JP2015160816A - Polymerizable monomer and monomer for manufacture of ophthalmological device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable monomer which contains a specified number of silicon atoms and a specified number of fluorine atoms, has high purity and is suitable as an ophthalmological monomer and good in compatibility with (meth)acrylic monomers to be used together and its production method.SOLUTION: A compound of formula (1) and its production method are provided. In formula (1), Rand Rare 1-4C monovalent hydrocarbon groups; n is 2 or 3; Ris a 1-10C divalent hydrocarbon group; Ris a 1-8C fluorine-substituted monovalent hydrocarbon group; Ris a 4-8C (meth)acryloxy-substituted monovalent hydrocarbon; and Ris a hydrogen atom or a 1-4C monovalent hydrocarbon group.

Description

  The present invention relates to a compound for producing an ophthalmic device, for example, a contact lens, an intraocular lens, and an artificial cornea (hereinafter also referred to as “ophthalmic monomer”) and a method for producing the compound. Specifically, it is a compound having a predetermined number of silicon atoms and a predetermined number of fluorine atoms, and is copolymerized with a polymerizable monomer such as a (meth) acrylic monomer so that the transparency and oxygen permeability are high and antifouling property is achieved. The present invention relates to an excellent compound that provides a polymer suitable for application to the eye, and a method for producing the same.

The following silicone compounds are known as ophthalmic monomers.

  The above TRIS (3- [tris (trimethylsiloxy) silyl] propyl methacrylate) has poor compatibility with hydrophilic monomers such as 2-hydroxyethyl methacrylate (HEMA), and when copolymerized with these hydrophilic monomers, There is a disadvantage that a transparent polymer cannot be obtained. On the other hand, the SiGMA is excellent in compatibility with a hydrophilic monomer such as HEMA, and the copolymer is characterized by relatively high oxygen permeability and high hydrophilicity. However, in recent years, ophthalmic polymers have been required to have higher oxygen permeability so that they can be worn continuously for a long time, and polymers obtained from SiGMA have insufficient oxygen permeability.

ＳｉＧＭＡにおいてビス（トリメチルシロキシ）メチルシリル部分をＳｉ部分とし、全体に占めるＳｉ部分の質量割合を求めると５２％となる。一方、上記式（ａ）において、トリス（トリメチルシロキシ）シリル部分をＳｉ部分とし、全体に占めるＳｉ部分の質量割合を求めると６０％となる。即ち、上記式（ａ）の化合物は、Ｓｉ部分の質量割合が多い。その為、得られる眼科デバイスに高い酸素透過性をもたらすことができる。 In order to solve this problem, Patent Document 1 describes a compound represented by the following formula (a).

In SiGMA, the bis (trimethylsiloxy) methylsilyl moiety is defined as the Si moiety, and the mass ratio of the Si moiety in the whole is 52%. On the other hand, in the above formula (a), the tris (trimethylsiloxy) silyl moiety is the Si moiety, and the mass ratio of the Si moiety in the whole is 60%. That is, the compound of the above formula (a) has a large mass ratio of the Si portion. Therefore, high oxygen permeability can be brought to the obtained ophthalmic device.

  However, when the mass ratio of the Si portion is increased in order to increase the oxygen permeability, there is a problem that the strength of the copolymer polymer is lowered because the molecular weight per polymerizable group is increased. In addition, Patent Document 2 describes that the compound represented by the above formula (a) is prepared by reacting an epoxy precursor with methacrylic acid, but this reaction has many side reactions and is obtained. There was also a problem that the fluctuation of the physical properties of the polymer was large.

  From the viewpoint of oxygen permeability, tetramer silicone or more is preferable, and tetramer silicone and pentamer silicone are considered preferable in order to achieve both oxygen permeability and the strength of the copolymer. Therefore, development of a method for obtaining a silicone monomer having a tetramer or higher silicone with high purity is required.

  Patent Document 3 describes 3- [tris (trimethylsiloxy) silyl] propyl methacrylamide (TRIS-Am). In the compound, when the amide groups form hydrogen bonds, the polymerization reactivity of the monomer and the mechanical strength of the polymer are improved. However, the compound has poor compatibility with other (meth) acrylic monomers, and a highly transparent polymer cannot be obtained. Moreover, the contamination resistance is not sufficient.

しかし上記化合物をモノマー成分として得られる重合体は、機械強度が不足することや、重合反応性に劣ることがあった。また、耐汚染性が十分ではない。 Patent Document 4 describes an ophthalmic lens using a silicone compound represented by the following formula and a polymer containing the compound as a polymerization component.

However, the polymer obtained using the above compound as a monomer component may have insufficient mechanical strength or inferior in polymerization reactivity. Moreover, the contamination resistance is not sufficient.

  In order to improve the oxygen permeability of the polymer or to impart antifouling properties, a monomer compound having a fluorine-substituted hydrocarbon group introduced has been developed. For example, Patent Document 5 describes a method of copolymerizing a hydrophilic monomer, a monomer having a tris (siloxysilyl) group, and a monomer having a fluorine-substituted hydrocarbon group. Patent Documents 6, 7 and 8 describe monomers in which a fluorine-substituted hydrocarbon group is introduced into the siloxane side chain of an organopolysiloxane.

JP 2007-186709 A Japanese Patent Laid-Open No. 2007-1918 Japanese National Patent Publication No. 8-501504 Japanese Patent No. 4882136 Special table 2003-516562 gazette JP-A-1-308419 Japanese Patent Laid-Open No. 2-304093 Special table 2013-507652 publication

  However, the above monomers described in Patent Document 5 have poor compatibility, and there is a problem that the polymer becomes cloudy or causes microphase separation. In addition, since the monomers described in Patent Documents 6 to 8 are difficult to control the number of repeating units of the siloxane chain into which the fluorine-substituted hydrocarbon group is introduced, the amount of fluorine introduced is a mixture having a distribution. In addition, since the amount of fluorine introduced is too large, the compatibility between the monomers is deteriorated, the polymer becomes cloudy, and microphase separation occurs.

  Therefore, the present invention is a polymerizable monomer having a predetermined number of silicon atoms and a predetermined number of fluorine atoms, having a high purity, suitable as an ophthalmic monomer, and compatible with a (meth) acrylic monomer used in combination. An object of the present invention is to provide a compound having a good surface roughness and a method for producing the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that the compound represented by the following formula (1) has good compatibility with other (meth) acrylic monomers, and is a colorless and transparent polymer. And a polymer having good mechanical strength and antifouling property was found, and the present invention was achieved.

（式（１）において、Ｒ^１は炭素数１〜４の一価炭化水素基であり、Ｒ^２は炭素数１〜４の一価炭化水素基であり、ｎは２または３であり、Ｒ^３は炭素数１〜１０の二価炭化水素基であり、Ｒ^４は炭素数１〜８のフッ素置換一価炭化水素基であり、Ｒ^５は炭素数４〜８の（メタ）アクリルオキシ基置換一価炭化水素基であり、Ｒ^６は水素原子または炭素数１〜４の一価炭化水素基である）。 That is, this invention provides the compound represented by following formula (1), and the manufacturing method of this compound.

(In Formula (1), R ¹ is a monovalent hydrocarbon group having 1 to 4 carbon atoms, R ² is a monovalent hydrocarbon group having 1 to 4 carbon atoms, n is 2 or 3, ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ⁴ is a fluorine-substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ⁵ is a (meth) acryloxy group having 4 to 8 carbon atoms. A substituted monovalent hydrocarbon group, and R ⁶ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms).

  The silicone compound of the present invention is highly pure and highly compatible with other (meth) acrylic monomers used in combination. This gives a colorless and transparent polymer. Moreover, since the compound of this invention has a urethane bond in a spacer part, it forms a hydrogen bond between polymers and improves the mechanical strength of a polymer. Furthermore, since the compound of the present invention has a fluorine-substituted monovalent hydrocarbon group, it gives a polymer having improved antifouling properties. In addition, the method of the present invention utilizes a reaction between an isocyanate group-containing silicone compound and a fluorine-substituted hydrocarbon group and a (meth) acryloxy group-substituted hydrocarbon group-containing alcohol compound. According to the production method, a silicone compound having high purity can be provided. Therefore, the silicone compound and the method for producing the compound of the present invention are suitable for producing an ophthalmic device.

1 is a ¹ H-NMR chart of a compound produced in Example 1.

The silicone compound of the present invention is represented by the above formula (1) and has a urethane bond as a center and a specific siloxane structure ((R ¹ ₃ SiO) _n R ² _3-n via a spacer (R ³ ) on one side. Si—) and a fluorine-substituted monovalent hydrocarbon group (R ⁴ ) and a (meth) acryloxy group-substituted monovalent hydrocarbon group (R ⁵ ) on the other side.

In the above formula (1), R ¹ is a monovalent hydrocarbon group having 1 to 4 carbon atoms. Examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, and a butyl group. Preferably, R ¹ is a methyl group.

In the above formula (1), R ² is a monovalent hydrocarbon group having 1 to 4 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, and a butyl group are mentioned. Preferably, it is a methyl group. n is 2 or 3. When n is less than the lower limit, the oxygen transmission rate is low.

R ³ is a C 1-10 divalent hydrocarbon group. Examples include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, and a decanylene group. Preferably, it is a propylene group.

R ⁴ is a C1-C8 fluorine-substituted monovalent hydrocarbon group. Preferably, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 2,2,3,3,4,4,5,5,6,6,7,7, A 7-tridecafluoroheptyl group or a 4-trifluoromethyl-2,2,3,3,4,4,5,5,5-nonafluoropentyl group.

R ⁵ is a (meth) acryloxy group-substituted monovalent hydrocarbon group having 4 to 8 carbon atoms, and one of the hydrogen atoms bonded to the carbon atom of the monovalent hydrocarbon group having 1 to 4 carbon atoms is (meth) acrylic. It is substituted with an oxy group. An acryloxymethyl group or a methacryloxymethyl group is preferable.

R ⁶ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms. Examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, and a butyl group. Preferably it is a hydrogen atom.

The present invention can provide a compound containing one kind of compound represented by the above formula (1) and having a specific structure with high purity by the method described later. One type having a specific structure means one kind of compound having a specific R ¹ , R ² , n, R ³ , R ⁴ , R ⁵ , and R ⁶ . High purity means that one kind of compound having one specific R ¹ , R ² , n, R ³ , R ⁴ , R ⁵ , and R ^{6 out} of the total mass of the compound is more than 95% by mass, preferably 99% by mass or more. In the present invention, the purity is determined by gas chromatography (hereinafter referred to as “GC”) analysis. Detailed conditions will be described later. When the compound has the high purity, a transparent polymer can be obtained without causing turbidity when mixed with a non-silicone monomer such as 2-hydroxyethyl methacrylate. If the purity is less than 95% by mass, for example, if there are more than 5% by mass of compounds having different structures, turbidity may occur when the compound of the present invention is mixed with a non-silicone monomer, and a transparent polymer may not be obtained. .

Particularly preferred are compounds in which R ¹ is a methyl group, n is 3, and R ³ is a propylene group. In the formula (1), R ¹ is a methyl group, n is 3, R ³ is a propylene group, and R ⁴ is 2,2,3,3,4,4,5,5,5-nona. When it is a fluoropentyl group, R ⁵ is an acryloxymethyl group, and R ⁶ is a hydrogen atom, the molecular weight of the compound is 727, and the mass ratio of siloxane to the total mass of the compound is about 40%. That is, since the compound has a high Si content, the resulting copolymer has high oxygen permeability.

（式中、Ｒ^１、Ｒ^２、ｎ、Ｒ^３は上述のとおりである）
下記式（３）で表されるアルコール化合物を

（式中、Ｒ^４、Ｒ^５、Ｒ^６は上述のとおりである）
反応させる工程を含む。該反応は、上記式（３）で表されるアルコール化合物の無溶媒下あるいはトルエンまたはヘキサン等の溶液中に、上記式（２）で表されるイソシアネート基含有シリコーン化合物を徐々に添加して、水浴等で冷却しながら０〜５０℃の温度で行なうことが好ましい。 The present invention further provides a method for producing the compound represented by the above formula (1).
The production method of the present invention comprises a silicone compound represented by the following formula (2):

(Wherein R ¹ , R ² , n and R ³ are as described above)
An alcohol compound represented by the following formula (3)

(Wherein R ⁴ , R ⁵ , and R ⁶ are as described above)
A step of reacting. In the reaction, the isocyanate group-containing silicone compound represented by the above formula (2) is gradually added to the solution of the alcohol compound represented by the above formula (3) without solvent or in a solution such as toluene or hexane, It is preferable to carry out at a temperature of 0 to 50 ° C. while cooling with a water bath or the like.

  The usage-amount of the isocyanate group containing silicone compound of Formula (2) is 1-3 mol with respect to 1 mol of alcohol compounds of Formula (3), Preferably, it is 1.05-2 mol. If it is less than the said lower limit, the alcohol compound of Formula (3) will remain as an unreacted substance, and high purity cannot be achieved. Moreover, when the said upper limit is exceeded, it is economically disadvantageous.

  In the reaction, a catalyst may be used as necessary. The catalyst may be a generally used isocyanate reaction catalyst, preferably a tin compound or an amine catalyst. As the tin catalyst, a carboxylate compound of tin (II) is preferable from the viewpoint of catalytic activity, and as the amine catalyst, a tertiary amine such as triethylamine, tributylamine, N-ethyldiisopropylamine is preferable. The usage-amount of a catalyst is 0.001-0.1 mass part with respect to 100 mass parts of alcohol compounds of Formula (3), More preferably, it is 0.005-0.05 mass part. Above the upper limit, the effect is saturated and uneconomical. Below the lower limit, the catalytic effect is insufficient, the reaction rate is low, and the productivity is reduced.

  In a preferred embodiment of the method of the present invention, the presence or absence of a residual alcohol compound (formula (3)) is monitored by GC measurement, and after confirming the disappearance of the peak, an alcohol such as methanol or ethanol is added to the reaction product. The isocyanate of the isocyanate compound of formula (2) is inactivated. An organic solvent and water are added and stirred, and then allowed to stand to separate into an organic layer and an aqueous layer. In the above reaction, side reactions are hardly observed. After washing the organic layer with water several times, the solvent in the organic layer is stripped to obtain a highly pure silicone compound of formula (1).

  The compound of the present invention has good compatibility with other compounds (hereinafter referred to as polymerizable monomers) having a group that polymerizes with the silicone compound, such as a (meth) acryl group. Therefore, a colorless and transparent polymer can be obtained by copolymerizing with a polymerizable monomer. In particular, a polymer having good compatibility with a fluorine substituent-containing (meth) acrylic monomer that imparts stain resistance, and excellent hydrophilicity and stain resistance can be provided.

  Examples of the polymerizable monomer include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (poly) ethylene glycol dimethacrylate, polyalkylene glycol mono (meth) acrylate, polyalkylene glycol monoalkyl ether ( Acrylic monomers such as (meth) acrylate, trifluoroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate; N, N-dimethylacrylamide, N, N-diethylacrylamide , N-acryloylmorpholine, acrylic acid derivatives such as N-methyl (meth) acrylamide; other unsaturated aliphatic or aromatic compounds such as crotonic acid, cinnamic acid, vinyl benzoic acid; and (meth) a Silicone monomers having a polymerizable group such as Lil group. These may be used alone or in combination of two or more.

  Copolymerization of the compound of the present invention with the other polymerizable monomer may be performed by a conventionally known method. For example, it can be carried out using a known polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator. Examples of the polymerization initiator include 2-hydroxy-2-methyl-1-phenyl-propan-1-one, azobisisobutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, tert-butyl hydroperoxide, cumene And hydroperoxide. These polymerization initiators can be used alone or in admixture of two or more. The compounding quantity of a polymerization initiator is 0.001-2 mass parts with respect to a total of 100 mass parts of a polymerization component, Preferably it is 0.01-1 mass part.

  A polymer containing the compound of the present invention as a polymerization component is excellent in oxygen permeability, mechanical strength, and antifouling property. Therefore, it is suitable for manufacturing ophthalmic devices such as contact lenses, intraocular lenses, and artificial corneas. The manufacturing method of the ophthalmic device using the polymer is not particularly limited, and may be a conventional ophthalmic device manufacturing method. For example, when forming into a lens shape such as a contact lens or an intraocular lens, a cutting method or a mold method can be used.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not restrict | limited to the following Example. In the following Examples, the viscosity was measured using a Canon Fenceke viscometer, and the specific gravity was measured using a buoyancy meter. The refractive index was measured using a digital refractometer RX-5000 (manufactured by Atago Co., Ltd.). ¹ H-NMR analysis was performed using JNM-ECP500 (manufactured by JEOL Ltd.) and deuterated chloroform as a measurement solvent.
In the following, the purity of the compound is determined by gas chromatography (GC) measurement under the following conditions.
Gas chromatography (GC) measurement conditions Gas chromatograph: Agilent detector: FID, temperature 300 ° C
Capillary column: HP-5MS (0.25 mm × 30 m × 0.25 μm) from J & W
Temperature rising program: 50 ° C. (5 minutes) → 10 ° C./minute→250° C. (holding)
Inlet temperature: 250 ° C
Carrier gas: Helium (1.0 ml / min)
Split ratio: 50: 1
Injection volume: 1 μl

[Example 1]
Synthesis of Silicone Compound 1 34.8 g (0.1 mol) of an alcohol compound represented by the following formula (4), 0.003 g (0.01% by mass) of dioctyltin oxide, 0.003 g of ionol, and 0.003 g of 4-methoxyphenol Was charged in a 1 liter flask equipped with a stirrer, a Dim funnel, a thermometer and a dropping funnel, and 39.8 g (0.105 mol) of an isocyanate group-containing silicone compound of the following formula (5) was added dropwise over 1 hour. The internal temperature rose from 20 ° C to 27 ° C. The mixture was aged at 40 ° C. while monitoring the peak of the alcohol compound of formula (4) by GC. After 4 hours, it was confirmed that the peak of the alcohol compound of formula (4) was below the detection limit in GC, and 1.7 g (0.0525 mol) of methanol was added to the reaction solution. Further, 100 g of hexane and 100 g of ion exchange water were added and washed with water. After standing and separating to cut the aqueous layer, it was further washed twice with water. The organic layer was stripped under reduced pressure with hexane or the like as a solvent to obtain 58.0 g (0.0798 mol, yield 79.8%) of a colorless transparent liquid product. It was confirmed by ¹ H-NMR analysis that it was a silicone compound (acrylic monomer) represented by the following formula (6). The purity of the silicone compound by GC was 97.1%, the viscosity was 185 mm ² / s (25 ° C.), the specific gravity was 1.147 (25 ° C.), and the refractive index was 1.4028. A ¹ H-NMR chart of the compound is shown in FIG.

[Example 2]
Synthesis of Silicone Compound 2 Example 1 was repeated except that 44.8 g (0.1 mol) of the alcohol compound of the following formula (7) was used instead of 34.8 g (0.1 mol) of the alcohol compound of the above formula (4). As a result, 67.0 g (0.081 mol, yield 81%) of a colorless transparent liquid product was obtained. It was confirmed by ¹ H-NMR analysis that it was a silicone compound (acrylic monomer) represented by the following formula (8). The purity of the silicone compound by GC was 96.6%, the viscosity was 260 mm ² / s (25 ° C.), the specific gravity was 1.238 (25 ° C.), and the refractive index was 1.423.

[Example 3]
Synthesis of Silicone Compound 3 Example 1 was repeated except that 39.8 g (0.1 mol) of the alcohol compound of the following formula (9) was used instead of 34.8 g (0.1 mol) of the alcohol compound of the above formula (4). As a result, 58.3 g (0.075 mol, yield 75%) of a colorless transparent liquid product was obtained. It was confirmed by ¹ H-NMR analysis that it was a silicone compound (acrylic monomer) represented by the following formula (10). The purity of the silicone compound by GC was 96.4%, the viscosity was 230 mm ² / s (25 ° C.), the specific gravity was 1.211 (25 ° C.), and the refractive index was 1.403.

[Synthesis Example 1]
Preparation of Silicone Compound 4 According to the method described in Example 1 of Japanese Patent No. 4882136 (Patent Document 4), a compound represented by the following formula (11) was synthesized. This compound is referred to as silicone compound 4.

（Ａはメタクリル基であり、Ｒｆはトリフルオロプロピル基であり、ｍ＋ｎ＝１００であり、ｎ＝４０である） [Synthesis Example 2]
Preparation of Silicone Compound 5 According to the method described in Example F of JP-A-1-308419 (Patent Document 6), a siloxane containing both terminal methacrylic group side chain Rf groups represented by the following formula (12) was synthesized. This compound is referred to as “silicone compound 5”.

(A is a methacryl group, Rf is a trifluoropropyl group, m + n = 100, and n = 40)

Preparation of monomer mixture [Examples 4-6]
Each silicone compound obtained in Examples 1 to 3 was mixed with another (meth) acrylate compound according to the composition shown in Table 1 below to prepare monomer mixtures 1 to 3. The monomer mixture was subjected to an evaluation test described later.

[Comparative Examples 1-4]
In Comparative Examples 1 to 4, the silicone compounds shown in Table 2 below were used in place of the silicone compounds 1 to 3 described above. The silicone compound was mixed with other (meth) acrylate compounds according to the composition shown in Table 2 below to prepare monomer mixtures 4 to 7. The monomer mixture was subjected to an evaluation test described later.

[Evaluation test]
(1) Compatibility with other polymerizable monomers Darocur 1173 (Ciba Specialty Chemicals, 0.5 parts by mass) was added to each monomer mixture obtained above and stirred. The appearance of the obtained mixture was visually observed. A mixture in which the compatibility between the silicone compound and the other (meth) acrylic compound is good becomes colorless and transparent, but a mixture in which the compatibility is poor causes turbidity. The results are shown in Table 3 below.

(2) Appearance of film (polymer) Each monomer mixture obtained above was deaerated in an argon atmosphere. The mixed solution was poured into a mold sandwiching two quartz glass plates, and irradiated with an ultrahigh pressure mercury lamp for 1 hour to obtain a film having a thickness of about 0.3 mm. The appearance of the film was visually observed. The results are shown in Table 3 below.

(3) Water wettability (surface hydrophilicity) of the film (polymer)
The contact angle meter CA-D type (manufactured by Kyowa Interface Science Co., Ltd.) was used for the film produced in (2) above, and the water contact angle was measured by a liquid appropriate method. The results are shown in Table 3 below.

(4) Contamination resistance of film (polymer) The film produced in (2) above was immersed in a 37 ° C. phosphate buffer solution (PBS (−)) for 24 hours. Each film was immersed in a known artificial lipid solution at 37 ° C. ± 2 ° C. for 8 hours before soaking in PBS (1) and after 24 hours. Thereafter, it was rinsed with PBS (−) and immersed in a 0.1% Sudan black-sesame oil solution. The case where no difference was observed in the dyeing state before and after the immersion was indicated as ◯, and the case where the difference was observed was indicated as ×. The results are shown in Table 3 below.

(5) Mechanical strength Two films were prepared according to (2) above, and after wiping off the surface moisture of one of them, the film was immersed in a 37 ° C. phosphate buffer solution (PBS (1)) for 24 hours. Each of the films before dipping in PBS (1) and after dipping for 24 hours was cut into a dumbbell shape having a width of 2.0 mm, the upper and lower ends of the test sample were sandwiched with jigs, and the breaking strength and breaking elongation were maintained at a constant speed. Was measured using a fracture tester AGS-50NJ (manufactured by Shimadzu Corporation). In the case where the breaking strength and breaking elongation before and after being immersed in PBS (one) change within 10%, it was evaluated as ◯, and when the decrease exceeding 10% was observed, it was marked as x. The results are shown in Table 3 below.

  The conventional silicone compounds used in Comparative Examples 1 to 4 have poor compatibility with other (meth) acrylic monomer compounds and cannot obtain a transparent polymer. Further, the obtained polymer is inferior in water wettability (surface hydrophilicity) and stain resistance. On the other hand, the silicone compound of the present invention has a good compatibility with other (meth) acrylic monomers and provides a colorless and transparent polymer. Moreover, since it is well compatible with the fluorine-substituted group-containing (meth) acrylic monomer, a polymer excellent in hydrophilicity and stain resistance is provided. In addition, since the silicone compound of the present invention has a fluorine-substituted hydrocarbon group, a polymer having excellent stain resistance can be obtained without including other fluorine-substituted group-containing (meth) acrylic monomers as polymerization components (Examples) 5). Furthermore, since the silicone compound of the present invention has a urethane bond, it gives a polymer having excellent mechanical strength.

The monomer of the present invention is a polymer having oxygen permeability and being colorless and transparent, and gives a polymer excellent in hydrophilicity, stain resistance, and mechanical strength. Moreover, according to the production method of the present invention, a monomer containing one kind of compound having a specific structure with high purity can be provided. Therefore, the compound of the present invention and the method for producing the compound are useful for producing ophthalmic devices such as contact lens materials, intraocular lens materials, and artificial cornea materials.

Claims (9)

Compound represented by the following formula (1)

(In Formula (1), R ¹ is a monovalent hydrocarbon group having 1 to 4 carbon atoms, R ² is a monovalent hydrocarbon group having 1 to 4 carbon atoms, n is 2 or 3, ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ⁴ is a fluorine-substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ⁵ is a (meth) acryloxy group having 4 to 8 carbon atoms. A substituted monovalent hydrocarbon group, and R ⁶ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms). In formula (1), R ¹ is a methyl group, R ² is a methyl group, n is 2 or 3, R ³ is a propylene group, and R ⁴ is a fluorine-substituted one having 1 to 8 carbon atoms. The compound according to claim 1, which is a valent hydrocarbon group, R ⁵ is a (meth) acryloxymethyl group, and R ⁶ is a hydrogen atom. In the formula (1), R ⁴ is 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 2,2,3,3,4,4,5,5,6 , 6,7,7,7-tridecafluoroheptyl group or 4-trifluoromethyl-2,2,3,3,4,4,5,5,5-nonafluoropentyl group. Or the compound according to 2. 1 type which has each specific one R < ¹ >, R < ² >, n, R < ³ >, R < ⁴ >, R < ⁵ >, R < ⁶ > in Formula (1) comprises more than 95 mass% with respect to the total mass of a compound. 1. The compound according to 1.   The monomer for ophthalmic devices which consists of a compound of any one of Claims 1-4.   The polymer obtained by superposing | polymerizing the compound of any one of Claims 1-4, and this and at least 1 sort (s) of the other compound which has a polymeric group.   An ophthalmic device using the polymer according to claim 6. A method for producing a compound represented by the following formula (1),

(In Formula (1), R ¹ is a monovalent hydrocarbon group having 1 to 4 carbon atoms, R ² is a monovalent hydrocarbon group having 1 to 4 carbon atoms, n is 2 or 3, ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ⁴ is a fluorine-substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ⁵ is a (meth) acryloxy group having 4 to 8 carbon atoms. A substituted monovalent hydrocarbon group, and R ⁶ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms)
An isocyanate group-containing silicone compound represented by the following formula (2):

(Wherein R ¹ , R ² , n and R ³ are as described above)
An alcohol compound represented by the following formula (3)

(Wherein R ⁴ , R ⁵ , and R ⁶ are as described above)
The manufacturing method including the process made to react. 1 type which has each specific one R < ¹ >, R < ² >, n, R < ³ >, R < ⁴ >, R < ⁵ >, R < ⁶ > in Formula (1) comprises more than 95 mass% with respect to the total mass of a compound. 8. The production method according to 8.

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