JPH0649140A - Fluorocopolymer and molded product thereof - Google Patents

Abstract

PURPOSE:To obtain a fluorocopolymer having excellent oxygen permeability, being useful for, e.g. an ophthalmic lens, and essentially consisting of two specified kinds of structural units in a specified molar ratio. CONSTITUTION:The fluorocopolymer essentially consists of structural units of formula I (wherein R<1> and R<2> are hydrocarbon groups which may be substituted with fluorine, and at least one of them is a hydrocarbon group substituted with at least three fluorine atoms) and structural units of formula II (wherein R<3> and R<4> are hydrocarbon groups which may contain silicon atoms and/or oxygen atoms, and at least one of them is a hydrocarbon group containing silicon atoms) in such amounts that the structural units of formula I account for 10-90mol% based on all the structural units, and the structural units of formula I account for 10-90mol% based on all the structural units. This copolymer can be produced, for example, by copolymerizing a compound of formula III with a compound of formula IV.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel fluorine-containing copolymer and a molded product using the same. The fluorine-containing copolymer provided by the present invention is excellent in transparency, shape stability, stain resistance, durability, and oxygen permeability, and is a highly oxygen-permeable molded product, particularly a contact lens, an intraocular lens,
It is also useful as an eye lens such as an artificial cornea.

[0002]

2. Description of the Related Art Conventionally, an ophthalmic lens composed of a composition containing polymethacrylate as a main component has been put into practical use. This polymethacrylate has great advantages such as excellent transparency, optical performance, and mechanical properties, but has a problem of poor oxygen permeability. Wearing a contact lens made of such a material having poor oxygen permeability reduces the amount of oxygen supplied to the eyeball, and wearing this for a long time often causes hyperemia, edema, and other corneal disorders.

In order to improve the oxygen permeability of the methacrylic acid ester-based polymer, a copolymer with a vinyl-based diester monomer capable of introducing a large amount of fluorine atom or silicon atom into the monomer molecule has been proposed. Attention has been paid to, for example, a fluoroalkyl itaconate-based monomer or an oligosiloxanyl itaconate-based monomer and a methacrylic acid ester-based monomer in which a fluorine atom or an oligosiloxane bond is introduced in the itaconic acid diester molecule. A contact lens made of a polymer has been proposed (JP-A-60-32022).
JP-A-62-92914 and JP-A-6-92914
3-210115 gazette).

However, although these copolymers have improved oxygen permeability as compared with conventional polymethacrylates such as polymethylmethacrylate (PMMA), they are not yet sufficient, and the oxygen permeability is further improved. Polymers are needed.

Further, a dialkyl fumarate, which is one of vinyl-based diester monomers, has been proposed, but this is inferior in copolymerizability with a methacrylic acid ester monomer and
Even if it can be copolymerized, there is a problem that this polymer is very brittle and inferior in mechanical properties (JP-A-62-99720 and JP-A-62-212).
618).

Further, in the specification of US Pat. No. 4,977,229, a contact lens and an intraocular lens using a polymer obtained by polymerizing a vinyl compound (for example, an acrylate) having a siloxane moiety introduced by an ether bond at the α-position. However, there is no clear description about the physical properties of the obtained polymer, especially the oxygen permeability.

The first object of the present invention is that the transparency, shape stability, stain resistance and durability are at a level at which it can be practically used as a highly oxygen permeable material such as an ophthalmic lens, and it has excellent oxygen permeability. It is to provide a novel fluorine-containing copolymer that provides a raw material. A second object of the present invention is to provide a highly oxygen-permeable molded article (particularly, an ophthalmic lens) made of the polymer.

[0008]

Means for Solving the Problems As a result of intensive investigations by the present inventors to develop a novel material having excellent polymerizability of raw material monomers and excellent oxygen permeability, a specific fluorine-containing α −
A molded product made of a polymer obtained by copolymerizing a substituted acrylate-based monomer and a specific silicon-containing α-substituted acrylate-based monomer as an essential component has a mechanical property and a thermal property that are practical as an ophthalmic lens. It has been found that it has transparency, stain resistance, and excellent oxygen permeability. According to the present invention, the above first object is to provide the following general formula (1):

[0009]

[Chemical 3]

(In the formula, R ¹ and R ² each represent a hydrocarbon group which may be substituted with a fluorine atom, and R 1
^At least one of ¹ and R ² represents a hydrocarbon group substituted with at least 3 fluorine atoms. ) One or more structural units (A) represented by the formula (II) and the following general formula (II)

[0011]

[Chemical 4]

(In the formula, R ³ and R ⁴ each represent a hydrocarbon group which may contain a silicon atom and / or an oxygen atom, and at least one of R ³ and R ⁴ is
It represents a hydrocarbon group containing at least one silicon atom. 1) or 2 or more kinds of structural units (B) represented by the formula (1) are essential structural units, and the structural unit (A) is 1 in all structural units.
0-90 mol%, the structural unit (B) is 10 in all structural units
This is accomplished by providing a fluorine containing polymer having 90 mol%.

The second object of the present invention is achieved by a molded article made of the above polymer.

The structural unit (A) corresponds to the corresponding general formula (I ')

[0015]

[Chemical 5]

It is derived from a fluorine-containing α-substituted acrylate monomer represented by the formula (wherein R ¹ and R ² are as defined above).

The hydrocarbon group which is the same as or different from R ² represented by R ¹ in the above general formulas (I) and (I ′) and which may be substituted with a fluorine atom usually has 1 carbon atom. -20, preferably 1-15, more preferably 1-
10 hydrocarbon groups, for example, the following groups can be mentioned.

[0018]

[Chemical 6]

Of these groups, particularly preferred groups are shown below.

[0020]

[Chemical 7]

Further, the above general formulas (I) and (I ')
The hydrocarbon group which is the same as or different from R ¹ represented by R ² and which may be substituted with a fluorine atom usually has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, and more preferably 1 to 12 carbon atoms. And the following groups can be given as examples.

[0022]

[Chemical 8]

Of these groups, particularly preferred groups are shown below.

[0024]

[Chemical 9]

Fluorine-containing α-represented by the general formula (I ')
Among the substituted acrylate-based monomers, preferable monomers are shown below.

[0026]

[Chemical 10]

[0027]

[Chemical 11]

[0028]

[Chemical 12]

Of these fluorine-containing α-substituted acrylate-based monomers, particularly preferable monomers are shown below.

[0030]

[Chemical 13]

[0031]

[Chemical 14]

When using these monomers (I '), one kind or two or more kinds can be used.

Further, the structural unit (B) corresponds to the corresponding general formula (II ')

[0034]

[Chemical 15]

(Wherein R ³ and R ⁴ are as defined above) and derived from a silicon-containing α-substituted acrylate monomer.

The above general formulas (II) and (II ')
In R ^{3, the} hydrocarbon group optionally containing a silicon atom and / or an oxygen atom is usually one having 1 carbon atom.
To 25, preferably a hydrocarbon group having 1 to 21 carbon atoms, and examples thereof include the following groups.

[0037]

[Chemical 16]

Of these groups, particularly preferred groups are shown below.

[0039]

[Chemical 17]

Further, the above general formulas (II) and (I
The hydrocarbon group which may contain a silicon atom and / or an oxygen atom represented by R ⁴ in I ′) is usually a hydrocarbon group having 1 to 25 carbon atoms, preferably 1 to 15 carbon atoms. The following groups can be given as examples.

[0041]

[Chemical 18]

Of these groups, particularly preferred groups are shown below.

[0043]

[Chemical 19]

Silicon-containing α represented by the general formula (II ')
Among the -substituted acrylate-based monomers, preferred monomers are shown below.

[0045]

[Chemical 20]

[0046]

[Chemical 21]

[0047]

[Chemical formula 22]

Of these silicon-containing α-substituted acrylate-based monomers, particularly preferred monomers are shown below.

[0049]

[Chemical formula 23]

[0050]

[Chemical formula 24]

When using these monomers (II '), one kind or two or more kinds can be used.

The fluorine-containing copolymer of the present invention comprises the structural unit (A) represented by the general formula (I) and the general formula (II).
The structural unit (B) represented by is an essential structural unit, the structural unit (A) is contained in 10 to 90 mol% in all structural units, and the structural unit (B) is contained in 10 to 90 mol% in all structural units.

The content ratio of the structural unit (A) and the structural unit (B) is in the range of 10 to 90 mol% with respect to all the structural units, and is appropriately determined according to the purpose of use of the fluorine-containing copolymer of the present invention. To be elected.

In order to use a molded product obtained from the copolymer as an oxygen permeable material, the structural unit (A) is preferably in the range of 10 to 80 mol% and preferably in the range of 20 to 70 mol% in all the structural units. More preferable. The structural unit (B) is preferably in the range of 10 to 80 mol% in all structural units,
The range of up to 70 mol% is more preferred.

When the content ratio of the structural unit (A) is less than 10 mol%, the oxygen permeability of the obtained molded article is lowered. On the other hand, if the content exceeds 80 mol%, the mechanical properties of the resulting molded article tend to deteriorate, which is not preferable for ophthalmic lenses.

When the content ratio of the structural unit (B) is less than 10 mol%, the oxygen permeability of the obtained molded article is lowered. On the other hand, if the content exceeds 80 mol%, the mechanical properties of the resulting molded article tend to deteriorate, which is not preferable for ophthalmic lenses.

In the fluorine-containing copolymer of the present invention, structural units other than one or more structural units (A) and one or more structural units (B) are:
Examples thereof include structural units derived from vinyl monomers such as radically polymerizable vinyl monomers, fluorine-containing vinyl monomers, silicon-containing vinyl monomers, and crosslinkable polyfunctional vinyl monomers. Preferred examples of vinyl monomers are shown below.

Methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, t-butyl (meth) acrylate, neopentyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, methyl (α) −
Hydroxymethyl) acrylate, ethyl (α-hydroxymethyl) acrylate, isopropyl (α-hydroxymethyl) acrylate, t-butyl (α-hydroxymethyl) acrylate, neopentyl (α-hydroxymethyl) acrylate, cyclohexyl (α-hydroxymethyl) Acrylate, methyl (α-acetyloxymethyl) acrylate, methyl (α-propionyloxymethyl) acrylate, methyl (α-isobutyryloxymethyl) acrylate, methyl (α-pivaloyloxymethyl) acrylate, methyl (α- Cyclohexanecarbonyloxymethyl) acrylate, ethyl (α-acetyloxymethyl) acrylate, ethyl (α-propionyloxymethyl) acrylate, ethyl (α-isobutyryloxime ) Acrylate, ethyl (α-pivaloyloxymethyl) acrylate, ethyl (α-cyclohexanecarbonyloxymethyl) acrylate, isopropyl (α-acetyloxymethyl) acrylate, isopropyl (α-propionyloxymethyl) acrylate, isopropyl (α -Isobutyryloxymethyl) acrylate, isopropyl (α
-Pivaloyloxymethyl) acrylate, isopropyl (α-cyclohexanecarbonyloxymethyl) acrylate, t-butyl (α-acetyloxymethyl) acrylate, t-butyl (α-propionyloxymethyl) acrylate, t-butyl (α- Isobutyryloxymethyl) acrylate, t-butyl (α-pivaloyloxymethyl) acrylate, t-butyl (α-cyclohexanecarbonyloxymethyl) acrylate, neopentyl (α-acetyloxymethyl) acrylate,
Neopentyl (α-propionyloxymethyl) acrylate, neopentyl (α-isobutyryloxymethyl) acrylate, neopentyl (α-pivaloyloxymethyl) acrylate, neopentyl (α-cyclohexanecarbonyloxymethyl) acrylate, vinyl acetate, propionic acid Vinyl, vinyl pivalate, ethyl vinyl ether, n-butyl vinyl ether, styrene, p-methylstyrene, o-chlorostyrene, p-chlorostyrene, (meth) acrylic acid amide, 2-hydroxyethyl (meth) acrylate, N-vinyl. Radical polymerizable vinyl monomers such as pyrrolidone, vinyl pyridine, methacrylic acid, acrylic acid, itaconic acid, (α-hydroxymethyl) acrylic acid; methylbis (trimethylsiloxy) silylpropyl ( (Meth) acrylate, tris (trimethylsiloxy) silylpropyl (meth) acrylate, tris (pentamethyldisiloxanyloxy)
Silylpropyl (meth) acrylate, methylbis (trimethylsiloxy) silylpropylglycerol mono (meth) acrylate, tris (trimethylsiloxy)
Silylpropyl glycerol mono (meth) acrylate, tris (pentamethyldisiloxanyloxy) silylpropyl glycerol mono (meth) acrylate, methylbis (trimethylsiloxy) silylpropyl (α-
Hydroxymethyl) acrylate, tris (trimethylsiloxy) silylpropyl (α-hydroxymethyl) acrylate, methylbis (trimethylsiloxy) silylpropylglycerol mono (α-hydroxymethyl) acrylate, tris (trimethylsiloxy) silylpropylglycerol mono (α-hydroxy Silicon-containing vinyl monomers such as methyl) acrylate; 2,2,2-trifluoroethyl (meth) acrylate, 2,2,2-
Trifluoro-1-trifluoromethylethyl (meth)
Acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2,2,3
4,4,4-hexafluorobutyl (meth) acrylate, 2,2,3,3,4,4,5,5-octafluoropentyl (meth) acrylate, 2,3,4,5,5,5
5-hexafluoro-2,4-bis (trifluoromethyl) pentyl (meth) acrylate, 2,2,3,3,
4,4,5,5,6,6,7,7-dodecafluoroheptyl (meth) acrylate, 2-hydroxy-4,4
5,5,6,7,7,7-octafluoro-6-trifluoromethylheptyl (meth) acrylate, 2-hydroxy-4,4,5,5,6,6,7,7,8,9,
9,9-Dodecafluoro-8-trifluoromethylnonyl (meth) acrylate, 2-hydroxy-4,4
5,5,6,6,7,7,8,8,9,9,10,1
1,11,11-hexadecafluoro-10-trifluoromethylundecyl (meth) acrylate, 3,3
4,4,5,5,6,6,6-nonafluorohexyl (meth) acrylate, 3,3,4,4,5,5,6
6,7,7,8,8,8-tridecafluorooctyl (meth) acrylate, 3,3,4,4,5,5,6,6
6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl (meth) acrylate, 2,2
2-trifluoroethyl (α-hydroxymethyl) acrylate, 2,2,2-trifluoro-1-trifluoromethylethyl (α-hydroxymethyl) acrylate, 2,2,3,3,3-pentafluoropropyl ( α
-Hydroxymethyl) acrylate, 3,3,4,4
5,5,6,6,6-nonafluorohexyl (α-hydroxymethyl) acrylate, 3,3,4,4,5
5,6,6,7,7,8,8,8-tridecafluorooctyl (α-hydroxymethyl) acrylate, 3,
3,4,4,5,5,6,6,7,7,8,8,9,
9,10,10,10-Heptadecafluorodecyl (α
-Fluorine-containing vinyl monomers such as -hydroxymethyl) acrylate; divinylbenzene, vinyl (meth) acrylate, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate , Dipropylene glycol di (meth)
Acrylate, neopentyl glycol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, bis (2-methoxycarbonyl-2-propenyl) ether, bis (2-ethoxycarbonyl-2-propenyl) ether, bis (2-t-butyloxycarbonyl-2-propenyl) ether, bis (2-neopentyloxycarbonyl-2-propenyl) ether,
Bis (2 '-(2,2,2-trifluoroethoxycarbonyl) -2'-propenyl) ether, diallyl phthalate, diallyl terephthalate, trimethylolpropane tri (meth) acrylate, triallyl trimellitate, triallyl cyanurate, etc. And the cross-linkable polyfunctional vinyl monomer. By using these alone or in combination, it is possible to improve the thermal stability, mechanical strength and processability of the obtained fluorine-containing copolymer. The content ratio of the structural unit derived from the vinyl monomer is appropriately selected within the range of 80 mol% or less based on the total structural units according to the purpose of use of the fluorine-containing copolymer of the present invention.

The fluorine-containing copolymer of the present invention includes, for example, a fluorine-containing α-substituted acrylate monomer represented by the general formula (I ') and a silicon-containing α-represented by the general formula (II').
It can be produced by carrying out a polymerization reaction in the presence of a polymerization initiator with a monomer mixture containing a substituted acrylate-based monomer and, if necessary, another copolymerization component.

The polymerization initiator can be selected from one or more members selected from the group consisting of organic peroxides and azo compounds. Examples of the organic peroxide include acetyl peroxide, benzoyl peroxide, p-
Chlorobenzoyl peroxide, isobutyryl peroxide, bis (3,5,5-trimethylhexanoyl) peroxide, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, dit-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,1 -Di-t-butylperoxy-3,3,5-trimethylcyclohexane,
1,1-di-t-butylperoxycyclohexane, 2,
2'-di-t-butylperoxybutane, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxydiisobutyrate, t-butylperacetate, t-butyl Examples thereof include perbenzoate, t-butyl peroxyisopropyl carbonate, diisopropyl peroxydicarbonate and lauroyl peroxide, and examples of the azo compound include azobisisobutyronitrile, azobiscyclohexanecarbonitrile and dimethylazobis. Examples thereof include isobutyrate and azobisdimethylvaleronitrile.

The temperature during the polymerization is preferably in the range of 30 to 150 ° C, more preferably 50 to 120 ° C. The time required for the polymerization is preferably in the range of 1 to 150 hours, more preferably 10 to 100 hours.

In addition to the above-mentioned polymerization method, a polymerization method such as photopolymerization or radiation polymerization may be adopted.

The molecular weight of the fluorine-containing copolymer of the present invention is
When a high oxygen-permeable molded article is intended, the number average molecular weight (converted to polystyrene) determined by gel permeation chromatography is usually 10,000 to 500.
It is preferably in the range of 000, and 100,000 to 5
The range of 00000 is more preferable.

Depending on the type of raw material monomer and the polymerization conditions, the obtained fluorine-containing copolymer may not be dissolved in the solvent for measuring the molecular weight, and the molecular weight may not be determined by the above method. Of course, fluorine-containing copolymers are also included in the present invention.

In order to obtain a molded product from the fluorine-containing copolymer of the present invention, the glass transition temperature (Tg) of the fluorine-containing copolymer measured by a differential scanning calorimeter (DSC) is 30 to 150 ° C. It is desirable to be in the range of, especially in the range of 60 to 100 ° C.

The molded product obtained from the fluorine-containing copolymer of the present invention has excellent oxygen permeability, and its oxygen permeability coefficient (DK value: unit 10 ⁻¹⁰ cc (STP) cm / cm ² · sec.
cmHg) is usually 60 or more. The oxygen permeability coefficient of the molded article having more excellent oxygen permeability is 70 or more, and the oxygen permeability coefficient of the molded article having particularly excellent oxygen permeability is 80 or more. Here, the oxygen permeability coefficient is a value obtained by measuring a homogeneous thin film sample (thickness: 200 to 400 μm) or an ophthalmic lens using a Seikaken-type film oxygen permeability meter. This technique measures the amount of oxygen that has permeated a film or an ophthalmic lens fixed on the tip of an oxygen electrode in pure water saturated with oxygen at 35 ° C. as the amount of change in reduction current.

It is also possible to add a colorant such as a dye and an additive such as an ultraviolet absorber to the raw material monomer to perform polymerization.

Fluorine-containing compound containing the structural unit (A) provided by the present invention in an amount of 10 to 80 mol% based on all structural units and the structural unit (B) in an amount of 10 to 80 mol% based on all structural units. The molded product obtained from the copolymer has mechanical properties and thermal properties that can be practically used as an ophthalmic lens, is excellent in oxygen permeability, and is excellent in transparency, wearing feeling and stain resistance.

In order to obtain a highly oxygen-permeable molded article comprising the fluorine-containing copolymer of the present invention, for example, an ophthalmic lens such as a contact lens, a fluorine-containing α-substituted acrylate group represented by the general formula (I ′) is used. A copolymer obtained by copolymerizing a monomer, a silicon-containing α-substituted acrylate-based monomer represented by the general formula (II ′), and a monomer mixture containing other copolymerization components as necessary, is obtained. A known method such as cutting and polishing may be performed from the coalescence. It is also possible to carry out the above copolymerization in a mold to obtain a contact lens or the like.

[0070]

EXAMPLES The present invention will be described in detail below with reference to reference examples and examples, but the present invention is not limited thereto. The fluorine content of the fluorine-containing polymer is measured by using ion chromatography.

Reference Example 1 3,3,4,4,5,5,6,6,7,7,8,8,8
-500 g of tridecafluorooctyl acrylate, 97 g of formalin, 1,4-diazabicyclo [2.2.
2] Add 4.9 g of octane to dioxane and add 5 at room temperature.
Reacted for days. After the reaction, dioxane was distilled off, the residue was dissolved in methylene chloride, washed with weakly acidic water and pure water, and the organic layer was dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the filtrate is distilled off to remove the solvent and purified by distillation.
4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl (α-hydroxymethyl) acrylate was obtained. This was dissolved in THF, pyridine was added, and a THF solution of pivaloyl chloride was added dropwise while stirring with ice cooling. After stirring overnight at room temperature, the precipitate was filtered off, THF was distilled off, the residue was dissolved in methylene chloride, washed with weakly acidic water and pure water, and the organic layer was dried over anhydrous magnesium sulfate. After magnesium sulfate was filtered off, the filtrate was distilled off to remove the solvent and purified by distillation to obtain a colorless and transparent viscous liquid. The liquid is ¹ H-NMR
The analysis confirmed that it was represented by the following structural formula.

[0072]

[Chemical 25]

Reference Example 2 Instead of pivaloyl chloride in Reference Example 1, 4,
The corresponding compound was obtained by using 4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononanoic acid chloride. It was confirmed by ¹ H-NMR analysis that this compound had the following structural formula.

[0074]

[Chemical formula 26]

Reference Example 3 Tris (trimethylsiloxy) silylpropyl (α-acetyloxymethyl) acrylate is obtained as follows. In a three-necked flask equipped with a stirrer, 500 g of acrylic acid allyl ester, 362 g of formalin (as formaldehyde), and 18.4 diazabicyclo [2.2.2] octane as a catalyst, 18.4 g, dioxane 1200 ml, and p-as a polymerization inhibitor. Allyl (α-hydroxymethyl) acrylate was obtained by charging 15.6 mg of methoxyphenol and stirring at room temperature for 5 days. Then, the allyl (α-hydroxymethyl)
Allyl (α-acetyloxymethyl) acrylate was obtained by the usual esterification method using acrylate and acetyl chloride.

A three-necked flask equipped with a reflux condenser, a thermometer, a dropping funnel and a stirrer was charged with 200 g of allyl (α-acetyloxymethyl) acrylate and 5.6 mg of hexachloroplatinate (IV) acid hexahydrate, and 70-80 Heat to ℃,
After dropping 162 g of trichlorosilane, the mixture was stirred at the same temperature for 5 hours. Unreacted allyl (α-acetyloxymethyl) acrylate and trichlorosilane are distilled off,
(Α-acetyloxymethyl) acryloxypropyltrichlorosilane was obtained. Next, 335 g of (α-acetyloxymethyl) acryloxypropyltrichlorosilane and 1 liter of dry diethyl ether were charged into a three-necked flask equipped with a stirrer, a thermometer, and a dropping funnel, and cooled to −50 ° C. in a dry ice-isopropanol bath. Then 2
After 49 g of pyridine was added over 1 hour and then 331 g of trimethylsilanol was added over 3 hours at the same temperature, the temperature was raised to 30 ° C. and the mixture was further stirred for 1 hour. Then, the pyridine hydrochloride formed thereafter was filtered off, the solvent and unreacted substances were distilled off under reduced pressure, the residue was washed with water, the organic layer was dehydrated and treated with activated carbon, and then filtered with a Menplan filter. A colorless transparent liquid was obtained by distilling the obtained liquid. It was confirmed by ¹ H-NMR analysis that the liquid had the following structural formula.

[0077]

[Chemical 27]

Reference Example 4 The reaction was performed in the same manner as in Reference Example 3 except that pivaloyl chloride was used instead of acetyl chloride in Reference Example 3, to obtain the corresponding compound. This compound is ¹
It was confirmed by 1 H-NMR analysis that the compound had the following structural formula.

[0079]

[Chemical 28]

Reference Example 5 Reaction was carried out in the same manner as in Reference Example 4 except that methyldichlorosilane was used in place of trichlorosilane, 83 g of pyridine and 113.5 g of trimethylsilanol were used in Reference Example 4, and the reaction was carried out. A compound was obtained. It was confirmed by ¹ H-NMR analysis that this compound had the following structural formula.

[0081]

[Chemical 29]

Example 1 Compound obtained in Reference Example 2 and tris obtained in Reference Example 4
(Trimethylsiloxy) silylpropyl (α-pivalloy
Luoxymethyl) acrylate, and ethyl (α-pi
Valoyloxymethyl) acrylate is mixed in the specified ratio.
Dimethyl azobisisobutyrate as a polymerization initiator
, Agitate and mix thoroughly, and freeze vacuum degas in the polymerization tube.
And sealed the tube. Put the polymerization tube in a constant temperature bath at 60 ° C for 24 hours.
Polymerization was performed by heating for a while. After polymerization, reprecipitation purification
The polymer was taken out. The polymerizability was good. Vacuum drying
After that, the polymer is sandwiched between flat metal plates and pressed in a heating and melting state,
A transparent film (thickness: 210μ
m) was prepared and the oxygen permeability coefficient was measured. Polymerization obtained
Body structure, number average molecular weight (polystyrene equivalent) and acid
The elementary transmission coefficient is shown in Table 1. The oxygen permeability coefficient is
It was measured at 35 ° C. using a film type oxygen permeation meter.
The composition ratio of the copolymer is that of a heavy chloroform solution. ¹H-
NMR spectrum measurement, elemental analysis and fluorine content analysis
(Ion chromatography).

[0083]

[Table 1]

The structural unit (C) in the table indicates a structural unit other than the structural unit (A) and the structural unit (B), and the same applies to the following tables.

Example 2 3,3,4,4,5,5,6,6 obtained in Reference Example 1
7,7,8,8,8-Tridecafluorooctyl (α-
Pivaloyloxymethyl) acrylate and tris (trimethylsiloxy) silylpropyl (α-acetyloxymethyl) acrylate obtained in Reference Example 3 and methyl (α-pivaloyloxymethyl) acrylate were mixed at a predetermined ratio, Dimethylazobisisobutyrate was added as a polymerization initiator, thoroughly mixed with stirring, freeze-vacuum degassed in a polymerization tube, and sealed. Put the polymerization tube in a constant temperature bath, 60 ℃
Polymerization was carried out by heating for 24 hours. After the polymerization was completed, the polymer was taken out by reprecipitation purification. The polymerizability was good.
After vacuum drying, the polymer is sandwiched between flat metal plates, heated in a molten state, pressurized and allowed to cool to give a transparent film (thickness: 2
20 μm) was prepared and the oxygen permeability coefficient was measured. Table 1 shows the structure, number average molecular weight (in terms of polystyrene), and oxygen permeability coefficient of the obtained polymer.

Examples 3 to 4 By the same method as in Example 2, various raw material monomer mixtures shown in Table 2 were polymerized to prepare films, and the oxygen permeation coefficient was measured. The structural unit composition, number average molecular weight and oxygen permeability coefficient are shown in Table 2.

[0087]

[Table 2]

Comparative Example 1 3, 3, 4, 4, obtained in Reference Example 1 in Example 2
5,5,6,6,7,7,8,8,8-tridecafluorooctyl (α-pivaloyloxymethyl) acrylate and methyl (α-pivaloyloxymethyl) acrylate and tris (trimethylsiloxy) Polymerization was performed in the same manner except that tris (trimethylsiloxy) silylpropyl methacrylate was used instead of silylpropyl (α-acetyloxymethyl) acrylate, and a film (thickness: 230 μm) was prepared from the obtained polymer, Similarly, the oxygen permeability coefficient was measured. Table 3 shows the structure, number average molecular weight (in terms of polystyrene), and oxygen permeability coefficient of the obtained polymer. The oxygen permeability coefficient was measured at 35 ° C. by using a film oxygen permeability meter of Seikaken type. Also,
The composition ratio of the copolymer is ¹ H-NMR of a heavy chloroform solution.
It was determined by spectral measurement, elemental analysis and fluorine content analysis (ion chromatography). The structural unit (C) and the structural unit (D) in the table are structural units other than the structural unit (A) and the structural unit (B).

[0089]

[Table 3]

Comparative Example 2 Using the tris (trimethylsiloxy) silylpropyl (α-acetyloxymethyl) acrylate and the methyl (α-pivaloyloxymethyl) acrylate obtained in Reference Example 3, the same procedure as in Example 2 was performed. Polymerization was carried out, a film (thickness: 220 μm) was prepared from the obtained polymer, and the oxygen permeability coefficient was measured in the same manner. Table 3 shows the structure, number average molecular weight (in terms of polystyrene), and oxygen permeability coefficient of the obtained polymer. The oxygen permeability coefficient was measured at 35 ° C. by using a film oxygen permeability meter of Seikaken type. Also,
The composition ratio of the copolymer is ¹ H-NMR of a heavy chloroform solution.
It was determined by spectral measurement, elemental analysis and fluorine content analysis (ion chromatography).

Example 5 35 parts by weight of the compound obtained in Reference Example 2 and the tris (trimethylsiloxy) silylpropyl (α obtained in Reference Example 3)
30 parts by weight of acetyloxymethyl) acrylate, 15 parts by weight of methyl (α-pivaloyloxymethyl) acrylate, 10 parts by weight of methyl methacrylate and 10 parts by weight of ethylene glycol dimethacrylate were mixed, and azobis was used as a polymerization initiator. 0.15 parts by weight of dimethylvaleronitrile were added. This mixture was placed in a 20 ml polypropylene test tube, the gas phase part was replaced with nitrogen, and the container was sealed. This was placed in a circulating constant temperature water tank, and polymerization was carried out at 35 ° C. for 65 hours, 40 ° C. for 24 hours, and 50 ° C. for 5 hours. Further, the test tube was transferred to a circulation type drier, and heat polymerization was carried out at 80 ° C. for 2 hours, 100 ° C. for 1 hour, and finally 110 ° C. for 1 hour. By cutting and polishing the obtained polymer, a colorless and transparent hard contact lens excellent in oxygen permeability was obtained.

[0092]

INDUSTRIAL APPLICABILITY The novel fluorine-containing copolymer provided by the present invention has excellent oxygen permeability, and its molded product is particularly useful as an ophthalmic lens or the like.

Claims (4)

[Claims] 1. The following general formula (I): (In the formula, R ¹ and R ² each represent a hydrocarbon group which may be substituted with a fluorine atom, and R ¹ and R ²
At least one of the above represents a hydrocarbon group substituted with at least three fluorine atoms. ) One or more structural units (A) represented by the following formula and the following general formula (II): (In the formula, R ³ and R ⁴ are a silicon atom and / or
Or represents a hydrocarbon group which may contain an oxygen atom,
And at least one of R ³ and R ⁴ represents a hydrocarbon group containing at least one silicon atom. ) 1 type or 2 or more types of structural unit (B) shown by these are made into an essential structural unit, and structural unit (A) is 10-90 mol% in all the structural units,
A fluorine-containing copolymer having 10 to 90 mol% of the structural unit (B) in all structural units. 2. A molded product comprising the fluorine-containing copolymer according to claim 1. 3. The molded article has high oxygen permeability.
The described molded article. 4. The molded product according to claim 3, wherein the molded product having high oxygen permeability is an ophthalmic lens.