JPH0312418A - Fluorine-containing resin and oxygen-permeable molded article - Google Patents

Abstract

PURPOSE:To provide the subject resin having dioxycyclobutane skeleton, selected from among high-molecular weight polycarbonate, polyester carbonate and polyester, having excellent oxygenpermeability, mechanical strength and hardness and useful for contact lens and artificial lung. CONSTITUTION:The objective resin is selected from polycarbonate, polyester carbonate and polyester containing 1,3-dioxycyclobutane skeleton of formula I (R<1> to R<4> are saturated aliphatic hydrocarbon group having F atom substituting at least one H atom) and having a number-average molecular weight of >=5,000 (preferably 10,000-100,000). The resin is preferably the polymer of formula II (A is <=20C hydrocarbon group; x and y are molar fractions and x:y is 0:100 to 100:0).

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a fluorine-containing resin and an oxygen permeable molded article made of the resin.

The oxygen permeable molded article provided by the present invention has excellent oxygen permeability and mechanical strength, and has sufficient hardness. The oxygen-permeable molded article of the present invention not only efficiently transmits oxygen, but also selectively transmits oxygen gas compared to nitrogen gas.

(Prior art and problems to be solved by the invention) In recent years, studies have been made to use polymeric materials that efficiently transmit oxygen for medical applications such as contact lenses and artificial lungs, and as oxygen-enriching membranes to increase combustion efficiency. Many things have been done.

For example, contact lenses include modified (soft) contact lenses that do not use hydrophilic polymers whose main components are 2-hydroxyethyl methacrylate and vinylpyrrolidone, and hard (hard) contact lenses that use hard polymers such as polymethyl methacrylate. Contact lenses are used.

Although hard contact lenses are less comfortable to wear than soft contact lenses, they are less susceptible to contamination and are therefore easier to clean, are more durable, and have superior vision correction effects. have a long length.

However, hard contact lenses containing polymethyl methacrylate as a main component have extremely poor oxygen permeability and have a serious drawback in that they are difficult to wear for long periods of time due to corneal physiology.

In order to improve the oxygen permeability of rigid contact lenses, a method to modify the material is to increase the content of silicone methacrylate.

A method of containing a fluorine atom and a method of coexisting a silicone methacrylate and a fluorine atom have been proposed. However, in any case, increasing the oxygen permeability lowers the hardness, resulting in poor processability as a lens, as well as the problem of not being easily contaminated by fat buying, etc., and the use of expensive raw materials. There is a point. For this reason, it is desired to develop a material for hard contact lenses that has good oxygen permeability and hardness.

As an oxygen-enriching membrane, siloxane-based polymers such as polydimethylsiloxane, bisphenol A polycarbonate/polydimethylsiloxane, and poly(
Polyolefins such as 4-methylpentene-1), poly(2,6-dimethyl-1,4-)unicine oxide)
etc. are known.

Siloxane-based polymers proposed as oxygen-enriched membranes have poor processability. Poly(4-methylpentene-1) is relatively brittle, and the mechanical strength of molded products is not necessarily sufficient, and furthermore, there are problems in that oxygen permeability decreases after heat treatment. In addition, yNl, 7(2,6-cymethyl-1
, 4-) Uniform oxide) K has a problem in that it lacks thermal stability during molding.

One object of the present invention is to provide a resin that provides a molded article with excellent oxygen permeability and mechanical strength and sufficient hardness.

Another object of the present invention is to provide a resin that provides a molded article that not only efficiently transmits oxygen gas but also selectively transmits oxygen gas compared to nitrogen gas.

Yet another object of the present invention is to provide a molded article that selectively and efficiently transmits oxygen gas, has excellent mechanical strength, and has sufficient hardness.

(Means for Solving the Problems) According to the present invention, the above-mentioned object is achieved by forming a compound having a 1,3-dioxycyclobutane skeleton represented by the following general formula (1) and having a number average molecular weight of 5,000. This is accomplished by providing a resin selected from the group consisting of polycarbonate, polyester carbonate, and polyester, and also by providing an entire oxygen-permeable molded article made of the resin.

(In the formula, R1, B21B3 and R4 each represent a saturated aliphatic hydrocarbon group in which at least one hydrogen atom is substituted with a fluorine atom.) The above general formula (1) K#
The saturated aliphatic hydrocarbon group in which at least one of the hydrogen atoms represented by each of the groups is substituted with a fluorine atom has 1 to 4 carbon atoms.
Those are preferable, and specific examples include the following groups.

-CH2F, -C! (F2.-CF3,-CHzCF
3, -CF2CF'3, -R1 in formula (1),)
t2Th [? A resin having a 1,3-dioxycyclobutane skeleton in which +' and R4 are all trifluoromethyl groups is preferred from the viewpoint of ease of production.

Among the resins of the present invention, resins represented by the following general formula ('') are preferable.

[In the formula, R', I, R3 and 4 are as defined above, and A is a divalent hydrocarbon having 20 or less carbon atoms -CH2
CHz-1-CHI CH2CH2-1-CH2CH2
CHI CH2-Among these, the following groups are more preferred.

=O:100 to Zoo:0. ] The hydrocarbon group represented by A in the above general formula (ll) includes a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. 2 to 20 divalent aliphatic hydrocarbon groups are preferred, and specific examples include the following groups.

Particularly preferred are groups represented by K. The present invention may be used, or 2fi1M or more may be mixed.

When X is 0, the resin is polyester, when y is 0, the resin is polycarbonate, and when both X and y are not KO, the resin is polyester carbonate. X and y are x:y=50:50-100:O
A molded article made of a resin having the following relationship is preferable because it has particularly excellent oxygen permeability.

[Kai The resin of the present invention may contain other structural units as long as the excellent properties described below are not impaired.

The resin of the present invention can be produced by a melt method or a solution method, which mainly involves transesterification, which is generally used in producing polycarbonate or polyester. The molecular weight of the resin of the present invention is not particularly limited as long as it has a slenderness that provides strength that can be used as a molded article.
Usually, the number average molecular weight (polystyrene equivalent) determined by gel permeation chromatography is s, ooo
that's all.

Preferably it is 10,000 or more. Although there is no critical meaning to the upper limit of the molecular weight, it is preferable that the number average molecular weight of the resin is usually 100.000 or less from the viewpoint of ease of production and moldability of the resin.

The resin of the present invention has excellent thermal stability and moldability.

The resin of the present invention can be processed into molded bodies having various shapes by any known method. A film-like or fibrous molded article can be obtained by subjecting the resin to a conventional melt molding method, or by dissolving the resin in a suitable solvent and then subjecting it to a conventional solution molding method. Note 1: Contact lenses can be made by molding the resin of the present invention into a molded body of an appropriate size by any method, and cutting the molded body by a conventional method.

Although the molded product obtained from the resin of the present invention varies depending on the chemical structure of the resin, it usually has a size of 5 x 10"-'-/
c! It has an oxygen permeability coefficient (Paw) of 0 argon R[() of a*5ec-tanHf or more.T also has an oxygen permeability coefficient (DK) of the molded body in water of usually 5XIQ'' d
・1: III/crA -sec -- or higher.

Furthermore, the molded body has sufficient hardness for cutting.
It also has excellent mechanical properties such as strength and elastic modulus. The molded product obtained from the resin of the present invention does not have a high oxygen permeability coefficient, but can selectively permeate oxygen compared to nitrogen (4g!). The ratio of the permeability coefficients of element and oxygen is usually 3 or more. The molded article obtained from the resin of the present invention has excellent thermal stability, and its oxygen permeability does not substantially change even after heat treatment.

Since the molded product obtained from the resin of the present invention has the above-mentioned excellent characteristics, it can be used as an oxygen-permeable molded product for medical use such as hard contact lenses and artificial lungs, or an oxygen-rich molded product for medical or industrial use. It can be used as an oxygen permeable molded body such as a chemical film.

(Examples) Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples in any way. In the examples, the IH brown spectra, number average molecular weights, and oxygen permeability coefficients PO2 and DK were determined according to the following methods.

■ 1H NMR spectrum = il in chloroform, 90
Hair length was measured in MHzK using a methyldisilazane standard.

■ Number average molecular weight: Determined by gel vermicin chromatography as a polystyrene equivalent value.

■ PO2: Using a GT-10 type gas permeation measuring device and a G-2800 type gas chromatograph manufactured by Yanagimoto Seisakusho,
Measured at 35°C. Try searching for a pot using oxygen as the sample gas. In addition, Pox and PN2 (nitrogen permeability coefficient) are calculated using 2 gas as the temple gas, and the formula α=
The ratio α of oxygen and nitrogen permeability coefficients was calculated using PO2/PN2.

(2) DK: Measured in water at 35° C. using a 1316W Seikaken film oxygen permeability meter manufactured by Rika Seiki Kogyo.

Example 1 2,2,44-tetrakis(trifluoromethyl)-1,3 was placed in a 100-container flask equipped with a stirrer i, a nitrogen gas inlet, and a cooling tube for solidifying the distilled phenol. -Cyclobutanediol 36.0O
y (0.10 mol), diphenyl carbonate) 19.2
6F (0,09 mol)% trans-1,4-cyclohexanedicarboxylic acid diphenyl a, 24r (o, ox mol) and lithium hydride 0.84 (0,1 mmol)
was charged, heated to 180°C in an oil bath in a nitrogen stream, and stirred for 30 minutes. Then, at 200°C for 45 minutes,
After stirring at 220"C for 45 minutes and at 250°C for 30 minutes, the temperature was maintained at 250°C and the pressure was reduced to 15 mHPK. Under this reduced pressure for 20 minutes, and further under reduced pressure of 0.6 wr H for 15 minutes. Stir to obtain a colorless and transparent polymer36.
I got 412.

As a result of measuring the INMI spectrum of the obtained polymer, it was reported in S magazine that this polymer had the following structure.

Rakis (trifluoromethyl)-1,3-cyclobutanediol 36.00? (0.10 mol), trans-
Diphenyl 1,4-cyclohexanedicarboxylate 32.
40f (0.10 mol) and lithium hydride 0.8~
(0.1 mmol, 17 mol) was prepared in the same manner as in Example 1 to obtain a colorless and transparent polymer 45.631i'.

The 1H NMR spectrum of the obtained polymer was measured, and the results confirmed that this polymer had the following structure.

Seriously, the number average molecular weight of this polymer is 20,800.

The above polymer was made into a film with a thickness of 200 μm by hot pressing, and %PO2 and α-mabi DK were measured. The results are shown in Table 1.

Example 2 2,2,4.4-tetoma was added to the reaction vessel used in Example 1, and the number average molecular weight of this polymer was 23,700.

The above polymer was heat-pressed into a 200 μm thick film, and PO2, α and DK were measured. Results first
Shown in the table.

Example 3 In the nine reaction vessels used in Example 1, 2,2,4.4-
Tetrakis(trifluoromethyl)-t,a-cyclobutanediol 18.01f (0.05 mol), 2,2,
4゜4-Tetrakis(2,2,2-)lifluoroethyl)-1,3-cyclobutanediol 20.80 Pc
0.05 mol), diphenyl carbonate) 21.405
1 (0,10 mol) and lithium hydride 0.8 to (0
, 1 mmol), and in the same manner as in Example 1, 37.68 t of a colorless and transparent polymer was obtained.

As a result of measuring the IHNMR spectrum of the obtained polymer, it was confirmed that this polymer had the following structure.

Rakis(trifluoromethyl)-1,3-cyclobutanediol 36.0Of (0.10 mol), diphenyl carbonate 19.26F (0.09 mol), diphenyl terephthalate 3.18P (0.01 mol) and Charge 0.84 (0.1 mmol) of lithium hydride,
A colorless and transparent polymer 36.84F was prepared in the same manner as in Example 1.
I got it.

As a result of measuring the 'HNMR and spectrum of the obtained poly-i-, it was confirmed that this polymer had the following structure.

The number average molecular weight of this polymer was 22,600.

The above polymer was formed into a 200 μm thick film by hot pressing, and PO2, α and DK were measured. Results first
Shown in the table.

Example 4 In the photoreaction vessel used in Example 1, s 2.2. ．． 4.4-
The number average molecular weight of this polymer is 19,000.
And that's it.

The above polymer was formed into a 200 μm thick film by hot pressing, and PO2, α and DK were measured. Results first
Shown in the table.

Table 1 Example 5 Molding into contact lenses The polymer obtained in Example 1 was heated to 151 m.
It was molded to a size of 15 m x 4 sam thick. The Vickers hardness (measured according to JIS Z2244) of this product is 9.0.
I hope so. This item is subjected to cutting and polishing processing.

Contact lenses were made. Both the cutting and polishing surfaces are good.

The polymers obtained in Examples 2 to 4 were similarly cut and polished to obtain contact lenses.

(Effects of the Invention) According to the present invention, oxygen gas is selectively and efficiently transmitted,
A resin is provided that provides a molded article with excellent mechanical strength and sufficient hardness. As described above, the molded article provided by the present invention selectively and efficiently transmits oxygen gas,
Since it has excellent mechanical strength and sufficient hardness, it can be used as an oxygen-permeable molded article such as a hard contact lens, an artificial lung, or an oxygen-enriching membrane for medical or industrial use.

Claims (1)

[Scope of Claims] 1. A resin selected from the group consisting of polycarbonate, polyester carbonate, and polyester having a 1,3-dioxycyclobutane skeleton represented by the following general formula and having a number average molecular weight of 5,000 or more. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1, R^2, R^3, and R^4 are each a saturated aliphatic hydrocarbon in which at least one hydrogen atom is substituted with a fluorine atom. 2. An oxygen-permeable molded article made of the resin according to claim 1. 3. The oxygen permeable molded article according to claim 2, which is an oxygen permeable molded article for medical use. 4. The oxygen permeable molded article according to claim 3, wherein the medical oxygen permeable molded article is a contact lens. 5. The oxygen-permeable molded article according to claim 2, which is an oxygen-enriched membrane.