JP2006193429A - Vinyl group-containing compound and method for producing the same - Google Patents
Vinyl group-containing compound and method for producing the same Download PDFInfo
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Abstract
Description
本発明は、コンタクトレンズ、眼内レンズ、人工角膜などの眼用レンズの製造など医療用途に好適に使用できる原料化合物およびその製造方法に関する。 The present invention relates to a raw material compound that can be suitably used for medical applications such as production of ophthalmic lenses such as contact lenses, intraocular lenses, and artificial corneas, and a method for producing the same.
従来、医療用材料として(メタ)アクリル系モノマーを重合して得られるポリマーが知られている。このポリマーは透明性や十分な硬度を有するため、特に眼科用途、歯科用途に用いられている。そのような化合物の一つとして下記式(b)または(b’) Conventionally, polymers obtained by polymerizing (meth) acrylic monomers as medical materials are known. Since this polymer has transparency and sufficient hardness, it is particularly used for ophthalmic use and dental use. As one of such compounds, the following formula (b) or (b ′)
で表される化合物が知られている(例えば、特許文献1)。この化合物は分子内に2種類の重合性基を有することから架橋剤としてポリマーの硬度を高めることができ、また、分子内に水酸基を有することからヒドロゲル材料の架橋として用いる際には親水性モノマーとの相溶性が得やすいといった特徴がある。また、分子内のビニル基、水酸基部位に種々の官能基を導入してポリマーに新たな物性を付与することも可能である。 Is known (for example, Patent Document 1). Since this compound has two kinds of polymerizable groups in the molecule, it can increase the hardness of the polymer as a crosslinking agent, and since it has a hydroxyl group in the molecule, it is a hydrophilic monomer when used as a crosslink for hydrogel materials. It is easy to obtain compatibility with. It is also possible to impart various physical properties to the polymer by introducing various functional groups into vinyl and hydroxyl groups in the molecule.
しかしながら、上記(b)または(b’)の化合物を得るため、アリルグリシジルエーテルと(メタ)アクリル酸を(メタ)アクリル酸の金属塩存在下で反応させたところ、粗生成物中に下式(a1) However, in order to obtain the above compound (b) or (b ′), allyl glycidyl ether and (meth) acrylic acid were reacted in the presence of a metal salt of (meth) acrylic acid. (A1)
で表される原料エポキシ化合物が残存していることが明らかになった。このエポキシ化合物は分子内に重合性基を有しないことから重合反応後もポリマー内に固定されず、医療用材料として用いた場合、使用中にしみ出してくる危険性があるという問題があった。
本発明者らは、未反応の前記の式(a1)で表される化合物の濃度を低減させるため、種々の検討を行った。例えば、反応時間を延長する方法では、別な不純物が生成し、却って品質の低下を招くことを認めた。 The present inventors have conducted various studies in order to reduce the concentration of the unreacted compound represented by the formula (a1). For example, in the method of extending the reaction time, it was recognized that other impurities are generated and the quality is deteriorated.
また、未反応の前記の式(a1)を単純に蒸留で分離しようとしても主生成物である化合物との親和性が高いため、主生成物の分解を抑制しつつ十分な純度とするには困難である。 Moreover, even if it is going to isolate | separate unreacted said formula (a1) simply by distillation, since it has high affinity with the compound which is a main product, in order to make it sufficient purity, suppressing decomposition | disassembly of a main product. Have difficulty.
すなわち、本発明の課題とするところは、使用中に前記の式(a1)で表されるエポキシ化合物がしみ出てこない医療用材料として使用可能なレベルの原料化合物及び該原料化合物の製造方法を提供することにある。 That is, the subject of the present invention is a raw material compound at a level that can be used as a medical material in which the epoxy compound represented by the formula (a1) does not ooze out during use, and a method for producing the raw material compound. It is to provide.
上記の目的を達成するために、本発明は下記の構成を有する。
(1)下記式(a1)
In order to achieve the above object, the present invention has the following configuration.
(1) The following formula (a1)
で表されるエポキシ化合物に、不飽和カルボン酸の金属塩存在下で前記不飽和カルボン酸の金属塩に対応する不飽和カルボン酸を反応させて下記一般式(a)及び/または(a’) Is reacted with an unsaturated carboxylic acid corresponding to the metal salt of the unsaturated carboxylic acid in the presence of the metal salt of the unsaturated carboxylic acid, and the following general formula (a) and / or (a ′):
で表される化合物を合成する工程、該合成された粗生成物に有機溶媒を添加し、該溶媒と共に未反応の前記エポキシ化合物を留去する工程を含むことを特徴とするビニル基含有化合物の製造方法。
(ここで、一般式(a)、(a’)において、R1は重合性基を有する炭素数1〜20の有機基を表す。)
(2)前記不飽和カルボン酸がアクリル酸またはメタクリル酸である前記(1)記載のビニル基含有化合物の製造方法。
(3)前記添加される有機溶媒の大気圧下での沸点が120〜190℃であることを特徴とする前記(1)または(2)記載のビニル基含有化合物の製造方法。
(4)前記添加される有機溶媒がシクロヘキサノン、乳酸エチル、酢酸エチレングリコールモノメチルエーテル、ジエチレングリコールジメチルエーテル、エチレングリコールジアセテート、ジメチルホルムアミド、プロピオン酸イソペンチルからなる群から選ばれた少なくとも1種の有機溶媒であることを特徴とする前記(1)〜(3)のいずれかに記載のビニル基含有化合物の製造方法。
(5)下記式(a1)
A vinyl group-containing compound comprising: a step of synthesizing a compound represented by the formula: and a step of adding an organic solvent to the synthesized crude product and distilling off the unreacted epoxy compound together with the solvent. Production method.
(Here, in the general formulas (a) and (a ′), R 1 represents a C 1-20 organic group having a polymerizable group.)
(2) The method for producing a vinyl group-containing compound according to (1), wherein the unsaturated carboxylic acid is acrylic acid or methacrylic acid.
(3) The method for producing a vinyl group-containing compound as described in (1) or (2) above, wherein the organic solvent to be added has a boiling point of 120 to 190 ° C. under atmospheric pressure.
(4) The added organic solvent is at least one organic solvent selected from the group consisting of cyclohexanone, ethyl lactate, ethylene acetate monomethyl ether, diethylene glycol dimethyl ether, ethylene glycol diacetate, dimethylformamide, and isopentyl propionate. The method for producing a vinyl group-containing compound according to any one of (1) to (3), wherein:
(5) The following formula (a1)
で表されるエポキシ化合物の含有量が100ppm以下である下記一般式(a)または(a’)で表されるビニル基含有化合物。 The vinyl group containing compound represented by the following general formula (a) or (a ') whose content of the epoxy compound represented by these is 100 ppm or less.
(ここで、一般式(a)、(a’)において、R1は重合性基を有する炭素数1〜20の有機基を表す。) (Here, in the general formulas (a) and (a ′), R 1 represents a C 1-20 organic group having a polymerizable group.)
本発明により、使用中に不純物がしみ出てこない医療用材料をえることができる。また、その原因物質の1つである不純物が低減された原料化合物を得ることができる。 According to the present invention, it is possible to obtain a medical material from which impurities do not ooze out during use. In addition, a raw material compound with reduced impurities, which is one of the causative substances, can be obtained.
本発明によれば、使用中に不純物がしみ出てこない医療用材料を得ることができるが、その中心となるところは、その原因物質である化合物が低減された原料を提供する点にある。 According to the present invention, it is possible to obtain a medical material in which impurities do not ooze out during use, but the main point is to provide a raw material in which a compound as a causative substance is reduced.
すなわち、本発明のビニル基含有化合物は、下記式(a1)で表される化合物の含有量が100ppm以下である。上記一般式(a1)で表される化合物の量としては、80ppm以下とすることが好ましく、50ppm以下とすることがより好ましい。 That is, in the vinyl group-containing compound of the present invention, the content of the compound represented by the following formula (a1) is 100 ppm or less. The amount of the compound represented by the general formula (a1) is preferably 80 ppm or less, and more preferably 50 ppm or less.
本発明の前記一般式(a)および/または(a’)で表される化合物は、例えば、次のような方法により得ることができる。 The compound represented by the general formula (a) and / or (a ′) of the present invention can be obtained, for example, by the following method.
すなわち、式(a1)の化合物を原料として一般式(a)及び/または(a’)の化合物を得る。 That is, the compound of the general formula (a) and / or (a ′) is obtained using the compound of the formula (a1) as a raw material.
(ここで、(a)、(a’)において、R1は重合性基を有する炭素数1〜20の置換基を表す。)
まず、第1の工程について説明する
第1の工程は、まず、前記の式(a1)で表される化合物に、不飽和カルボン酸の金属塩、好ましくはアクリル酸の金属塩またはメタクリル酸の金属塩、の存在下で、不飽和カルボン酸、好ましくはアクリル酸またはメタクリル酸、を反応させる。このR1における重合性基とは、好適にラジカル重合可能な炭素−炭素二重結合を表す。このようなR1を有したカルボン酸単位であるR1−COO−の例としては、ビニロキシ酢酸基、アリロキシ酢酸基、(メタ)アクリル酸基、クロトン酸基、2−(メタ)アクリロイルプロパン酸基、3−(メタ)アクリロイルブタン酸基、4−ビニル安息香酸基などを挙げることができる。これらのうち、R1−COO−としては、該基を導入できる化合物の入手が容易であることと共に重合して得られるポリマーの弾性率が眼用レンズ、特にソフトコンタクトレンズとして用いるのに好適であることから、アクリル酸基およびメタクリル酸基とすることが好ましい。この場合、使用するアクリル酸あるいはメタアクリル酸の量は、原料のエポキシ化合物に対して1〜50当量とすることが好ましく、1.5〜40当量とすることがより好ましく、2〜30当量とすることが最も好ましい。かかる範囲とすることで、未反応の化合物の生成が比較的少量ですみ、純度および収率の点で有利である。なお、不飽和カルボン酸金属塩に対応する不飽和カルボン酸とは、当該不飽和カルボン酸金属塩の金属元素が水素に置き換わったものの意味である。
(Here, in (a) and (a ′), R 1 represents a substituent having 1 to 20 carbon atoms having a polymerizable group.)
First, the first step will be described. In the first step, first, the compound represented by the formula (a1) is added to a metal salt of an unsaturated carboxylic acid, preferably a metal salt of acrylic acid or a metal of methacrylic acid. In the presence of a salt, an unsaturated carboxylic acid, preferably acrylic acid or methacrylic acid, is reacted. The polymerizable group in R 1 represents a carbon-carbon double bond that can be suitably radically polymerized. Examples of such R 1 -COO- is a carboxylic acid unit having a R 1 is a vinyloxy acetate group, allyloxy acetate group, (meth) acrylic acid, crotonic acid group, 2- (meth) acryloylpropanesulfonic acid Group, 3- (meth) acryloylbutanoic acid group, 4-vinylbenzoic acid group and the like. Among these, R 1 —COO— is suitable for use as an ophthalmic lens, particularly a soft contact lens, since the compound capable of introducing the group is easily available and the polymer has a modulus of elasticity obtained by polymerization. For this reason, an acrylic acid group and a methacrylic acid group are preferable. In this case, the amount of acrylic acid or methacrylic acid to be used is preferably 1 to 50 equivalents, more preferably 1.5 to 40 equivalents, and 2 to 30 equivalents with respect to the raw material epoxy compound. Most preferably. By setting the amount within this range, a relatively small amount of unreacted compound is required, which is advantageous in terms of purity and yield. The unsaturated carboxylic acid corresponding to the unsaturated carboxylic acid metal salt means that the metal element of the unsaturated carboxylic acid metal salt is replaced with hydrogen.
また、触媒に用いる不飽和カルボン酸金属塩は前記の不飽和カルボン酸に合わせて適宜選択されるものであるが、好ましくは、アクリル酸またはメタアクリル酸の金属塩、好ましくはアルカリ金属塩、である。不飽和カルボン酸金属塩の添加量は、原料のエポキシ化合物に対して0.001〜5当量が好ましく、0.005〜3当量がより好ましく、0.01〜1当量が最も好ましい。かかる範囲とすることで、反応速度が向上し、経時的に生成する不純物を抑制できることから純度および収率の点で有利である。 In addition, the unsaturated carboxylic acid metal salt used for the catalyst is appropriately selected according to the unsaturated carboxylic acid, and is preferably a metal salt of acrylic acid or methacrylic acid, preferably an alkali metal salt. is there. The amount of the unsaturated carboxylic acid metal salt added is preferably 0.001 to 5 equivalents, more preferably 0.005 to 3 equivalents, and most preferably 0.01 to 1 equivalents with respect to the raw material epoxy compound. By setting this range, the reaction rate is improved, and impurities generated with time can be suppressed, which is advantageous in terms of purity and yield.
本発明のビニル基含有化合物の合成段階の開始から終了の間までの任意の段階においては重合が進行することを防ぐため重合禁止剤を加えてもよい。重合禁止剤の具体例としてはハイドロキノン、ハイドロキノンモノメチルエーテル、2,6−ジ−t−ブチル−4−メチルフェノール、N−ニトロソフェニルヒドロキシルアミンアルミニウムなどを挙げることができる。また、重合禁止剤を用いる場合の添加量は前記の不飽和カルボン酸に対して0.0005〜5重量%が好ましく、0.001〜3重量%がより好ましく、0.005〜1重量%が最も好ましい。かかる範囲とすることで、ビニル基含有化合物合成反応中の重合を抑制でき、また該化合物をラジカル重合してポリマーを得る際の重合反応を著しくは阻害しない。 A polymerization inhibitor may be added in any stage from the start to the end of the synthesis stage of the vinyl group-containing compound of the present invention in order to prevent the polymerization from proceeding. Specific examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-4-methylphenol, N-nitrosophenylhydroxylamine aluminum and the like. In addition, when the polymerization inhibitor is used, the addition amount is preferably 0.0005 to 5% by weight, more preferably 0.001 to 3% by weight, and 0.005 to 1% by weight based on the unsaturated carboxylic acid. Most preferred. By setting it as this range, the polymerization during the vinyl group-containing compound synthesis reaction can be suppressed, and the polymerization reaction when the polymer is obtained by radical polymerization of the compound is not significantly inhibited.
ビニル基含有化合物の合成において、前記式(a1)で示される化合物に前記不飽和カルボン酸を化合せしめるときの反応温度は低すぎると反応時間が長くなり過ぎ、高すぎると生成物が重合してしまう危険性があることから、50〜180℃が好ましく、60〜170℃がより好ましく、70〜160℃が最も好ましい。 In the synthesis of the vinyl group-containing compound, if the reaction temperature when combining the unsaturated carboxylic acid with the compound represented by the formula (a1) is too low, the reaction time becomes too long, and if it is too high, the product is polymerized. 50 to 180 ° C is preferable, 60 to 170 ° C is more preferable, and 70 to 160 ° C is most preferable.
本発明においては、こうして得られた前記の一般式(a)および/または(a’)で表される化合物(粗生成物)中に含まれる未反応の前記一般式(a1)で表される化合物を留去するため、該粗生成物に有機溶媒を添加して該有機溶媒と共に留去する工程を有する。ここで有機溶媒と共に留去するとは、添加した有機溶媒を留去する操作を行う過程で、同時に前記式(a1)で示される化合物の粗生成物中の濃度が低減する(すなわち留去される)ため、このように表現するものである。用いる有機溶媒としては、沸点が低いと前記式(a1)で表された化合物を十分に除去することができず、高いと熱分解あるいは重合反応が進行したりして、純度の低下を招くことがあるため大気圧下で120〜190℃であるものを用いることが好ましい。本発明では、このように有機溶剤を添加して留去を行うことにより、単に精密蒸留を行うなど有機溶媒を添加せずにかかる未反応の前記式(a1)で示される化合物の除去を行う場合よりも低温度でかつ迅速・効果的に留去を行うことが可能であり、結果、この式(a1)で示される化合物に由来する不純物を低減せしめ、また、分解物の生成なども無い。特に好ましい溶媒としては、シクロヘキサノン、乳酸エチル、酢酸エチレングリコールモノメチルエーテル、ジエチレングリコールジメチルエーテル、エチレングリコールジアセテート、ジメチルホルムアミド、プロピオン酸イソペンチルからなる群から選ばれた少なくとも1種の有機溶媒である。有機溶媒としては1種でも2種以上が併用されたものであっても良い。 In the present invention, the unreacted general formula (a1) contained in the compound (crude product) represented by the general formula (a) and / or (a ′) thus obtained is represented. In order to distill off the compound, an organic solvent is added to the crude product and distilled off together with the organic solvent. Distilling together with the organic solvent is a process of distilling off the added organic solvent, and at the same time, the concentration of the compound represented by the formula (a1) in the crude product is reduced (that is, distilled off). Therefore, it is expressed in this way. As the organic solvent to be used, if the boiling point is low, the compound represented by the formula (a1) cannot be sufficiently removed, and if it is high, the thermal decomposition or polymerization reaction proceeds, leading to a decrease in purity. Therefore, it is preferable to use one having a temperature of 120 to 190 ° C. under atmospheric pressure. In the present invention, the unreacted compound represented by the formula (a1) is removed without adding an organic solvent such as by performing precision distillation simply by adding and distilling the organic solvent. It is possible to perform distillation more quickly and effectively at a lower temperature than in the case. As a result, impurities derived from the compound represented by the formula (a1) are reduced, and there is no generation of decomposition products. . A particularly preferable solvent is at least one organic solvent selected from the group consisting of cyclohexanone, ethyl lactate, ethylene acetate monomethyl ether, diethylene glycol dimethyl ether, ethylene glycol diacetate, dimethylformamide, and isopentyl propionate. The organic solvent may be one type or a combination of two or more types.
前記一般式(a)および/または(a’)で表されるビニル基含有化合物中に含まれる前記式(a1)で表される化合物の含有量は100ppm以下である。しみだしを低減した医療用材料が得られるので、好ましくは80ppm以下であり、歯科用途、眼科用途として好ましく使用するには50ppm以下である。 The content of the compound represented by the formula (a1) contained in the vinyl group-containing compound represented by the general formula (a) and / or (a ′) is 100 ppm or less. Since a medical material with reduced bleeding is obtained, it is preferably 80 ppm or less, and 50 ppm or less for preferred use in dental and ophthalmic applications.
本発明のビニル基含有化合物は、そのまま用いても良いが、活性な末端基を有しているので、公知の方法により、各種の官能基、例えば、シロキサニル基や水酸基、カルボキシル基もしくはアミノ基などを有したアルキル基もしくはアリール基を有した化合物を付加せしめて用いることが可能である。特に、酸素透過性に優れたシロキサニル基を化合せしめることは好ましい態様である。 The vinyl group-containing compound of the present invention may be used as it is, but since it has an active end group, various functional groups such as a siloxanyl group, a hydroxyl group, a carboxyl group, an amino group, and the like can be obtained by known methods. It is possible to add and use a compound having an alkyl group or aryl group having In particular, it is a preferred embodiment to combine siloxanyl groups having excellent oxygen permeability.
以下、実施例により本発明を具体的に説明するが、本発明はこれによって限定されるものではない。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
測定方法
ガスクロマトグラフ(GC)測定
GC測定は本体に島津製作所製GC−18A(FID検出器)、キャピラリーカラムにJ&W社DB−5(0.25mm×30m×1μm)を用いた。キャリアガスはヘリウム(138kPa)、注入口温度280℃、検出器温度280℃、昇温プログラムは60℃(5分)→10℃/分→325℃(19分)で測定した。サンプルは測定試料100μLをイソプロピルアルコール1mLに溶解して調製し、1μL注入した。
Measurement Method Gas Chromatograph (GC) Measurement For GC measurement, GC-18A (FID detector) manufactured by Shimadzu Corporation was used as the main body, and J & W DB-5 (0.25 mm × 30 m × 1 μm) was used as the capillary column. The carrier gas was helium (138 kPa), the inlet temperature was 280 ° C., the detector temperature was 280 ° C., and the temperature raising program was 60 ° C. (5 minutes) → 10 ° C./minute→325° C. (19 minutes). A sample was prepared by dissolving 100 μL of a measurement sample in 1 mL of isopropyl alcohol, and 1 μL was injected.
実施例1
1Lの3つ口フラスコにアリルグリシジルエーテル140g(1.23mol)、メタクリル酸422.38g(4.91mol)、メタクリル酸ナトリウム39.77g(0.37mol)、p−メトキシフェノール1.99g(16.3mmol)を加え、空気雰囲気下で100℃に加熱して7時間撹拌した。反応液を室温まで冷却し、トルエン600mLを加え、0.5N水酸化ナトリウム水溶液1200mLで4回、飽和食塩水1200mLで2回洗浄し、有機層に硫酸ナトリウムを加えて乾燥し、ろ過してエバポレータで溶媒を留去した。得られた液体にエチレングリコールジアセテートを得られた粗生成物に対して20重量%添加し、エバポレータで1mmHg以下に減圧しながら70℃で30分間、該溶媒の留去を行った。得られた液体中に含まれるエポキシ化合物の量をGCを用いて定量した結果は表1の通りであった。
Example 1
In a 1 L three-necked flask, 140 g (1.23 mol) of allyl glycidyl ether, 422.38 g (4.91 mol) of methacrylic acid, 39.77 g (0.37 mol) of sodium methacrylate, 1.99 g of p-methoxyphenol (16. 3 mmol) was added, heated to 100 ° C. in an air atmosphere and stirred for 7 hours. The reaction solution is cooled to room temperature, added with 600 mL of toluene, washed 4 times with 1200 mL of 0.5N aqueous sodium hydroxide solution and twice with 1200 mL of saturated brine, dried over sodium sulfate added to the organic layer, filtered and evaporated. The solvent was distilled off. 20% by weight of ethylene glycol diacetate was added to the obtained liquid with respect to the obtained crude product, and the solvent was distilled off at 70 ° C. for 30 minutes while reducing the pressure to 1 mmHg or less with an evaporator. The amount of the epoxy compound contained in the obtained liquid was quantified using GC as shown in Table 1.
実施例2
エチレングリコールジアセテートをジグライムに変える以外は実施例1と同様の方法で実験を行った。GC測定結果は表1のとおりであった。
Example 2
The experiment was conducted in the same manner as in Example 1 except that ethylene glycol diacetate was changed to diglyme. The GC measurement results are shown in Table 1.
実施例3
エチレングリコールジアセテートを酢酸エチレングリコールモノメチルエーテルに変える以外は実施例1と同様の方法で実験を行った。GC測定結果は表1のとおりであった。
Example 3
The experiment was conducted in the same manner as in Example 1 except that ethylene glycol diacetate was changed to ethylene glycol monomethyl ether acetate. The GC measurement results are shown in Table 1.
実施例4
エチレングリコールジアセテートを乳酸エチルに変える以外は実施例1と同様の方法で実験を行った。GC測定結果は表1のとおりであった。
Example 4
The experiment was conducted in the same manner as in Example 1 except that ethylene glycol diacetate was changed to ethyl lactate. The GC measurement results are shown in Table 1.
実施例5
エチレングリコールジアセテートをプロピオン酸イソペンチルに変える以外は実施例1と同様の方法で実験を行った。GC測定結果は表1のとおりであった。
Example 5
The experiment was conducted in the same manner as in Example 1 except that ethylene glycol diacetate was changed to isopentyl propionate. The GC measurement results are shown in Table 1.
比較例1
溶媒を添加しない以外は実施例1と同様の方法で実験を行った。GC測定結果は表1のとおりであった。
Comparative Example 1
The experiment was performed in the same manner as in Example 1 except that no solvent was added. The GC measurement results are shown in Table 1.
比較例2
エチレングリコールジアセテートをヘキサンに変える以外は実施例1と同様の方法で実験を行った。GC測定結果は表1のとおりであった。
Comparative Example 2
The experiment was conducted in the same manner as in Example 1 except that ethylene glycol diacetate was changed to hexane. The GC measurement results are shown in Table 1.
比較例3
エチレングリコールジアセテートをトルエンに変える以外は実施例1と同様の方法で実験を行った。GC測定結果は表1のとおりであった。
Comparative Example 3
The experiment was performed in the same manner as in Example 1 except that ethylene glycol diacetate was changed to toluene. The GC measurement results are shown in Table 1.
Claims (5)
(ここで、一般式(a)、(a’)において、R1は重合性基を有する炭素数1〜20の有機基を表す。) The following formula (a1)
(Here, in the general formulas (a) and (a ′), R 1 represents a C 1-20 organic group having a polymerizable group.)
下記一般式(a)または(a’)で表されるビニル基含有化合物。
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JP2009542674A (en) * | 2006-06-30 | 2009-12-03 | 東レ株式会社 | Acryloyl raw material for plastic moldings |
JP2010248225A (en) * | 2010-06-25 | 2010-11-04 | Toray Ind Inc | Manufacturing method of medical device |
JP2013208437A (en) * | 2013-04-26 | 2013-10-10 | Toray Ind Inc | Method for manufacturing vinyl-group containing compound and medical instrument |
WO2020045225A1 (en) | 2018-08-30 | 2020-03-05 | 信越化学工業株式会社 | (meth)acryloyl compound and method for producing same |
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JPS5186413A (en) * | 1975-01-23 | 1976-07-29 | Toa Gosei Chem Ind | |
JP2000297062A (en) * | 1999-04-14 | 2000-10-24 | Dainippon Ink & Chem Inc | Production of hydroxyalkyl (meth)acrylate |
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JP2000297062A (en) * | 1999-04-14 | 2000-10-24 | Dainippon Ink & Chem Inc | Production of hydroxyalkyl (meth)acrylate |
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2009542674A (en) * | 2006-06-30 | 2009-12-03 | 東レ株式会社 | Acryloyl raw material for plastic moldings |
JP2010248225A (en) * | 2010-06-25 | 2010-11-04 | Toray Ind Inc | Manufacturing method of medical device |
JP2013208437A (en) * | 2013-04-26 | 2013-10-10 | Toray Ind Inc | Method for manufacturing vinyl-group containing compound and medical instrument |
WO2020045225A1 (en) | 2018-08-30 | 2020-03-05 | 信越化学工業株式会社 | (meth)acryloyl compound and method for producing same |
US11919987B2 (en) | 2018-08-30 | 2024-03-05 | Shin-Etsu Chemical Co., Ltd. | (Meth)acryloyl compound and a method for preparing the same |
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