JP6045515B2 - Monomers for ophthalmic device manufacturing - Google Patents

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 silicone structure having a predetermined molecular weight and a (meth) acryl group, and is copolymerized with another monomer having a polymerizable group to be applied to the eye with high transparency and oxygen permeability. The present invention relates to a compound giving a suitable polymer and a method for producing the same. In particular, the present invention relates to a compound that becomes a crosslinking component of a polymerizable silicone monomer.

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 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. 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 a copolymer polymer obtained. There was also a problem that the physical properties of the camera were greatly blurred.

  As described in the background art section of Patent Document 5, tetramer silicone or more is preferable from the viewpoint of oxygen permeability, and in order to achieve both oxygen permeability and strength of the copolymer, the tetramer is preferable. Silicones and pentameric silicone are considered preferred. Therefore, development of a method for obtaining a silicone monomer having a tetramer or higher silicone with high purity is required.

該方法で得られた生成物は、２−ヒドロキシエチルメタクリレート等の親水性モノマーと混合した時に白濁する場合がある。さらに、クロロシランによる該シリコーン鎖の末端封鎖率が高くない。 In Patent Document 3, chlorosilane having a (meth) acryl group such as 3- (2-methacryloyloxyethoxy) propyldimethylchlorosilane is reacted with anion-polymerized cyclic siloxane using lithium trialkylsilanolate as an initiator. A method for preparing a silicone compound represented by the following formula (b) is described.

The product obtained by this method may become cloudy when mixed with a hydrophilic monomer such as 2-hydroxyethyl methacrylate. Furthermore, the terminal blocking rate of the silicone chain by chlorosilane is not high.

（ｒは３以上の整数）
しかし、上記方法では、エステル化率が不十分で末端封鎖率が低く、また、シリコーンの重合度に分布ができる。 Patent Document 4 describes a method for preparing a silicone compound represented by the following formula (c) by esterification or transesterification of one-terminal hydroxyl group-containing organopolysiloxane and (meth) acrylic acid (ester).

(R is an integer of 3 or more)
However, in the above method, the esterification rate is insufficient, the end-capping rate is low, and the degree of polymerization of silicone can be distributed.

（ここでｍは３〜１０の整数のうちの一つ、ｎは１または２のうちの一つ、Ｒ^１は炭素数１〜４のアルキル基のうちの一つ、Ｒ^２は水素及びメチル基のうちの一つである） Patent Document 5 describes a method for producing a silicone compound represented by the following formula (d) by esterification of a one-terminal hydroxyl group-containing organopolysiloxane and a (meth) acrylic acid halide. Patent Document 5 can produce a high-purity silicone compound containing more than 95% by weight of one kind of silicone compound represented by the following formula (d) and having specific m, n, R ¹ and R ² by the method. It is described.

(Where m is one of integers from 3 to 10, n is one of 1 or 2, R ¹ is one of alkyl groups having 1 to 4 carbon atoms, R ² is hydrogen and methyl. One of the groups)

Patent Document 6 describes an ophthalmic lens using a silicone compound represented by the following formula and a polymer containing the compound as a polymerization component.

［式中、Ｒは（メタ）アクリル基を含まない非置換又は置換の炭素数１〜２０の１価炭化水素基又はアルコキシ基である。Ｑは下記Ａ又はＸの何れかであり、異なったものを含んでもよく、ただし、Ｑの少なくとも１つはＡである。Ａは式：−Ｒ^１−ＣＯＮＨ−Ｃ（Ｒ^２）［ＣＨ_２−Ｏ−ＣＯ−ＣＨ＝ＣＨ_２］_２又は−Ｒ^１−ＣＯＮＨ−Ｃ（Ｒ^２）［ＣＨ_２−Ｏ−ＣＯ−Ｃ（ＣＨ_３）＝ＣＨ_２］_２（Ｒ^１は２価有機基であり、Ｒ^２は（メタ）アクリル基を含まない非置換又は置換の炭素数１〜２０の１価炭化水素基又はアルコキシ基である。）であり、ＸはＲ又は（メタ）アクリル基を含まない活性水素含有の１価有機基である。ａ、ｂは、０≦ａ≦１，０００、０≦ｂ≦１００である。］ Further, Patent Document 7 describes (meth) acryl group-containing organopolysiloxane represented by the following formula (I).

[Wherein, R represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group that does not contain a (meth) acryl group. Q is either A or X below, and may include a different one, provided that at least one of Q is A. A is represented by the formula: —R ¹ —CONH—C (R ² ) [CH ₂ —O—CO—CH═CH ₂ ] ₂ or —R ¹ —CONH—C (R ² ) [CH ₂ —O—CO—C (CH ₃ ) ═CH ₂ ] ₂ (R ¹ is a divalent organic group, and R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group not containing a (meth) acryl group. X is an active hydrogen-containing monovalent organic group that does not contain R or a (meth) acryl group. a and b are 0 ≦ a ≦ 1,000 and 0 ≦ b ≦ 100. ]

JP 2007-186709 A Japanese Patent Laid-Open No. 2007-1918 JP 59-78236 A JP 2001-55446 A Japanese Patent No. 4646152 Japanese Patent No. 4882136 JP 2013-12776 A

  In order to improve the mechanical strength by increasing the degree of crosslinking of a polymer containing an ophthalmic silicone monomer as a polymerization component, use of another polymerizable monomer as a crosslinking component is performed. For example, polyfunctional (meth) acrylates such as ethylene glycol dimethacrylate are used. However, since these polymerizable monomers do not contain a silicone chain, there are cases where the oxygen permeability of the resulting polymer is lowered, or the crosslinking density is too high, resulting in shrinkage due to curing and deterioration in dimensional stability.

  Therefore, a silicone compound that functions suitably as a crosslinking component of a polymerizable silicone monomer and gives a polymer excellent in oxygen permeability, mechanical strength, dimensional stability, and the like is desired. However, since the silicone compound described in Patent Document 5 has only one (meth) acryl group, it does not become a crosslinking component. Moreover, the polymer obtained from this monomer may lack mechanical strength. Since the monomer compound described in Patent Document 6 also has only one (meth) acryl group, it does not become a crosslinking component. Moreover, the silicone compound of patent document 6 has an ethylene oxide-ethylene oxide structure between a siloxane structure and a (meth) acrylate structure. In this structure, the hydrophilicity is too high and the compatibility with the (meth) acrylic monomer, particularly the fluorine substituent-containing (meth) acrylic monomer that imparts stain resistance may be poor.

  Since the silicone compound described in Patent Document 7 has a plurality of (meth) acryl groups in the molecule, the crosslinking efficiency is high. However, the silicone compound is inferior in compatibility with other polymerizable monomers. The silicone compound has a large number of siloxane units. The silicone compound is produced by reacting an organopolysiloxane modified with a monovalent organic group containing active hydrogen and a hydrocarbon group-substituted isocyanate compound having two acrylic groups or methacrylic groups. The purity is low because the number of siloxane units is large and the molecular weight distribution is large. Therefore, the obtained monomer becomes a mixture. Moreover, the polymer obtained by using the monomer as a polymerization component is inferior in transparency. Furthermore, a monomer containing a silicone chain having a high degree of polymerization may become cloudy due to poor compatibility with other polymerizable monomers.

  Then, an object of this invention is to provide the silicone compound which functions suitably as a crosslinking component of a polymerizable monomer. More specifically, the present invention provides a silicone compound that can provide a polymer having good compatibility with a polymerizable silicone monomer and other polymerizable monomers, and excellent in oxygen permeability, mechanical strength, and dimensional stability. Objective. Furthermore, it aims at providing the silicone compound which has high purity, and its manufacturing method.

  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 the polymerizable silicone monomer and with other polymerizable monomers. It was found that a colorless and transparent polymer was obtained, and the present invention was achieved.

（式（１）において、ｍは２〜１０の整数であり、Ｒ^１は炭素数１〜４のアルキル基であり、Ｒ^２は水素原子又はメチル基であり、Ｒ^３は（メタ）アクリル基を含まない非置換又は置換の炭素数１〜２０の１価炭化水素基、又は炭素数１〜１０のアルコキシ基であり、Ｒ^４は水素原子又はメチル基であり、Ｒ^５は水素原子又はメチル基である）。 That is, this invention provides the compound represented by following formula (1), and the manufacturing method of this compound.

(In Formula (1), m is an integer of 2 to 10, R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is a hydrogen atom or a methyl group, and R ³ is a (meth) acryl group. Is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, R ⁴ is a hydrogen atom or a methyl group, and R ⁵ is a hydrogen atom or methyl. Group).

  The silicone compound of the present invention is highly compatible with other polymerizable monomers, particularly polymerizable silicone monomers, and further suitably acts as a crosslinking component. Furthermore, the silicone compound has a high purity. Therefore, copolymerization with a polymerizable monomer gives a polymer that is colorless and transparent and has excellent mechanical strength. In particular, the polymer has good compatibility with the fluorine-substituted group-containing (meth) acrylic monomer that imparts stain resistance, and is excellent in hydrophilicity and stain resistance. Furthermore, the silicone compound of the present invention has high oxygen permeability. Moreover, according to the production method of the present invention, it is possible to provide a silicone compound having a high terminal blocking rate and high purity. 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 spectrum of a silicone compound obtained in Example 1. FIG.

  The silicone compound of the present invention is represented by the above formula (1), has one ethylene oxide in the spacer portion between the siloxane structure and the (meth) acrylic structure, has a urethane bond in the spacer portion, and (meta ) It has two acrylic groups. Due to these characteristics, the compatibility with the silicone monomer having a polymerizable group and the compatibility with other polymerizable monomers are improved. Further, since the urethane bond forms a hydrogen bond between the polymers, a polymer having better mechanical strength can be provided. Furthermore, the polymer which can act suitably as a crosslinking component by two (meth) acryl groups and is excellent in mechanical strength and dimensional stability is provided.

  Since the silicone compound of the present invention has only one ethylene oxide in the spacer portion, the hydrophilicity balance of the compound is good. Without ethylene oxide, the hydrophilicity becomes insufficient. Further, when two or more ethylene oxides are contained, the hydrophilicity is too high, and the compatibility with the (meth) acrylic monomer, particularly the fluorine substituent-containing (meth) acrylic monomer that imparts stain resistance is deteriorated. When propylene oxide is used instead of ethylene oxide, the compatibility of the compound with the fluorine-containing group-containing (meth) acrylic monomer is good, but the hydrophobicity of the polymer becomes too high and the hydrophilicity is impaired. Moreover, the intensity | strength of the copolymer obtained will become low when it has a polyalkylene oxide structure instead of ethylene oxide.

  In the above formula (1), m is an integer of 2 to 10, preferably 3 to 7, and most preferably 3. When m is in the above range, the compound has a chain siloxane structure having a desired silicon atom weight, so that the oxygen permeability or shape recoverability when a polymer is obtained is good. When m is less than the above lower limit, the oxygen permeability is low. On the other hand, if m exceeds the above upper limit value, the hydrophilicity of the compound is lowered, which is not preferable. On the other hand, if m exceeds the upper limit, siloxane as a raw material has a molecular weight distribution, so that the purity of the obtained compound may be lowered.

In the above formula (1), R ¹ is an alkyl group having 1 to 4 carbon atoms, preferably a butyl group, and R ² is a hydrogen atom or a methyl group. R ³ is an unsubstituted or substituted C 1-20, preferably 1-10 monovalent hydrocarbon group that does not contain a (meth) acryl group, or C 1-10, preferably C 1-6. An alkoxy group; Examples of monovalent hydrocarbon groups include methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups and other alkyl groups; cyclopentyl groups, cyclohexyl groups, etc. A cycloalkyl group; an aryl group such as a phenyl group and a tolyl group; an alkenyl group such as a vinyl group and an allyl group; and a part or all of the hydrogen atoms bonded to the carbon atoms of these groups are chlorine, fluorine, etc. Examples thereof include a halogenated alkyl group substituted with a halogen atom, and a halogenated alkenyl group. Of these, alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group are preferable, and a methyl group is particularly preferable. R ⁴ is one of a hydrogen atom and a methyl group, and R ⁵ is one of a hydrogen atom and a methyl group.

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 compound having a specific one of m, R ¹ , R ² , R ³ , R ⁴ and R ⁵ . High purity means that one kind of compound having one specific m, R ¹ , R ² , R ³ , R ⁴ and R ^{5 out} of the total mass of the compound is more than 95% by mass, preferably 99% by mass or more It is to make. 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.

In particular, a compound in which m is 3 is preferable, and a compound in which m is 3 and R ¹ is a butyl group is more preferable. In Formula (1), when R ¹ is a butyl group, R ² , R ⁴ , and R ⁵ are hydrogen, R ³ is a methyl group, and m is 3, the molecular weight of the compound is 753 Yes, the mass ratio of the dimethylpolysiloxane chain portion to the total mass of the compound is about 47%. That is, since the compound has a high Si content, the resulting copolymer has high oxygen permeability.

（ｍ、Ｒ^１及びＲ^２は上述のとおりである）
下記式（３）で表される（メタ）アクリル基含有イソシアネート化合物を

（Ｒ^３、Ｒ^４、Ｒ^５は上述のとおりである）
反応させる工程を含む。該反応は、式（２）のポリオルガノシロキサンの、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、式（３）の（メタ）アクリル基含有イソシアネート化合物を、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):

(M, R ¹ and R ² are as described above)
(Meth) acrylic group-containing isocyanate compound represented by the following formula (3)

(R ³ , R ⁴ and R ⁵ are as described above)
A step of reacting. The reaction is carried out by gradually adding the (meth) acrylic group-containing isocyanate compound of the formula (3) to a solution of the polyorganosiloxane of the formula (2) 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 in the step.

  The amount of the (meth) acrylic group-containing isocyanate compound of the formula (3) is 1 to 3 mol, preferably 1.05 to 2 mol with respect to 1 mol of the polyorganosiloxane of the formula (2). If it is less than the said lower limit, the polyorganosiloxane of Formula (2) will remain as an unreacted substance, and high purity cannot be achieved. Moreover, it is economically disadvantageous if the upper limit is exceeded.

  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 amount of the catalyst used is 0.001 to 0.1% by mass, more preferably 0.005 to 0.05% by mass, based on the polyorganosiloxane of formula (2). When used exceeding the upper limit, the effect is saturated and uneconomical. When it is less than the lower limit, the catalytic effect is insufficient, the reaction rate is low, and the productivity is lowered.

  In a preferred embodiment of the method of the present invention, the presence or absence of a residual silicone compound (formula (2)) 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 (meth) acrylic group-containing isocyanate compound is deactivated. 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).

（ｍ及びＲ^１は上述のとおりである）
下記式（５）で表されるエチレングリコールモノ（メタ）アリルエーテルを付加反応させて、調製することができる。

（Ｒ^２は上述のとおりである） The silicone compound of the above formula (2) is a polyorganohydrogensiloxane represented by the following formula (4):

(M and R ¹ are as described above)
It can be prepared by addition reaction of ethylene glycol mono (meth) allyl ether represented by the following formula (5).

(R ² is as described above)

  The addition reaction may be performed according to a conventionally known method. For example, the reaction is performed in the presence of an addition reaction catalyst such as a platinum group compound. At that time, a solvent may be used. For example, aliphatic solvents such as hexane and toluene, and aromatic solvents such as ethanol and IPA can be preferably used. The allyl ether compound is used in an amount of 1.2 mol or more, preferably 1.5 mol or more per mol of the polyorganohydrogensiloxane.

  Examples of ethylene glycol mono (meth) allyl ether include ethylene glycol monoallyl ether and ethylene glycol monomethallyl ether.

  As a preferred embodiment of the addition reaction, for example, an allyl ether compound is diluted with a solvent as necessary, and a platinum-based hydrosilylation catalyst is added thereto. The kind in particular of platinum-type hydrosilylation catalyst is not restrict | limited, A conventionally well-known thing can be used. Furthermore, polyorganohydrogensiloxane is dropped and reacted at room temperature or higher. After completion of the dropwise addition, after aging under heating, the presence or absence of the starting polyorganohydrogensiloxane is confirmed by the disappearance of the peak in, for example, GC measurement. By confirming the reaction end point by GC measurement, since the polyorganohydrogensiloxane does not remain in the product, a high-purity silicone compound can be obtained. The above reaction may be carried out in a lump.

  After completion of the addition reaction, excess allyl ether compound is removed from the reaction solution. Examples of the method include stripping under reduced pressure, or a method in which the reaction product is washed with ion-exchanged water or sodium nitrate water to extract and remove the allyl ether compound into the aqueous layer. At this time, in order to obtain good two-layer separation, it is preferable to use an appropriate amount of a solvent such as toluene or hexane. In particular, by stripping the solvent from the organic layer under reduced pressure, the silicone compound of the above formula (2) can be obtained with a high purity of more than 95% by mass, and more than about 97% by mass. In order to increase the purity, distillation may be performed a plurality of times.

The polyorganohydrogensiloxane represented by the above formula (4) can be prepared by a known method. For example, a compound (monobutyldecamethylhydropentasiloxane) in which R ¹ is a butyl group and m = 3 in the formula (4) first synthesizes BuMe ₂ SiOLi using BuLi, and uses this as an initiator. The methylcyclotrisiloxane is opened and quenched with dimethylchlorosilane. This is purified by distillation to obtain monobutyldecamethylhydropentasiloxane having a purity of 99% or more. Further, monobutyldecamethylhydropentasiloxane may be distilled after an addition reaction with ethylene propylene glycol mono (meth) allyl ether represented by the formula (5). However, the boiling point of monobutyldecamethylhydropentasiloxane is 110 ° C./2 mmHg, and the addition reaction product has a higher boiling point. It is preferable to keep it. Thereby, the silicone compound of the above formula (2) can also be obtained with high purity.

  Moreover, the hydroxyl group in ethylene propylene glycol mono (meth) allyl ether is converted into a silyl ester with a silylating agent such as hexamethyldisilazane, and the silyl ester is hydrolyzed after the addition reaction to obtain a silicone compound of formula (2). May be.

  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.

  Since the silicone compound of the present invention has two (meth) acryl groups, it suitably functions as a crosslinking component. Therefore, it can be suitably used as a crosslinking component for the polymerizable monomer, and gives a polymer that is colorless and transparent and has high mechanical strength. In particular, the compound of the present invention has good compatibility with a silicone monomer having a polymerizable group such as a (meth) acryl group. As the polymerizable silicone monomer, those conventionally known as ophthalmic monomers can be used. In particular, it is a silicone monomer having a (meth) acryl group at one end and a siloxane structure at the other end. For example, the silicone monomer of patent documents 1-6 is mentioned.

  When using the silicone compound of this invention as a crosslinking component, it is preferable that the silicone compound of this invention is 0.1-50 mass parts with respect to a total of 100 mass parts of a polymerizable monomer, More preferably, it is 0.5-20. Part by mass. In particular, the amount of the silicone compound of the present invention is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable silicone monomer. Since the silicone compound of the present invention has a high purity, it gives a highly transparent polymer.

  The polymer of the silicone compound of the present invention and the above polymerizable monomer can be further polymerized with one or more of other compounds serving as a crosslinking component. Examples of the compound include bifunctional (meth) acrylate and polyfunctional (meth) acrylate. Examples of the bifunctional acrylate include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, hydroxypivalate neopentyl glycol diacrylate, and dicyclopentanyl diacrylate. Examples include acrylate, caprolactone-modified dicyclopentenyl diacrylate, ethylene oxide-modified phosphoric acid diacrylate, allylated cyclohexyl diacrylate, and isocyanurate diacrylate. Examples of the polyfunctional acrylate include trimethylolpropane triacrylate, dipentaerythritol triacrylate, propionic acid-modified dipentaerythritol triacrylate, pentaerythritol triacrylate, propylene oxide-modified trimethylolpropane triacrylate, and tris (acryloxyethyl) isocyanurate. Dipentaerythritol pentaacrylate, propionic acid-modified dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, and the like. Examples of the bifunctional methacrylate include ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1.4-butanediol dimethacrylate, neopentylglycol dimethacrylate, 1.6-hexanediol dimethacrylate, 1.9-nonanedioldi. Examples include methacrylate, 1.10-decanediol dimethacrylate, glycerin dimethacrylate, dimethylol-tricyclodecane dimethacrylate, and the like. Examples of the polyfunctional methacrylate include trimethylolpropane trimethacrylate and ethoxylated trimethylolpropane trimethacrylate. The amount of the crosslinking component is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  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 dimensional stability. 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 increase program: 50 ° C (5 minutes) → 10 ° C / minute → 250 ° C (hold)
Inlet temperature: 250 ° C
Carrier gas: Helium (1.0 ml / min)
Split ratio: 50: 1
Injection volume: 1 μl

[Synthesis Example 1]
76.5 g (0.75 mol) of ethylene glycol monoallyl ether and 100 g of toluene were charged into a 1 liter flask equipped with a stirrer, a Dim funnel, a thermometer, and a dropping funnel, and the temperature was raised to 70 ° C. After adding 0.38 g of an alkali chloroplatinic acid neutralized vinylsiloxane complex catalyst toluene solution (platinum content 0.5%) to the flask, using a dropping funnel, 1-butyl-9-hydro-1, 1,3,3,5,5,7,7,9,9-decamethylpentasiloxane (206 g, 0.5 mol) was dropped into the flask over 1 hour. The internal temperature rose to 85 ° C. When the reaction product was analyzed by GC after aging at 100 ° C. for 1 hour, the peak of the raw material monobutyldecamethylhydropentasiloxane disappeared, indicating that the reaction was complete. 200 g of ion-exchanged water was added to the reaction product, washed with stirring, allowed to stand and phase-separated, and the aqueous layer containing excess ethylene glycol monoallyl ether was removed. Similarly, it was washed twice with 200 g ion-exchanged water, and toluene in the organic layer was stripped under reduced pressure to obtain 242 g (yield 94%) of a silicone compound which is a colorless transparent liquid and represented by the following formula (6). The purity of the silicone compound as measured by GC was 99.4% by mass.

[Example 1]
A silicone compound of the above formula (6) 128.5 g (0.25 mol), dioctyl tin oxide 0.01 g (0.01% by mass), ionol 0.01 g, 4-methoxyphenol 0.01 g, stirrer, Dimroth, temperature The total was charged into a 1 liter flask equipped with a dropping funnel, and 62.1 g (0.26 mol) of a (meth) acrylic group-containing isocyanate compound of the following formula (7) was added dropwise over 1 hour. The internal temperature rose from 20 ° C to 40 ° C. The silicone compound of formula (6) was aged at 40 ° C. while monitoring the peak of the compound by GC. After 4 hours, it was confirmed that the peak of the silicone compound of formula (6) was below the detection limit in GC, and 4.0 g (0.125 mol) of methanol was added to the reaction solution. Furthermore, 180 g of hexane and 180 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 from a solvent such as hexane to obtain 150.6 g (0.2 mol, yield 80%) of a colorless transparent liquid product. It was confirmed by ¹ H-NMR analysis that it was a silicone compound represented by the following formula (8) (hereinafter referred to as silicone compound 1). The purity of the silicone compound by GC was 97.5%, the viscosity was 90.0 mm ² / s (25 ° C.), the specific gravity was 1.017 (25 ° C.), and the refractive index was 1.4440. A ¹ H-NMR spectrum of the obtained silicone compound is shown in FIG.

[Synthesis Example 2]
205.6 g (0.4 mol) of the silicone compound of the above formula (6) used in Example 1, 50.6 g (0.5 mol) of the dehydrochlorinating agent, and 500 g of hexane were added to a stirrer, a Dim funnel, a thermometer, and a dropping funnel. A mixture of 48.1 g (0.46 mol) of methacrylic acid chloride and 50 g of hexane was added dropwise over 1 hour while the flask was charged into a 2 liter flask and cooled in a water bath. The internal temperature rose from 20 ° C to 30 ° C. The water bath was removed, and the mixture was aged at room temperature while monitoring the peak of the silicone compound of formula (6) with GC. After 10 hours, the peak of the silicone compound of formula (6) was below the detection limit in GC, so 500 g of ion-exchanged water was added to the reaction solution 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 206 g of a colorless transparent liquid product. It was confirmed by ¹ H-NMR analysis that it was a silicone compound represented by the following formula (9) (yield 89%) (hereinafter referred to as silicone compound 2). The purity of the silicone compound by GC measurement is 98.5%, the viscosity is 5.9 mm ² / s (25 ° C.), the specific gravity is 0.944 (25 ° C.), and the refractive index is 1.4260. there were.

[Synthesis Example 3]
In Example 1, instead of 62.1 g (0.26 mol) of the (meth) acrylic group-containing isocyanate compound of the above formula (7), 40.3 g (0) of the (meth) acrylic group-containing isocyanate compound represented by the following formula (10) Example 1 was repeated except that .26 mol) was used to obtain 147 g (0.22 mol, yield 88%) of a colorless transparent liquid product. It was confirmed by ¹ H-NMR analysis that it was a silicone compound represented by the following formula (11) (hereinafter referred to as silicone compound 3). The purity of the silicone compound by GC was 97.3%, the viscosity was 32.6 mm ² / s (25 ° C.), the specific gravity was 0.993 (25 ° C.), and the refractive index was 1.4381.

で示される片末端水酸基含有ポリシロキサン２３４．４ｇ、下記式
ＯＣＮ−Ｃ（ＣＨ_３）［ＣＨ_２−Ｏ−ＣＯ−ＣＨ＝ＣＨ_２］_２
で示されるイソシアネート化合物（昭和電工製：カレンズＢＥＩ）１１．９５ｇ、トルエン２４６ｇ、ジオクチルスズジアセテート０．２５ｇを仕込み、１００℃で８時間加熱攪拌を行なった。ＩＲにてイソシアネートのピークが消失したことを確認し、１００℃／１０ｍｍＨｇの条件にて減圧ストリップを行ない、トルエンを溜去し、無色透明な生成物を得た。^１Ｈ−ＮＭＲ分析で、下記式（１２）で表されるシリコーン化合物であることが確認された（以下、シリコーン化合物４という）。ＧＰＣ測定の結果、下記式においてｎが平均６０である分布を有する混合物であった。粘度：８７ｍｍ^２／ｓ、揮発分（１０５℃／３時間）：０．４％、屈折率：１．４０８２であった。

[Synthesis Example 4]
A silicone compound described in Example 1 of Patent Document 7 was synthesized.
In a 1 L glass flask equipped with a stirrer, thermometer and reflux condenser,

234.4 g of one-terminal hydroxyl group-containing polysiloxane represented by the following formula: OCN—C (CH ₃ ) [CH ₂ —O—CO—CH═CH ₂ ] ₂
11.95 g of an isocyanate compound (Showa Denko: Karenz BEI), 246 g of toluene and 0.25 g of dioctyltin diacetate were charged, and the mixture was heated and stirred at 100 ° C. for 8 hours. After confirming that the isocyanate peak disappeared by IR, stripping under reduced pressure was performed at 100 ° C./10 mmHg, and toluene was distilled off to obtain a colorless and transparent product. It was confirmed by ¹ H-NMR analysis that it was a silicone compound represented by the following formula (12) (hereinafter referred to as silicone compound 4). As a result of GPC measurement, it was a mixture having a distribution in which n is 60 on average in the following formula. Viscosity: 87 mm ² / s, volatile matter (105 ° C./3 hours): 0.4%, refractive index: 1.4082.

上記式（６）のシリコーン化合物１２８．５ｇ（０．２５ｍｏｌ）にかえて、上記式（１３）のシリコーン化合物１１７．５ｇ（０．２５ｍｏｌ）を用いた他は実施例１を繰返し、無色透明液体の生成物１４５．３ｇ（０．２ｍｏｌ、収率８２％）を得た。^１Ｈ−ＮＭＲ分析で、下記式（１４）で表されるシリコーン化合物であることが確認された（以下、シリコーン化合物５という）。ＧＣによる該シリコーン化合物の純度は９７．８％であり、粘度７５．６ｍｍ^２／ｓ（２５℃）、比重１．０２３（２５℃）、屈折率１．４４５１であった。

[Synthesis Example 5]
Synthetic Example 1 was repeated except that 43.5 g (0.75 mol) of allyl alcohol was used instead of 76.5 g (0.75 mol) of ethylene glycol monoallyl ether, which was a colorless transparent liquid represented by the following formula (13). 223 g (yield 95%) of a silicone compound was obtained. The purity of the silicone compound as measured by GC was 99.6% by mass.

Example 1 was repeated except that 117.5 g (0.25 mol) of the silicone compound of the above formula (13) was used instead of 128.5 g (0.25 mol) of the silicone compound of the above formula (6). 145.3 g (0.2 mol, 82% yield) of was obtained. It was confirmed by ¹ H-NMR analysis that it was a silicone compound represented by the following formula (14) (hereinafter referred to as silicone compound 5). The purity of the silicone compound by GC was 97.8%, the viscosity was 75.6 mm ² / s (25 ° C.), the specific gravity was 1.023 (25 ° C.), and the refractive index was 1.4451.

上記式（６）のシリコーン化合物１２８．５ｇ（０．２５ｍｏｌ）にかえて、上記式（１５）のシリコーン化合物１５０．５ｇ（０．２５ｍｏｌ）を用いた他は実施例１を繰返して無色透明液体の生成物１６８．２ｇ（０．２ｍｏｌ、収率８０％）を得た。^１Ｈ−ＮＭＲ分析で、下記式（１６）で表されるシリコーン化合物であることが確認された（以下、シリコーン化合物６という）。ＧＣによる該シリコーン化合物の純度は９７．８％であり、粘度９６．２ｍｍ^２／ｓ（２５℃）、比重１．０１０（２５℃）、屈折率１．４３７であった。

[Synthesis Example 6]
Synthetic Example 1 was repeated except that 142.5 g (0.75 mol) of triethylene glycol monoallyl ether was used instead of 76.5 g (0.75 mol) of ethylene glycol monoallyl ether. 273.9 g (yield 91%) of the silicone compound represented by (15) was obtained. The purity of the silicone compound as measured by GC was 99.1% by mass.

Example 1 was repeated except that 150.5 g (0.25 mol) of the silicone compound of the above formula (15) was used instead of 128.5 g (0.25 mol) of the silicone compound of the above formula (6). 168.2 g (0.2 mol, 80% yield) of was obtained. It was confirmed by ¹ H-NMR analysis that it was a silicone compound represented by the following formula (16) (hereinafter referred to as silicone compound 6). The purity of the silicone compound by GC was 97.8%, the viscosity was 96.2 mm ² / s (25 ° C.), the specific gravity was 1.010 (25 ° C.), and the refractive index was 1.437.

[Evaluation test]
The following evaluation test was performed using the silicone compound 1 obtained in Example 1 and the silicone compounds 2 to 6 obtained in Synthesis Examples 2 to 6. In Comparative Example 6, triethylene glycol dimethacrylate was used instead of the silicone compound. The results are shown in Table 1.
In the following, polymerizable group-containing silicone monomers, N, N-dimethylacrylamide, and trifluoroethyl methacrylate were used as other polymerizable monomers. As the polymerizable group-containing silicone monomer, the silicone compound 2 obtained in Synthesis Example 2 was used.

(1) Compatibility with other polymerizable monomers 60 parts by mass of a polymerizable group-containing silicone monomer, 35 parts by mass of N, N-dimethylacrylamide, 5 parts by mass of trifluoroethyl methacrylate, and any one of silicone compounds 1-6 Or 1 part by mass of triethylene glycol dimethacrylate (crosslinking component) and Darocur 1173 (photopolymerization initiator, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, manufactured by Ciba Specialty Chemicals) 0.5 parts by mass was mixed and stirred. The appearance of the obtained mixture was visually observed. A mixture having good compatibility between the silicone compound, the silicone monomer, and the other (meth) acrylic compound becomes colorless and transparent, but a mixture having poor compatibility causes turbidity.

(2) Appearance of film (polymer) The mixture prepared in (1) above was degassed under 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.

(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.

(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 before immersion and after immersion for 24 hours was incubated at 37 ° C. ± 2 ° C. for 8 hours in a known artificial lipid solution. 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 ×.

(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.

  As shown in Table 1, the silicone compound of the present invention is well compatible with silicone monomers and other (meth) acrylic monomers to give colorless and transparent polymers. In particular, since it is compatible with the fluorine-substituted group-containing (meth) acrylic monomer, a polymer having excellent stain resistance is obtained. Moreover, the polymer obtained has excellent mechanical strength and good water wettability.

  As shown in the results of Comparative Example 1 in Table 1, the silicone compound 2 (silicone monomer) obtained in Synthesis Example 2 has poor compatibility with other (meth) acrylic monomers, and a transparent mixture and polymer can be obtained. Absent. On the other hand, as shown in the results of Example 1, when the silicone compound of the present invention is mixed with a mixture of a silicone monomer and another (meth) acrylic monomer, a colorless and transparent mixture and polymer can be obtained. That is, the silicone compound of the present invention acts as a compatibilizer in addition to acting as a crosslinking agent.

  Silicone compound 3 has only one methacryl group. As shown in the result of Comparative Example 2, even when the silicone compound 3 is mixed with a mixture of a silicone monomer and another (meth) acrylic monomer, a transparent mixture and polymer cannot be provided. Further, the polymer is inferior in stain resistance and water wettability.

  Silicone compound 4 has low purity, and has a long silicone chain and low hydrophilicity. Therefore, compatibility with other (meth) acrylic monomers is poor. Therefore, as shown in the result of Comparative Example 3, when the silicone compound 4 is mixed with a mixture of a silicone monomer and another (meth) acrylic monomer, the polymer becomes cloudy and cannot give a transparent polymer. Further, the polymer is inferior in mechanical strength, stain resistance and water wettability.

  Silicone compound 5 does not have ethylene oxide in the spacer portion. The silicone compound has low hydrophilicity and is inferior in compatibility with other (meth) acrylic monomers. Therefore, as shown in the result of Comparative Example 4, a transparent polymer cannot be provided. Further, the polymer is inferior in stain resistance and water wettability.

  The silicone compound 6 has two or more ethylene oxides in the spacer portion. The silicone compound is highly hydrophilic and inferior in compatibility with the silicone monomer. Therefore, as shown in the result of Comparative Example 5, a transparent polymer cannot be provided. Further, since the silicone compound 6 has a long polyether spacer chain length, the resulting polymer is inferior in mechanical strength. Further, the polymer is inferior in stain resistance.

  As shown in the results of Comparative Example 6, triethylene glycol dimethacrylate does not contain a silicone chain and is inferior in compatibility with the silicone monomer. Therefore, a transparent polymer cannot be given.

  The compound of the present invention is well compatible with other polymerizable monomers, in particular, (meth) acrylic silicone monomers and fluorine substituent-containing (meth) acrylic monomers. The polymer containing the compound of the present invention as a polymerization component has oxygen permeability, is colorless and transparent, and has excellent mechanical strength. Further, the polymer is excellent in hydrophilicity (water wettability) and stain resistance. Moreover, according to the production method of the present invention, a compound containing one kind of compound having a specific structure with high purity can be provided, and a polymer having high transparency 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 (10)

Compound represented by the following formula (1)

(In Formula (1), m is an integer of 2 to 10, R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is a hydrogen atom or a methyl group, and R ³ is a (meth) acryl group. Is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, R ⁴ is a hydrogen atom or a methyl group, and R ⁵ is a hydrogen atom or methyl. Group). The compound according to claim 1, wherein one of the specific m, R ¹ , R ² , R ³ , R ⁴ and R ⁵ in formula (1) comprises more than 95% by mass of the total mass of the compound. Compound.   The compound according to claim 1 or 2, wherein m is 3.   The polymer obtained by superposing | polymerizing the compound of any one of Claims 1-3, and this and at least 1 sort (s) of the other compound which has a polymeric group.   The polymer of claim 4, wherein the other compound comprises a silicone monomer.   The polymer of Claim 5 whose quantity of the compound of any one of Claims 1-3 is 0.1-50 mass parts with respect to 100 mass parts of silicone monomers.   An ophthalmic device using the polymer according to any one of claims 4 to 6. A method for producing a compound represented by the following formula (1),

In (Equation (1), m is an integer from 2 to 10, ^{R 1} is an alkyl group having 1 to 4 carbon atoms, ^{R 2,} independently of one another, .R ³ is a hydrogen atom or a methyl group ( An unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, which does not contain a (meth) acryl group, and R ⁴ is one of a hydrogen atom and a methyl group, R ⁵ is one of a hydrogen atom and a methyl group)
A silicone compound represented by the following formula (2):

(M, R ¹ and R ² are as described above)
(Meth) acrylic group-containing isocyanate compound represented by the following formula (3)

(R ³ , R ⁴ and R ⁵ are as described above)
The manufacturing method including the process made to react. Each particular one of ^m in the formula ^{(1), R 1, R} 2, R 3, 1 or with ^{R 4} and ^{R 5,} form a 95 wt percent of the total mass of the compound, according to claim 8 Production method.   The production method according to claim 9, wherein m is 3. 10.

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