyrene acrylate. Among these esters, diesters of polyhydric alcohol and methacrylic acid or acrylic acid,
Triesters and tetraesters are mainly used as crosslinking components, and esters of monohydric alcohol and methacrylic acid or acrylic acid, or diesters of monohydric alcohol and itaconic acid are mainly used as crosslinking components. It is used to improve processability and toughness, and monoesters of polyhydric alcohol and imethacrylic acid or acrylic acid, or monoesters of monohydric alcohol and itaconic acid are mainly used to improve the hydrophilicity of polymer materials. It is used to improve sex. 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. Also, linear or branched fluoroalkyl alcohol having 1 to 20 fluorine atoms, fluoroalkylbenzyl alcohol and methacrylic acid,
Examples of esters consisting of an acid selected from the group consisting of acrylic acid and itaconic acid include 2, 2,
2-tolylfluoroethyl methacrylate, 2,
2,2-trifluoroethyl acrylate, bis-2,2,2-trifluoroethyl itaconate, 2,2,2-trifluoroethyl itaconate, 2,2,3,3-tetrafluoropropyl methacrylate, 2, 2,3-tetrafluoropropyl acrylate, bis-2,2,3,3-tetrafluoropropyl itaconate, 2,2,
3,3-tetrafluoropropyl itaconate,
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, 1H, 1H, 2H, 2H
- heptadecafluorodecyl methacrylate,
1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate, bis-1H, 1H, 2H, 2H-heptadecafluorodecyl itaconate, 1H, 1H,
2H,2H-heptadecafluorooctyl itaconate, 1H,1H-pentadecafluorooctyl methacrylate, 1H,1H-pentadecafluorooctyl acrylate, 1H,1H-pentadecafluorooctyl itaconate, bis-1H,1H-pentadeca Fluorooctyl itaconate, 1H, 1H
-pentafluoropropyl methacrylate, 1H,
1H-pentafluoropropyl itaconate, bis-1H, 1H-pentafluoropropyl itaconate, hexafluoroisopropyl methacrylate, hexafluoroisopropyl acrylate,
Bishexafluoroisopropyl itaconate,
Hexafluoroisopropyl itaconate, 1H,
1H-hexafluorobutyl methacrylate,
1H,1H-heptafluorobutyl acrylate,
Bis-1H,1H-heptafluorobutyl itaconate, o-trifluoromethylbenzyl methacrylate, o-trifluoromethylbenzyl acrylate, bis-o-trifluoromethylbenzyl itaconate, o-trifluoromethylbenzyl itaconate, p- Examples include trifluoromethylbenzyl methacrylate, p-trifluoromethylbenzyl acrylate, bis-p-trifluoromethylbenzyl itaconate, and p-trifluoromethylbenzyl itaconate. These esters mainly act together with the organosiloxane to improve the oxygen permeability of the polymer material, and also improve the optical transparency. The ratio of the organosiloxane and ester constituting the copolymer as a material for contact lenses is preferably about 95 to 20 parts by weight to about 5 to 80 parts by weight, and even more preferably. For 5 to 80 parts by weight of organosiloxane,
Approximately 5 to 95 parts by weight of esters of monohydric alcohols and methacrylic acid or acrylic acid or diesters of monohydric alcohols and itaconic acid, esters of fluoroalkyl alcohols or fluoroalkylbenzyl alcohols and methacrylic acid, acrylic acid or itaconic acid. (particularly when itaconic acid is used, diesters are preferable), up to 50 parts by weight, about 0.5 to 15 parts by weight of diesters, triesters, and tetraesters of polyhydric alcohols and methacrylic acid or acrylic acid; Monoesters of alcohol and methacrylic acid or acrylic acid, monoesters of monohydric alcohol and itaconic acid, monoesters of fluoroalkyl alcohol or fluoroalkylbenzyl alcohol and itaconic acid, or methacrylic acid etc. in place of these esters. A copolymer of about 5 to 10 parts by weight of a hydrophilic monomer is 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,
A polymerization initiator such as diisopropyl peroxydicarbonate is blended, and polymerization is carried out by an ordinary radical polymerization method. The organosiloxane, for example, methacryloxyethoxypropyltris(trimethylsiloxy)silane, can be obtained as follows. First, methacrylic acid allyloxyethyl ester (boiling point 2 mmHg - 64 to 65°C, n ²⁶ _D = 1.4463) was produced with a yield of about 80% using methacrylic acid and allyloxyethanol under a sulfuric acid catalyst. Get it at a rate. Then, about 1 mole of the above allyloxyethyl methacrylate and 10 ^-5 moles of platinum catalyst were added to a three-necked flask equipped with a reflux condenser, thermometer, dropping funnel, and stirrer, and heated to about 75°C. Then 1.1 mol 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 methacryloxyethoxypropyltrichlorosilane. Next, in a three-necked flask equipped with a stirrer, thermometer, and dropping funnel, 0.3 mol of the above methacryloxyethoxypropyl triccorosilane dissolved in 400 ml of dry diethyl ether was added, and this solution was poured into a dry ice isopropanol cooling bath. Cool to 50°C, then add 1 mole of pyridine (approximately 11% excess) in this state over a period of about 2.5 hours, then add 1.2 moles of trimethylsilanol from the dropping funnel, and reduce the temperature after adding trimethylsilanol.
Raise to 30°C and stir for 30 minutes. Then, the pyridinium hydrochloride was separated, the filter cake was washed with diethyl ether, the ether solvent and unreacted substances were distilled off under reduced pressure, the reactant was washed with water, the upper organic layer was separated, and anhydrous When dehydrated with sodium sulfate, then decolorized by adding an appropriate amount of activated carbon, and then filtered through a membrane filter (0.2 μ), methacryloxyethoxypropyltris(trimethylsiloxy)silane (n ²⁰ _D = 1.4240), which is expressed by the following formula, is obtained. ) is obtained with a yield of 80%. The IR and NMR spectra of methacryloxyethoxypropyltris(trimethylsiloxy)silane were measured as shown in FIGS. 1 and 2. For example, methacryloxyethoxypropyltetramethyltripropylcyclotetrasiloxane can be obtained as follows. First, allyloxyethyl methacrylate was obtained in the same manner as above, and in a three-neck flask equipped with a reflux condenser, thermometer, dropping funnel, and stirrer, about 1 mol of allyloxyethyl methacrylate and 10 ^- of platinum catalysts were placed. Add ⁵ moles and
After heating to 90°C, about 1.1 mol of tetramethyltripropylcyclotetrasiloxane is added dropwise.
Then, the reaction was carried out while being kept at 90°C and stirred, and then the unreacted allyloxy methacrylate and tetramethyltripropylcyclotetrasiloxane were distilled off under reduced pressure, and the methacrylic acid aryloxypropyl compound represented by the following formula was distilled off. Tetramethyltripropylcyclotetrasiloxane (n ²⁰ _D
= 1.4413) is obtained. In addition, IR of methacryloxyethoxypropyltetramethyltripropylcyclotetrasiloxane
When the NMR spectrum was measured, the results were as shown in FIGS. 3 and 4. Examples 1 to 10 5 to 80 parts by weight of methacryloxyethoxypropyltris(trimethylsiloxy)silane (hereinafter abbreviated as METS-1), dimethyl itaconate (hereinafter referred to as ester of monohydric alcohol and itaconic acid)
Di-MITA) 7 to 82 parts by weight, 8 parts by weight of methacrylic acid (hereinafter referred to as MA) as a hydrophilic monomer, and triethylene glycol dimethacrylate (abbreviated as MA), an ester of polyhydric alcohol and methacrylic acid, as a crosslinking agent. 0.01 part by weight of a polymerization initiator of V-65 (trade name: 2,2'-azobis(2,4-dimethylvaleronitrile)) was added to 5 parts by weight of the mixture (hereinafter abbreviated as TGD), and the 16mm, height
After pouring into a 10 mm cylindrical polypropylene polymerization mold and purging the upper space with nitrogen, it was kept at 40°C for 20 hours in an oven purged with nitrogen, then kept at 70°C and 90°C for 10 hours each, and then Polymerization is completed by holding at 100°C for 10 hours to obtain a colorless, transparent, hard rod-shaped block. Then, this rod-shaped block is subjected to normal processing to obtain a contact lens. The characteristics of the contact lenses thus obtained are shown in Table 1.

[Table] Examples 11 to 18 45 parts by weight of METS-1, 42 parts by weight of an ester containing an ester consisting of a monohydric alcohol and itaconic acid shown in Table 2, 8 parts by weight of MA as a hydrophilic monomer, and polyester as a crosslinking agent. In the same manner as in Example 1, using 5 parts by weight of TGD, which is an ester of alcohol and methacrylic acid, and 0.03 parts by weight of V-601 (trade name: dimethyl-2,2'-azobisisobutyrate). A colorless, transparent, hard rod-shaped block is obtained, and this is processed to obtain a contact lens. The characteristics of the contact lenses thus obtained are shown in Table 2.

【table】

[Table] Examples 19-40 30-60 parts by weight of various organosiloxanes, 27-57 parts by weight of ester consisting of a monohydric alcohol and an acid selected from the group consisting of methacrylic acid, acrylic acid, and itaconic acid, MA8 weight parts, TGD5 parts by weight,
Using 0.01 parts by weight of V-65, a colorless, transparent and hard rod-shaped block was obtained in the same manner as in Example 1, and this was processed to obtain a contact lens. The characteristics of the contact lenses thus obtained are shown in Table 3.

【table】

[Table] Examples 41-59 30-60 parts by weight of various organosiloxanes as esters of monohydric alcohol and methacrylic acid
EMA52 parts by weight or less, esters of linear or branched fluoroalkyl alcohols or fluoroalkylbenzyl alcohols having 1 to 20 fluorine atoms and methacrylic acid, acrylic acid, itaconic acid, 5 to 35 parts by weight, MA8 A colorless and transparent hard rod-shaped block was obtained in the same manner as in Example 1 using 5 parts by weight of TGD, 5 parts by weight of V-65, and 0.01 part by weight of V-65, and this was processed to obtain a contact lens. The characteristics of the contact lenses thus obtained are shown in Table 4.

【table】

[Table] Examples 60 to 79 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, fluoroalkyl alcohols or fluoroalkylzylben alcohols and methacrylic acid , 95 parts by weight or less of esters with acrylic acid or itaconic acid, diesters, triesters, and tetraesters of polyhydric alcohol and methacrylic acid or acrylic acid as crosslinking agents15
Parts by weight or less, as a hydrophilic monomer, a monoester of a polyhydric alcohol and methacrylic acid or acrylic acid, a monoester of a monohydric alcohol and itaconic acid, a monoester of fluoroalkyl alcohol or fluoroalkylbenzyl alcohol and itaconic acid, Using 10 parts by weight or less of methacrylic acid, acrylic acid or N-vinylpyrrolidone and 0.01 part by weight or less of a free radical polymerization initiator, a colorless, transparent and hard rod-shaped block was obtained in the same manner as in Example 1, and this was processed. Get contact lenses. The characteristics of the contact lenses thus obtained are shown in Table 5.

【table】

【table】

【table】 [Brief explanation of the drawing]

Figures 1 and 3 show the IR of organosiloxane.
The spectra, Figures 2 and 4 are NMR spectra of organosiloxanes.

Claims (1)

[Claims] 1. General formula (However, R ₃ is a C ₁ to C ₆ alkyl group, an aromatic group,
X group is [Formula], R ₂ and R ₂ ' are selected from the group consisting of C ₁ to C ₆ alkyl groups and aromatic groups, and n is 1
is an integer of ~3, m is a number of 0 or 1,
R ₅ is CH ₃ or H, R ₁ and R ₄ do not represent a group but represent a bonding chain connecting R ₁ - R ₄ , or R ₁ is C ₁ to C ₆
selected from the group consisting of alkyl groups, aromatic groups,
R ₄ is selected from the group consisting of a C ₁ to C ₆ alkyl group, an aromatic group, and an X group. ), an ester consisting of an organosiloxane represented by _C1 to _C10 monohydric or polyhydric alcohol, and an acid selected from the group consisting of methacrylic acid, acrylic acid, and itaconic acid, and/or 1 to 20 fluorine atoms. using at least an ester consisting of a linear or branched fluoroalkyl alcohol or fluoroalkylbenzyl alcohol having atoms and an acid selected from the group consisting of methacrylic acid, acrylic acid, and itaconic acid (however,
A contact lens characterized by being copolymerized with methacryloxyethoxypropyltris(trimethylsiloxy)silane and an ester of a _C1 to _C10 monohydric or polyhydric alcohol and methacrylic acid or acrylic acid. material. 2. The contact lens material according to claim 1, wherein the ester is present in a ratio of about 20 to 95 parts by weight to 5 to 80 parts by weight of organosiloxane.