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CN114516941A - Polymerization method of polymer material for rigid oxygen permeable contact lens - Google Patents

Polymerization method of polymer material for rigid oxygen permeable contact lens
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CN114516941A
CN114516941ACN202011295088.6ACN202011295088ACN114516941ACN 114516941 ACN114516941 ACN 114516941ACN 202011295088 ACN202011295088 ACN 202011295088ACN 114516941 ACN114516941 ACN 114516941A
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polymerization method
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lens
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林文宾
黄雪芳
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Brighten Optix Corp
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Abstract

Translated fromChinese

本发明公开了一种硬式透氧隐形眼镜高分子材料的聚合方法,该镜片的成份为包含有预设比例组成的甲基丙稀酸六氟异丙酯、3-(异丁烯酰氧)丙基三(三甲基硅氧烷)硅烷、新戊二醇二甲基丙烯酸酯、甲基丙烯酸、交联剂、2,5-二甲基-2,5-双(2-乙基己酸过氧化)己烷及2,2’-二羟基-4,4’-二甲氧基二苯甲酮,通过此些复数单体聚合而成的高分子材料制成的隐形眼镜镜片具有优良的透氧度,且亦具有较高的硬度及机械强度,以使配戴该隐形眼镜时能提升使用者的舒适度,并减少角膜病变。The invention discloses a polymerization method for a polymer material of a rigid oxygen-permeable contact lens. The lens is composed of hexafluoroisopropyl methacrylate and 3-(methacryloyloxy)propyl group in a preset ratio. Tris(trimethylsiloxane)silane, neopentyl glycol dimethacrylate, methacrylic acid, crosslinking agent, 2,5-dimethyl-2,5-bis(2-ethylhexanoic acid) Oxide) hexane and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, contact lenses made of polymer materials obtained by polymerizing these plural monomers have excellent permeability. It also has high hardness and mechanical strength, so that the user's comfort can be improved when wearing the contact lens, and corneal lesions can be reduced.

Description

Translated fromChinese
硬式透氧隐形眼镜高分子材料的聚合方法Polymerization method of polymer material for rigid oxygen permeable contact lens

技术领域technical field

本发明涉及一种硬式透氧隐形眼镜高分子材料的聚合方法,还涉及由复数单体聚合而成的镜片,且此镜片具有优良的透氧度,并具有较高的硬度及机械强度,以使配戴硬式透氧隐形眼镜时能提升使用者的舒适度,并减少角膜病变。The invention relates to a method for polymerizing a polymer material for a rigid oxygen-permeable contact lens, and also relates to a lens polymerized from a plurality of monomers, and the lens has excellent oxygen permeability, high hardness and mechanical strength, and Improves user comfort and reduces corneal pathology when wearing rigid oxygen-permeable contact lenses.

背景技术Background technique

目前,随着各种电子、电气产品的研发、创新,带给人们在日常生活及工作上许多便捷,尤其是电子产品的大量问世,更造成在通讯及因特网的应用的普及化,以致许多人沉浸在电子产品的使用领域中,长时间大量应用电子产品,不论是上班族、学生族群或是中老年人等,涵盖的范围也相当广泛,进而衍生出低头族的现象,也因此造就许多人的眼睛视力减损、伤害等情况日趋严重,近视人口也就相对提高。At present, with the development and innovation of various electronic and electrical products, it has brought people a lot of convenience in daily life and work, especially the advent of a large number of electronic products. Immersed in the field of use of electronic products, a large number of electronic products are used for a long time, whether it is office workers, students, middle-aged and elderly people, etc., covering a wide range, and then the phenomenon of bow-headed people has been derived, which has also created many people. The vision loss and injury of the eyes are becoming more and more serious, and the myopic population is relatively increasing.

再者,人们的所以会发生近视,是由于眼睛的光线曲折能力与眼睛的长度不匹配所导致,其可能是眼轴超长或角膜弧度过陡,造成视物成像点落在视网膜前方处,导致视物成像时产生模糊的情况,所以为了矫正近视需要降低眼睛光线的曲折能力,由于角膜的光线曲折能力约占全眼的80%,所以仅须降低角膜的屈光力便可达到矫正近视的效用。Furthermore, people's myopia is caused by the mismatch between the eye's ability to bend light and the length of the eye. It may be that the eye axis is too long or the corneal arc is too steep, causing the visual imaging point to fall in front of the retina. Causes blurring of vision when imaging, so in order to correct myopia, it is necessary to reduce the bending ability of the eye light. Since the corneal light bending ability accounts for about 80% of the whole eye, it is only necessary to reduce the refractive power of the cornea to achieve the effect of correcting myopia. .

目前矫正屈光不正的方式主要有配戴眼镜矫正、配戴隐形镜片矫正、角膜近视手术或配戴角膜塑型片矫正这几种方法,然而,一般隐形镜片有软式及硬式两种,过去常见的硬式透氧隐形眼镜的材料为聚甲基丙烯酸甲酯(poly(me thylmethacrylate),PMMA),该聚甲基丙烯酸甲酯为具有相当好的光学性能,其优点有高透明度、价格低及易于加工等,但是,聚甲基丙烯酸甲酯虽然透氧性相当好,但却相当疏水,易于镜片表面产生沉淀物,导致影响配戴者的舒适性与安全性。At present, the main methods of correcting refractive errors include wearing glasses, wearing contact lenses, corneal myopia surgery, or wearing orthokeratology lenses. However, there are generally two types of contact lenses: soft and hard. The material of common hard oxygen-permeable contact lenses is poly(methylmethacrylate) (PMMA), which has quite good optical properties, and its advantages are high transparency, low price and It is easy to process, etc. However, although the oxygen permeability of polymethyl methacrylate is quite good, it is quite hydrophobic, and it is easy to produce deposits on the surface of the lens, which will affect the comfort and safety of the wearer.

所以为了改善疏水性的问题,隐形眼镜的制造原料发展至使用甲基丙烯酸羟乙酯(2-hydroxyethyl methacrylate,HEM A),该甲基丙烯酸羟乙酯的结构中含有-OH官能基,其-OH官能基可与水产生氢键,因此可改善疏水性的问题,并且,甲基丙烯酸羟乙酯具有透氧系数(D K值)高的优点,以可提升配戴舒适度,然而,虽然透氧系数愈高愈透氧,但是机械强度却会越来越差,最为明显是硬度低的缺点,如图5所示,甲基丙烯酸羟乙酯的硬度最高也才到70duro,硬度较低的材料不适用于制造硬式隐形眼镜。Therefore, in order to improve the problem of hydrophobicity, the raw materials for the manufacture of contact lenses have been developed to use 2-hydroxyethyl methacrylate (HEM A). The structure of hydroxyethyl methacrylate contains -OH functional groups, which - The OH functional group can generate hydrogen bonds with water, so it can improve the hydrophobicity problem, and hydroxyethyl methacrylate has the advantage of high oxygen permeability coefficient (D K value), which can improve wearing comfort, however, although the permeability The higher the oxygen coefficient, the more oxygen permeable, but the mechanical strength will be worse and worse. The material is not suitable for making hard contact lenses.

因此,要如何设法解决上述现有技术的缺失与不便,即为从事此行业的相关业者所亟欲研究改善的方向所在。Therefore, how to solve the above-mentioned deficiencies and inconveniences of the prior art is an urgent research direction for relevant practitioners engaged in this industry.

发明内容SUMMARY OF THE INVENTION

故,发明人有鉴于上述缺失,乃搜集相关资料,经由多方评估及考虑,并以从事于此行业累积的多年经验,经由不断试作及修改,提出了一种硬式透氧隐形眼镜高分子材料结构的聚合方法。Therefore, in view of the above deficiencies, the inventor collected relevant information, evaluated and considered from various parties, and based on years of experience accumulated in this industry, through continuous trial production and revision, a rigid oxygen-permeable contact lens polymer material was proposed. Aggregation methods for structures.

为了达到上述目的,本发明采用了以下技术手段:In order to achieve the above object, the present invention adopts the following technical means:

本发明的一种硬式透氧隐形眼镜高分子材料的聚合方法,其包含下列的步骤:A polymerization method of a rigid oxygen-permeable contact lens polymer material of the present invention comprises the following steps:

(A)先将复数种单体加入容器中,以使容器内部容置有包含复数种单体的溶液,并通过加热装置将溶液加热至默认温度,以使溶液包含的复数种单体产生聚合反应,进而固化形成高分子固化物,而该复数种单体为包括有预设比例组成的甲基丙稀酸六氟异丙酯、3-(异丁烯酰氧)丙基三(三甲基硅氧烷)硅烷、新戊二醇二甲基丙烯酸酯、甲基丙烯酸、交联剂、2,5-二甲基-2,5-双(2-乙基己酸过氧化)己烷及2,2’-二羟基-4,4’-二甲氧基二苯甲酮;(A) firstly adding a plurality of monomers into a container, so that a solution containing a plurality of monomers is contained in the container, and the solution is heated to a default temperature by a heating device, so that a plurality of monomers contained in the solution are polymerized react, and then solidify to form a polymer cured product, and the plurality of monomers are composed of hexafluoroisopropyl methacrylate, 3-(methacryloyloxy)propyltris(trimethylsilicon) in a preset ratio oxane) silane, neopentyl glycol dimethacrylate, methacrylic acid, crosslinking agent, 2,5-dimethyl-2,5-bis(2-ethylhexanoic acid peroxy)hexane and 2 , 2'-dihydroxy-4,4'-dimethoxybenzophenone;

(B)并将容器内的溶液倒入器皿中,且将器皿放置于烘箱中以默认温度进行默认时间的热固化作业,以使溶液包含的复数种单体产生纯化反应,进而形成内部无单体的高分子固化物;(B) Pour the solution in the container into a vessel, and place the vessel in an oven to perform a heat curing operation at a default temperature for a default time, so that a plurality of monomers contained in the solution are purified and reacted, thereby forming an internal monolithic The polymer solidified product of the body;

(C)再将内部无单体的高分子固化物放置于退火装置中,以对内部无单体的高分子固化物进行退火处理,而经由退火处理后的高分子固化物即为所述的硬式透氧隐形眼镜高分子材料。(C) Place the polymer cured product without monomers in the annealing device to perform annealing treatment on the polymer cured product without monomers, and the polymer cured product after annealing treatment is the above Hard oxygen permeable contact lens polymer material.

其中,优选的,该步骤(A)中该甲基丙稀酸六氟异丙酯的重量比例为介于1%~50%,该3-(异丁烯酰氧)丙基三(三甲基硅氧烷)硅烷的重量比例为介于1%~40%,该新戊二醇二甲基丙烯酸酯的重量比例为介于1%~15%,该甲基丙烯酸的重量比例为介于1%~20%,该交联剂的重量比例为介于1%~10%,该2,5-二甲基-2,5-双(2-乙基己酸过氧化)己烷的重量比例为介于0.1%~1%,该2,2’-二羟基-4,4’-二甲氧基二苯甲酮的重量比例为介于0.1%~1%,各成分之和等于100%。Wherein, preferably, in the step (A), the weight ratio of the hexafluoroisopropyl methacrylate is between 1% and 50%, and the 3-(methacryloyloxy)propyltris(trimethylsilicon) The weight proportion of oxane) silane is between 1% and 40%, the weight proportion of the neopentyl glycol dimethacrylate is between 1% and 15%, and the weight proportion of the methacrylic acid is between 1% and 1%. ~20%, the weight proportion of the crosslinking agent is between 1% and 10%, and the weight proportion of the 2,5-dimethyl-2,5-bis(2-ethylhexanoic acid peroxy)hexane is The weight ratio of the 2,2'-dihydroxy-4,4'-dimethoxybenzophenone is between 0.1% and 1%, and the sum of the components is equal to 100%.

其中,优选的,该交联剂为聚二甲基硅氧烷甲基丙烯酸酯或聚二甲基硅氧烷甲基丁烯酸酯。Among them, preferably, the crosslinking agent is polydimethylsiloxane methacrylate or polydimethylsiloxane methacrylate.

其中,优选的,该步骤(A)容器中的复数种单体还包括有聚甲基丙烯酸(乙二醇)脂、N-乙烯基吡咯烷酮或丙烯酰胺,且该聚甲基丙烯酸(乙二醇)脂的重量比例为介于0.1%~1%,该N-乙烯基吡咯烷酮的重量比例为介于0.1%~1%,且该丙烯酰胺的重量比例为介于0.1%~1%,各成分之和等于100%。Wherein, preferably, the plurality of monomers in the container in this step (A) also include polymethacrylic acid (ethylene glycol) ester, N-vinylpyrrolidone or acrylamide, and the polymethacrylic acid (ethylene glycol) ) The weight proportion of the fat is between 0.1% and 1%, the weight proportion of the N-vinylpyrrolidone is between 0.1% and 1%, and the weight proportion of the acrylamide is between 0.1% and 1%. The sum equals 100%.

其中,优选的,该步骤(A)中的容器为先装有溶剂,且该溶剂为二环氧乙烷。Wherein, preferably, the container in this step (A) is firstly filled with a solvent, and the solvent is diene oxide.

其中,优选的,该步骤(A)中的加热装置为加热板或酒精灯,且加热装置加热的默认温度为100℃。Wherein, preferably, the heating device in this step (A) is a heating plate or an alcohol lamp, and the default temperature for heating by the heating device is 100°C.

其中,优选的,该步骤(B)中的器皿放置于烘箱中进行热固化作业时,该器皿为先放置于65℃烘箱中至少68小时进行热固化,再使温度加热至大于100℃,以使器皿中的单体固化,之后再加热至220℃,便使硅跟氟的键结断键,进而使溶液的分子重新排列而产生纯化反应,进而形成高分子固化物。Wherein, preferably, when the vessel in this step (B) is placed in an oven for thermal curing, the vessel is first placed in an oven at 65° C. for at least 68 hours for thermal curing, and then heated to a temperature greater than 100° C. The monomer in the vessel is cured, and then heated to 220°C to break the bond between silicon and fluorine, and then the molecules of the solution are rearranged to generate a purification reaction, thereby forming a polymer cured product.

其中,优选的,该步骤(B)中执行前为添加可逆行加成分裂链转移聚合反应试剂,且该可逆行加成分裂链转移聚合反应试剂为二硫代苯甲酸酯、三硫代碳酸盐、二硫代胺基甲酸酯或黄原酸盐。Wherein, preferably, in this step (B), a reversible addition-splitting chain transfer polymerization reagent is added before execution, and the reversible addition-splitting chain transfer polymerization reagent is dithiobenzoate, trithiobenzoate, Carbonate, dithiocarbamate or xanthate.

其中,优选的,该步骤(B)聚合反应执行后,即使用gamma射线来照射高分子固化物。Wherein, preferably, after the step (B) the polymerization reaction is performed, the polymer cured product is irradiated with gamma rays.

其中,优选的,该步骤(C)的镜片原料的透氧度为介于170~200b arrer之间,且硬度为介于76~81duro之间。Wherein, preferably, the oxygen permeability of the lens material in the step (C) is between 170-200 barrer, and the hardness is between 76-81 duro.

进一步的,本发明还提出了一种硬式透氧隐形眼镜镜片,其由本发明所述的方法制备得到的硬式透氧隐形眼镜高分子材料制成,该镜片一侧为形成有贴覆于眼球的角膜表面上的内表面,而镜片另一侧则形成有供眼皮接触的外表面。Further, the present invention also proposes a hard oxygen permeable contact lens lens, which is made of the hard oxygen permeable contact lens polymer material prepared by the method of the present invention, and one side of the lens is formed with a lens attached to the eyeball. The inner surface on the surface of the cornea, while the other side of the lens forms the outer surface for the eyelid to contact.

相较于先有技术,本发明的有益效果是:Compared with the prior art, the beneficial effects of the present invention are:

通过本发明的方法制备得到的高分子材料制成的隐形眼镜镜片具有优良的透氧度,且亦具有较高的硬度及机械强度,以使配戴硬式透氧隐形眼镜时能提升使用者的舒适度,并减少角膜病变。The contact lens made of the polymer material prepared by the method of the present invention has excellent oxygen permeability, and also has high hardness and mechanical strength, so that when wearing the hard oxygen-permeable contact lens, the user's safety can be improved. Comfort and reduce corneal pathology.

附图说明Description of drawings

图1为本发明镜片的侧视图;Fig. 1 is the side view of the lens of the present invention;

图2为本发明的流程图;Fig. 2 is the flow chart of the present invention;

图3为本发明的透氧率测试图;Fig. 3 is the oxygen permeability test chart of the present invention;

图4为本发明的硬度测试图;Fig. 4 is the hardness test chart of the present invention;

图5为现有HEMA的硬度测试图。Figure 5 is a hardness test chart of the existing HEMA.

符号说明:Symbol Description:

1:镜片1: Lens

11:内表面11: inner surface

12:外表面12: Outer surface

具体实施方式Detailed ways

为达成上述目的及功效,本发明所采用的技术手段及其构造,兹绘图就本发明的较佳实施例详加说明其特征与功能如下,俾利完全了解。In order to achieve the above objects and effects, the technical means and structures adopted by the present invention are described in detail with reference to the preferred embodiments of the present invention, and the features and functions are as follows, so as to be fully understood.

请参阅图1,为本发明镜片的侧视图,由图中可清楚看出,该镜片1为可供配戴于眼球上的硬式隐形眼镜片(如:角膜塑型镜片或巩膜镜片等),并由高透氧材料所制成,其镜片1一侧为形成有贴覆于眼球的角膜表面上的内表面11,而镜片1另侧则形成有供眼皮接触的外表面12,且镜片1的成份为包含有预设比例组成的甲基丙稀酸六氟异丙酯、3-(异丁烯酰氧)丙基三(三甲基硅氧烷)硅烷、新戊二醇二甲基丙烯酸酯、甲基丙烯酸、聚二甲基硅氧烷甲基丙烯酸酯、2,5-二甲基-2,5-双(2-乙基己酸过氧化)己烷、2,2’-二羟基-4,4’-二甲氧基二苯甲酮、聚甲基丙烯酸(乙二醇)脂﹝Poly(ethy lene glycol)methacrylate﹞、N-乙烯基吡咯烷酮及丙烯酰胺。Please refer to FIG. 1, which is a side view of the lens of the present invention. It can be clearly seen from the figure that the lens 1 is a hard contact lens (such as an orthokeratology lens or a sclera lens, etc.) that can be worn on the eyeball, It is made of high oxygen permeable material. One side of the lens 1 is formed with aninner surface 11 attached to the corneal surface of the eyeball, and the other side of the lens 1 is formed with anouter surface 12 for eyelid contact. The ingredients are hexafluoroisopropyl methacrylate, 3-(methacryloyloxy)propyltris(trimethylsiloxane)silane, neopentyl glycol dimethacrylate in preset proportions. , methacrylic acid, polydimethylsiloxane methacrylate, 2,5-dimethyl-2,5-bis(2-ethylhexanoic acid peroxy)hexane, 2,2'-dihydroxy -4,4'-Dimethoxybenzophenone, poly(ethylene glycol) methacrylate (Poly(ethy lene glycol) methacrylate), N-vinylpyrrolidone and acrylamide.

上述的甲基丙稀酸六氟异丙酯的重量比例为40%,该3-(异丁烯酰氧)丙基三(三甲基硅氧烷)硅烷的重量比例为25%,该新戊二醇二甲基丙烯酸酯的重量比例为9%,甲基丙烯酸的重量比例为15%,该聚二甲基硅氧烷甲基丙烯酸酯的重量比例为8%,该2,5-二甲基-2,5-双(2-乙基己酸过氧化)己烷的重量比例为1%,该2,2’-二羟基-4,4’-二甲氧基二苯甲酮的重量比例为0.5%,该聚甲基丙烯酸(乙二醇)脂的重量比例为0.5%,该N-乙烯基吡咯烷酮的重量比例为0.5%,该丙烯酰胺的重量比例为0.5%。The weight proportion of the above-mentioned hexafluoroisopropyl methacrylate is 40%, the weight proportion of the 3-(methacryloyloxy)propyltris(trimethylsiloxane)silane is 25%, and the neopentyl The weight proportion of alcohol dimethacrylate is 9%, the weight proportion of methacrylic acid is 15%, the weight proportion of the polydimethylsiloxane methacrylate is 8%, the 2,5-dimethyl methacrylate The weight ratio of -2,5-bis(2-ethylhexanoic acid peroxy)hexane is 1%, and the weight ratio of the 2,2'-dihydroxy-4,4'-dimethoxybenzophenone is 0.5%, the weight proportion of the polymethacrylate (ethylene glycol) is 0.5%, the weight proportion of the N-vinylpyrrolidone is 0.5%, and the weight proportion of the acrylamide is 0.5%.

再请参阅图2、3、4所示,为本发明的流程图、透氧率测试图及硬度测试图,由图中可清楚看出,本发明镜片1原料的制造方法为包含下列的步骤:Please refer to FIGS. 2, 3, and 4 again, which are the flow chart, oxygen permeability test chart and hardness test chart of the present invention. It can be clearly seen from the figures that the manufacturing method of the raw material of the lens 1 of the present invention includes the following steps :

(A)先将复数种单体加入容器(如:烧杯或批次加热搅拌器)中,以使容器内部容置有包含复数种单体的溶液,并通过加热装置将溶液加热至默认温度,以使溶液包含的复数种单体产生聚合反应,进而固化形成高分子固化物,而该复数种单体为包括有预设比例组成的甲基丙稀酸六氟异丙酯、3-(异丁烯酰氧)丙基三(三甲基硅氧烷)硅烷、新戊二醇二甲基丙烯酸酯、甲基丙烯酸、交联剂、2,5-二甲基-2,5-双(2-乙基己酸过氧化)己烷及2,2’-二羟基-4,4’-二甲氧基二苯甲酮。(A) first adding a plurality of monomers into a container (such as a beaker or a batch heating stirrer), so that a solution containing a plurality of monomers is contained in the container, and the solution is heated to a default temperature by a heating device, A plurality of monomers contained in the solution are polymerized and then cured to form a polymer cured product, and the plurality of monomers are composed of hexafluoroisopropyl methacrylate, 3-(isobutylene, etc. in a preset ratio. Acyloxy)propyltris(trimethylsiloxane)silane, neopentyl glycol dimethacrylate, methacrylic acid, crosslinking agent, 2,5-dimethyl-2,5-bis(2- ethylhexanoic acid peroxy) hexane and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

(B)并将容器内的溶液倒入器皿(如:棒状模具)中,且将器皿放置于烘箱中以默认温度进行默认时间的热固化作业,以使溶液包含的复数种单体产生纯化反应,进而形成内部无单体的高分子固化物。(B) Pour the solution in the container into a vessel (such as a rod-shaped mold), and place the vessel in an oven to perform a thermal curing operation at a default temperature for a default time, so that a plurality of monomers contained in the solution are purified and reacted , and then form a polymer cured product without monomers inside.

(C)再将内部无单体的高分子固化物放置于退火装置(如:退火炉)中,以对内部无单体的高分子固化物进行退火处理,而经由退火处理后的高分子固化物便可成为镜片1的原料,藉此完成本发明的制造作业。(C) Place the polymer cured product without monomer inside in an annealing device (such as an annealing furnace) to anneal the polymer cured product without monomer inside, and the polymer cured after the annealing treatment is cured The material can become the raw material of the lens 1, thereby completing the manufacturing operation of the present invention.

上述步骤(A)中的容器为可先装有溶剂,且该溶剂可为二环氧乙烷(an hydrousdioxane)。The container in the above step (A) can be filled with a solvent first, and the solvent can be an hydrousdioxane.

而上述步骤(A)中的交联剂可为聚二甲基硅氧烷甲基丙烯酸酯或聚二甲基硅氧烷甲基丁烯酸酯。The crosslinking agent in the above step (A) can be polydimethylsiloxane methacrylate or polydimethylsiloxane methacrylate.

又上述步骤(A)中容器内的复数单体为可进一步添加有聚甲基丙烯酸(乙二醇)脂、N-乙烯基吡咯烷酮或丙烯酰胺,且该镜片1材料添加有聚甲基丙烯酸(乙二醇)脂、N-乙烯基吡咯烷酮或丙烯酰胺,便可提升整体亲水性。In the above step (A), the plurality of monomers in the container can be further added with polymethacrylate (ethylene glycol), N-vinylpyrrolidone or acrylamide, and the lens 1 material is added with polymethacrylic acid ( Glycol) ester, N-vinylpyrrolidone or acrylamide can improve the overall hydrophilicity.

再者,上述步骤(A)中的加热装置可为加热板、酒精灯或其它可提供热能的装置,且该加热装置加热的默认温度可为100℃,而该加热装置加热的过程中,为可进一步利用搅拌装置来进行搅拌动作。Furthermore, the heating device in the above-mentioned step (A) can be a heating plate, an alcohol lamp or other devices that can provide thermal energy, and the default temperature of the heating device heating can be 100 ° C, and during the heating process of the heating device, it is The stirring action can be further performed by using a stirring device.

且上述步骤(A)中的容器若为批次加热搅拌器时,便可配合蠕动帮浦使用,以可通过蠕动帮浦来将容器内的溶液倒入器皿中。And if the container in the above step (A) is a batch heating mixer, it can be used with a peristaltic pump, so that the solution in the container can be poured into the vessel through the peristaltic pump.

然而,上述步骤(B)中的器皿放置于烘箱中进行热固化作业时,该器皿为先放置于65℃烘箱中至少68小时进行热固化,再使温度加热至大于100℃,以使器皿中的单体再固化,之后再加热至220℃,便可使硅跟氟的键结断键,进而使溶液的分子重新排列而产生纯化反应,进而形成高分子固化物。However, when the vessel in the above step (B) is placed in an oven for thermal curing, the vessel is first placed in an oven at 65° C. for at least 68 hours for thermal curing, and then heated to a temperature greater than 100° C. The monomer is re-solidified, and then heated to 220 ° C, the bond between silicon and fluorine can be broken, and the molecules of the solution can be rearranged to generate a purification reaction, thereby forming a polymer cured product.

另外,上述步骤(B)中执行前为可添加可逆行加成分裂链转移聚合反应(reverseaddition-fragmentation tran sfer polymerization,RAFT)试剂,以使聚合反应可为可逆行加成分裂链转移聚合反应,其可逆行加成分裂链转移聚合反应可将含有亲水单元的-OH基及含有长碳链的单体聚合,且通过可逆行加成分裂链转移聚合反应的方式可使聚合速度较慢,进而使溶液中各种单体有效进行接触,藉此形成分子量大、分散性高且稳定的高分子聚合物,从而可提高材料的亲水性,且该可逆行加成分裂链转移聚合反应试剂可为二硫代苯甲酸酯(Dithioben zoates)、三硫代碳酸盐(Trithiocarbonates)、二硫代胺基甲酸酯(Dithiocarbamates)或黄原酸盐(Xanth ates)等。In addition, before the execution of the above step (B), a reversible addition-fragmentation transfer polymerization (RAFT) reagent can be added, so that the polymerization can be a reversible addition-fragmentation chain transfer polymerization reaction, The reversible addition-splitting chain transfer polymerization can polymerize -OH groups containing hydrophilic units and monomers containing long carbon chains, and the polymerization speed can be slowed by the reversible addition-splitting chain transfer polymerization. Further, various monomers in the solution are effectively contacted, thereby forming a high molecular weight, high dispersibility and stable high molecular polymer, thereby improving the hydrophilicity of the material, and the reversible addition and splitting chain transfer polymerization reaction reagent It can be Dithioben zoates, Trithiocarbonates, Dithiocarbamates or Xanthates.

且上述步骤(B)中的纯化反应较佳可为可逆行加成分裂链转移聚合反应,但于实际应用时,亦可为自由基聚合(free radical polym erization)、离子聚合(ionicpolymerizatio n)、缩合聚合(condensation polymerization)、逐步加成聚合(stepwiseaddition polymeriza tion)或加成缩合聚合(addition condensation)等聚合反应。And the purification reaction in the above-mentioned step (B) is preferably a reversible addition-splitting chain transfer polymerization reaction, but in practical applications, it can also be a free radical polymerization (free radical polymerization), an ionic polymerization (ionicpolymerization), Polymerization reactions such as condensation polymerization, stepwise addition polymerization or addition condensation polymerization.

又上述步骤(B)聚合反应执行后,即可进一步使用gamma射线来照射高分子固化物,以确保未聚合的复数单体再次聚合,以可提升聚合率。After the above-mentioned step (B) of the polymerization reaction is performed, the polymer cured product can be further irradiated with gamma rays to ensure that the unpolymerized monomers are re-polymerized, so that the polymerization rate can be improved.

而上述步骤(C)的镜片1原料的透氧度(DK值)为介于170~200barrer之间,且该硬度为介于76~81duro之间,且参阅图3、4所示,为本发明的透氧率测试图及硬度测试图,由图中可清楚看出,该镜片1原料的透氧度测试后的平均值为189barrer,而该镜片1原料的硬度测试后的平均值为77duro。The oxygen permeability (DK value) of the raw material of the lens 1 in the above step (C) is between 170 and 200 barrer, and the hardness is between 76 and 81 duro, and as shown in FIGS. In the oxygen permeability test chart and hardness test chart of the invention, it can be clearly seen from the figures that the average value of the oxygen permeability test of the raw material of the lens 1 after the test is 189 barrer, and the average value of the hardness test of the raw material of the lens 1 after the test is 77duro .

本发明为可先将复数种单体加入容器中,并通过加热装置加热至默认温度,以使复数种单体产生聚合反应,进而固化形成高分子固化物,此时,容器内的溶液呈浓稠状,并将溶液倒入器皿中,再将器皿放置于烘箱中热固化作业,以使溶液中的复数单体产生纯化反应,进而重新排列形成内部无单体的高分子固化物,再将高分子固化物放置于退火装置中,以对高分子固化物进行退火处理,而经由退火处理后的高分子固化物便可成为镜片1的原料,其因复数种单体为包含有预设比例组成的甲基丙稀酸六氟异丙酯、3-(异丁烯酰氧)丙基三(三甲基硅氧烷)硅烷、新戊二醇二甲基丙烯酸酯、甲基丙烯酸、交联剂、2,5-二甲基-2,5-双(2-乙基己酸过氧化)己烷及2,2’-二羟基-4,4’-二甲氧基二苯甲酮,所以可通过此些复数单体聚合而成的高分子固化物可具有优良的透氧度,且亦具有较高的硬度及机械强度,以使配戴镜片1时能提升使用者的舒适度,并减少角膜病变。In the present invention, a plurality of monomers can be added into a container first, and heated to a default temperature by a heating device, so that a plurality of monomers can be polymerized and then cured to form a polymer cured product. At this time, the solution in the container is concentrated. It is thick, pour the solution into a vessel, and then place the vessel in an oven for thermal curing, so that the plural monomers in the solution undergo a purification reaction, and then rearrange to form a polymer solidified product without monomers inside, and then The polymer cured product is placed in the annealing device to anneal the polymer cured product, and the polymer cured product after the annealing treatment can become the raw material of the lens 1 , because a plurality of monomers contain a preset ratio Composition Hexafluoroisopropyl methacrylate, 3-(methacryloyloxy)propyltris(trimethylsiloxane)silane, neopentyl glycol dimethacrylate, methacrylic acid, crosslinking agent , 2,5-dimethyl-2,5-bis(2-ethylhexanoic acid peroxy)hexane and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, so The polymer cured product that can be polymerized by these plural monomers can have excellent oxygen permeability, and also have high hardness and mechanical strength, so as to improve the comfort of the user when wearing the lens 1, and Reduce corneal lesions.

且上述的镜片1为可通过步骤(A)及(B)多段式加热制成,且步骤(B)的加热温度为大于步骤(A)的加热温度,即可利用多段式加热来避免镜片1表面结构因一次高温加热而发生损坏的情况,进而可提升产品良率。And the above-mentioned lens 1 can be made by multi-stage heating in steps (A) and (B), and the heating temperature in step (B) is greater than the heating temperature in step (A), and the multi-stage heating can be used to avoid the lens 1. The surface structure is damaged due to one high temperature heating, which can improve the product yield.

上所述仅为本发明的较佳实施例而已,非因此即局限本发明的专利范围,故举凡运用本发明说明书及图式内容所为的简易修饰及等效结构变化,均应同理包含于本发明的专利范围内,合予陈明。The above is only a preferred embodiment of the present invention, which does not limit the scope of the patent of the present invention. Therefore, any simple modifications and equivalent structural changes made by using the contents of the description and drawings of the present invention should be included in the same way. Within the scope of the patent of the present invention, it is expressly stated.

Claims (10)

Translated fromChinese
1.一种硬式透氧隐形眼镜高分子材料的聚合方法,其特征在于,包含下列的步骤:1. a polymerization method of a rigid oxygen-permeable contact lens macromolecule material, is characterized in that, comprises the following steps:(A)先将复数种单体加入容器中,以使容器内部容置有包含复数种单体的溶液,并通过加热装置将溶液加热至默认温度,以使溶液包含的复数种单体产生聚合反应,进而固化形成高分子固化物,而该复数种单体为包括有预设比例组成的甲基丙稀酸六氟异丙酯、3-(异丁烯酰氧)丙基三(三甲基硅氧烷)硅烷、新戊二醇二甲基丙烯酸酯、甲基丙烯酸、交联剂、2,5-二甲基-2,5-双(2-乙基己酸过氧化)己烷及2,2’-二羟基-4,4’-二甲氧基二苯甲酮;(A) firstly adding a plurality of monomers into a container, so that a solution containing a plurality of monomers is contained in the container, and the solution is heated to a default temperature by a heating device, so that a plurality of monomers contained in the solution are polymerized react, and then solidify to form a polymer cured product, and the plurality of monomers are composed of hexafluoroisopropyl methacrylate, 3-(methacryloyloxy)propyltris(trimethylsilicon) in a preset ratio oxane) silane, neopentyl glycol dimethacrylate, methacrylic acid, crosslinking agent, 2,5-dimethyl-2,5-bis(2-ethylhexanoic acid peroxy)hexane and 2 , 2'-dihydroxy-4,4'-dimethoxybenzophenone;(B)并将容器内的溶液倒入器皿中,且将器皿放置于烘箱中以默认温度进行默认时间的热固化作业,以使溶液包含的复数种单体产生纯化反应,进而形成内部无单体的高分子固化物;(B) Pour the solution in the container into a vessel, and place the vessel in an oven to perform a heat curing operation at a default temperature for a default time, so that a plurality of monomers contained in the solution are purified and reacted, thereby forming an internal monolithic The polymer solidified product of the body;(C)再将内部无单体的高分子固化物放置于退火装置中,以对内部无单体的高分子固化物进行退火处理,而经由退火处理后的高分子固化物即为所述的硬式透氧隐形眼镜高分子材料。(C) Place the polymer cured product without monomers in the annealing device to perform annealing treatment on the polymer cured product without monomers, and the polymer cured product after annealing treatment is the above Hard oxygen permeable contact lens polymer material.2.如权利要求1所述的聚合方法,其特征在于,该步骤(A)中该甲基丙稀酸六氟异丙酯的重量比例为介于1%~50%,该3-(异丁烯酰氧)丙基三(三甲基硅氧烷)硅烷的重量比例为介于1%~40%,该新戊二醇二甲基丙烯酸酯的重量比例为介于1%~15%,该甲基丙烯酸的重量比例为介于1%~20%,该交联剂的重量比例为介于1%~10%,该2,5-二甲基-2,5-双(2-乙基己酸过氧化)己烷的重量比例为介于0.1%~1%,该2,2’-二羟基-4,4’-二甲氧基二苯甲酮的重量比例为介于0.1%~1%,各成分之和等于100%。2 . The polymerization method of claim 1 , wherein the weight ratio of the hexafluoroisopropyl methacrylate in the step (A) is between 1% and 50%, and the 3-(isobutylene) The weight proportion of acyloxy)propyl tris(trimethylsiloxane) silane is between 1% and 40%, the weight proportion of the neopentyl glycol dimethacrylate is between 1% and 15%, and the weight proportion of the neopentyl glycol dimethacrylate is between 1% and 15%. The weight proportion of methacrylic acid is between 1% and 20%, the weight proportion of the crosslinking agent is between 1% and 10%, the 2,5-dimethyl-2,5-bis(2-ethyl) The weight proportion of hexanoic acid peroxy) hexane is between 0.1% and 1%, and the weight proportion of the 2,2'-dihydroxy-4,4'-dimethoxybenzophenone is between 0.1% and 0.1%. 1%, the sum of the components is equal to 100%.3.如权利要求1所述的聚合方法,其特征在于,该交联剂为聚二甲基硅氧烷甲基丙烯酸酯或聚二甲基硅氧烷甲基丁烯酸酯。3 . The polymerization method of claim 1 , wherein the crosslinking agent is polydimethylsiloxane methacrylate or polydimethylsiloxane methacrylate. 4 .4.如权利要求1所述的聚合方法,其特征在于,该步骤(A)容器中的复数种单体还包括有聚甲基丙烯酸(乙二醇)脂、N-乙烯基吡咯烷酮或丙烯酰胺,且该聚甲基丙烯酸(乙二醇)脂的重量比例为介于0.1%~1%,该N-乙烯基吡咯烷酮的重量比例为介于0.1%~1%,且该丙烯酰胺的重量比例为介于0.1%~1%,各成分之和等于100%。4 . The polymerization method according to claim 1 , wherein the plurality of monomers in the container in the step (A) further comprise polymethacrylate (ethylene glycol), N-vinylpyrrolidone or acrylamide. 5 . , and the weight proportion of the polymethacrylate (ethylene glycol) resin is between 0.1% and 1%, the weight proportion of the N-vinylpyrrolidone is between 0.1% and 1%, and the weight proportion of the acrylamide is between 0.1% and 1%. It is between 0.1% and 1%, and the sum of each component is equal to 100%.5.如权利要求1所述的聚合方法,其特征在于,该步骤(A)中的容器为先装有溶剂,且该溶剂为二环氧乙烷。5 . The polymerization method of claim 1 , wherein the container in the step (A) is first filled with a solvent, and the solvent is diethylene oxide. 6 .6.如权利要求1所述的聚合方法,其特征在于,该步骤(A)中的加热装置为加热板或酒精灯,且加热装置加热的默认温度为100℃。6 . The polymerization method according to claim 1 , wherein the heating device in the step (A) is a heating plate or an alcohol lamp, and the default temperature for heating by the heating device is 100° C. 7 .7.如权利要求1所述的聚合方法,其特征在于,该步骤(B)中的器皿放置于烘箱中进行热固化作业时,该器皿为先放置于65℃烘箱中至少68小时进行热固化,再使温度加热至大于100℃,以使器皿中的单体固化,之后再加热至220℃,便使硅跟氟的键结断键,进而使溶液的分子重新排列而产生纯化反应,进而形成高分子固化物。7. polymerization method as claimed in claim 1 is characterized in that, when the vessel in this step (B) is placed in oven to carry out thermal curing operation, this vessel is first placed in 65 ℃ of ovens for at least 68 hours for thermal curing , and then heat the temperature to more than 100 ° C to solidify the monomer in the vessel, and then heat it to 220 ° C to break the bond between silicon and fluorine, and then rearrange the molecules of the solution to produce a purification reaction, and then A polymer cured product is formed.8.如权利要求1所述的聚合方法,其特征在于,该步骤(B)中执行前为添加可逆行加成分裂链转移聚合反应试剂,且该可逆行加成分裂链转移聚合反应试剂为二硫代苯甲酸酯、三硫代碳酸盐、二硫代胺基甲酸酯或黄原酸盐。8. polymerization method as claimed in claim 1 is characterized in that, before carrying out in this step (B), is to add reversible addition and cleavage chain transfer polymerization reaction reagent, and this reversible addition and cleavage chain transfer polymerization reaction reagent is Dithiobenzoates, trithiocarbonates, dithiocarbamates or xanthates.9.如权利要求1所述的聚合方法,其特征在于,该步骤(B)聚合反应执行后,即使用gamma射线来照射高分子固化物。9 . The polymerization method of claim 1 , wherein the polymer cured product is irradiated with gamma rays after the polymerization reaction in step (B) is performed. 10 .10.如权利要求1所述的聚合方法,其特征在于,该步骤(C)的镜片原料的透氧度为介于170~200barrer之间,且硬度为介于76~81duro之间。10 . The polymerization method of claim 1 , wherein the oxygen permeability of the lens material in step (C) is between 170 and 200 barrer, and the hardness is between 76 and 81 duro. 11 .
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CN114516942A (en)*2020-11-182022-05-20亨泰光学股份有限公司Hard oxygen-permeable contact lens polymer material and polymerization method thereof

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CN106749877A (en)*2016-12-202017-05-31无锡蕾明视康科技有限公司A kind of high oxygen permeability optical lens material and preparation method thereof
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GB2163173A (en)*1982-05-081986-02-19Toyo Contact Lens Co LtdOxygen permeable hard contact lens of silicon copolymer
US4540761A (en)*1982-07-271985-09-10Hoya Lens CorporationOxygen-permeable hard contact lens
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* Cited by examiner, † Cited by third party
Publication numberPriority datePublication dateAssigneeTitle
CN114516942A (en)*2020-11-182022-05-20亨泰光学股份有限公司Hard oxygen-permeable contact lens polymer material and polymerization method thereof

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