CN113109894A - 一种可染色1.74树脂镜片及其制备方法 - Google Patents

一种可染色1.74树脂镜片及其制备方法 Download PDF

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CN113109894A
CN113109894A CN202110356100.8A CN202110356100A CN113109894A CN 113109894 A CN113109894 A CN 113109894A CN 202110356100 A CN202110356100 A CN 202110356100A CN 113109894 A CN113109894 A CN 113109894A
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dyeable
hours
layer
resin lens
resin
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王传宝
刘心标
杜秋
鲍余雷
鲁渊
严清波
黄健
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Shanghai Conant Optics Co Ltd
Jiangsu Conant Optical Co Ltd
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Shanghai Conant Optics Co Ltd
Jiangsu Conant Optical Co Ltd
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Priority to CN202110356100.8A priority Critical patent/CN113109894A/zh
Priority to PCT/CN2021/087237 priority patent/WO2022205505A1/zh
Priority to US17/334,955 priority patent/US11772341B2/en
Publication of CN113109894A publication Critical patent/CN113109894A/zh
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Abstract

本发明公开了一种可染色1.74树脂镜片及其制备方法,该树脂镜片包括折射率为1.74的模块层,所述模块层的上表面浇注一层折射率为1.60的可染色层,所述可染色层的上弯弯度与模块层的上弯弯度一致,所述可染色层的中心厚度为0.5~1.2mm。本发明所述可染色1.74树脂镜片是在1.74镜片表面贴合一层可染色的1.60plus树脂镜片,染色性能好,可见光的透过率可以达到10~30%,填补了1.74镜片不能染色的空白。对所述可染色层进行了弯度和厚度的限制,使其不影响镜片的光度等光学性能,同时避免了后续加工时镜片磨穿等问题。

Description

一种可染色1.74树脂镜片及其制备方法
技术领域
本发明属于树脂镜片领域,更具体地,涉及一种可染色1.74树脂镜片及其制备方法。
背景技术
树脂镜片具有质轻、抗冲击性好、透光性好、成本低等优点,而且还能满足特殊需要,如增加染色性能、变色性能、防蓝光性能等。太阳镜,也称遮阳镜,有遮阳作用。人在阳光下通常要靠调节瞳孔大小来调节光通量,当光线强度超过人眼调节能力,就会对人眼造成伤害。所以在户外活动场所,特别是在夏天,许多人都采用遮阳镜来遮挡阳光,以减轻眼睛调节造成的疲劳或强光刺激造成的伤害。目前,全世界折射率最高的是日本三井公司的1.74镜片,由于生产原料和工艺的特殊性,1.74树脂镜片的聚合度高、分子量大,导致了其几乎不能染色。
发明内容
本发明的目的是针对以上不足,提供一种可染色1.74树脂镜片,并公开了其制备方法,可以使得1.74树脂镜片进行染色处理,可见光的透过率可以达到15~30%。
为实现上述目的,本发明是通过以下技术方案实现的:
一种可染色1.74树脂镜片,该树脂镜片包括折射率为1.74的模块层,所述模块层的上表面浇注一层折射率为1.60的可染色层,所述可染色层的上弯弯度与模块层的上弯弯度一致,所述可染色层的中心厚度为0.5~1.2mm,优选为0.6~1.0mm。
优选地,所述树脂镜片的模块层表面经过碱处理,以提高两个镜片层之间的粘合力。
一种上述的可染色1.74树脂镜片的制备方法,包括以下步骤:
(1)制备折射率为1.74的模块层树脂镜片;
(2)将制备得到的模块层在NaOH溶液中浸泡处理,然后清洗、烘干;
(3)以上述处理过的模块层为下模,玻璃模具为上模,进行合模;
(4)在合模后的模具中注入折射率为1.60的可染色层的原料,然后固化,制得。
上述制备方法中,步骤(1)所述折射率为1.74的模块层包括以下组分:
树脂单体A料100重量份,树脂单体B料10重量份,引发剂0.06~0.11重量份,紫外吸收剂0.2~0.3重量份,蓝色补色剂0.002重量份,红色补色剂0.014重量份,所述树脂单体A料为双(2,3-环硫丙基)二硫化物,树脂单体B料为双(巯甲基)-3,6,9-三硫杂十一烷-1,11-二硫醇。
优选地,所述引发剂为N,N-二已基甲胺和N,N-二甲基环已胺的混合物,其质量比为0.01~0.03:0.05~0.08。
优选地,所述紫外吸收剂是2-(2H-苯并三唑-2-基)-6-(1-甲基-1-苯乙基)-4-(1,1,3,3-四甲基丁基)苯酚、2'-(2'-羟基-3'-叔丁基-5'-甲基苯基)-5-氯苯并三唑、2-(2'-羟基5'-叔辛基苯基)苯并三唑中的一种或者几种。
优选地,所述模块层树脂镜片的制备中固化曲线为:
一次固化:15~18℃保温10~15小时;1小时升温度到30℃,并保温3~5小时;8~10小时升温到110℃,并保温2小时后,1.5小时冷却到40℃;所述升温及降温过程均为匀速;
二次固化:120℃保温3小时。
上述制备方法中,步骤(4)所述折射率为1.60的可染色层包括以下组分:
树脂单体100重量份,引发剂0.03~0.06重量份,紫外线吸收剂0.01~0.03重量份,所述树脂单体为2,5(或2,6)-双(异氰酸酯基甲基)双环[2.2.1]庚烷、六亚甲基二异氰酸酯、四(3-巯基丙酸)季戊四醇酯和4-巯甲基-3,6-二硫杂-1,8-辛二硫醇的混合物,其质量比为30:20:27:23。
优选地,所述引发剂为二甲基二氯化锡。
优选地,所述紫外吸收剂是2-(2H-苯并三唑-2-基)-6-(1-甲基-1-苯乙基)-4-(1,1,3,3-四甲基丁基)苯酚、2'-(2'-羟基-3'-叔丁基-5'-甲基苯基)-5-氯苯并三唑、2-(2'-羟基5'-叔辛基苯基)苯并三唑中的一种或者几种。
优选地,所述步骤(2)中NaOH溶液的比重为1.15~1.25,浸泡时间为3~15分钟,温度60~80℃,浸泡的同时超声处理,超声波的强度是5~15w/cm2
优选地,所述步骤(4)中固化的固化曲线为:
一次固化:20~22℃保温4~5小时;5~6小时升温度到60℃;3~4小时升温到90℃,0.5小时升温度100℃;1~2小时升温度到120℃,并保温4~5小时后,1小时降温到80℃;所述升温及降温过程均为匀速;
二次固化:120℃保温2小时。
上述制备步骤完成后,可按照染色镜片最终的样品片颜色调整好染色槽颜料配比,把上述的镜片进行染色,染色温度为80~95℃,浸泡时间为0.5~2.0小时;然后再进行固色,固色温度90~120℃,维持时间3.5h。
与现有技术相比,本发明的有益效果为:
(1)本发明所述可染色1.74树脂镜片是在1.74镜片表面贴合一层可染色的1.60plus树脂镜片,染色性能好,可见光的透过率可以达到10~30%,填补了1.74镜片不能染色的空白。
(2)本发明对所述可染色层进行了弯度和厚度的限制,使其不影响镜片的光度等光学性能,同时避免了后续加工时镜片磨穿等问题。
(3)本发明采用浇注的方法将可染色层与模块层结合起来,镜片粘合性能好,且不影响其光学性能,对1.74模块层进行表面碱处理,进一步增加了两层镜片的粘合力,结合固化工艺,避免染色层脱落。
(4)本发明制备工艺简单易操作,价格便宜,容易推广。
具体实施方式
下面将结合具体实施例更详细地描述本发明的优选实施方式。
下列为实施例中用到的原料及助剂:
1.74模块层和1.60可染色层的原料来源于日本三井株式会社;
N,N-二已基甲胺,N,N-二甲基环已胺来源于上海联硕生物科技有限公司;
紫外线吸收剂来源于上海同金化工有限公司;
蓝色和红色补色剂来源于东莞市晧海化工有限公司,
二甲基二氯化锡来源于天津中信凯泰化工有限公司。
实施例1
一种可染色1.74树脂镜片,包括折射率为1.74的模块层,所述模块层的上表面浇注一层折射率为1.60的可染色层,所述可染色层的上弯弯度与模块层的上弯弯度一致,所述可染色层的中心厚度为0.8mm。
本实施例所述可染色1.74树脂镜片的制备方法,包括以下步骤:
(1)制备折射率为1.74的模块层树脂镜片;
该模块层树脂镜片的原料为:双(2,3-环硫丙基)二硫化物100g,双(巯甲基)-3,6,9-三硫杂十一烷-1,11-二硫醇10g,引发剂N,N-二已基甲胺0.02g,N,N-二甲基环已胺0.06g,紫外吸收剂2-(2H-苯并三唑-2-基)-6-(1-甲基-1-苯乙基)-4-(1,1,3,3-四甲基丁基)苯酚0.2g,蓝色补色剂0.002g,红色补色剂0.014g。
该制备过程中的固化曲线为:
一次固化:18℃保温15小时;1小时升温度到30℃,并保温3小时;8~10小时升温到110℃,并保温2小时后,1.5小时冷却到40℃;所述升温及降温过程均为匀速;
二次固化:120℃保温3小时。
(2)将制备得到的模块层在比重为1.15的NaOH溶液中浸泡处理10分钟,处理温度75℃,浸泡同时超声处理,超声波强度是10w/cm2,然后清洗、烘干;
(3)以上述处理过的模块层为下模,玻璃模具为上模,进行合模;
(4)在合模后的模具中注入折射率为1.60的可染色层的原料,然后固化,制得;
该可染色层的原料为:树脂单体100重量份2,5(或2,6)-双(异氰酸酯基甲基)双环[2.2.1]庚烷30g,六亚甲基二异氰酸酯20g,四(3-巯基丙酸)季戊四醇酯27g,4-巯甲基-3,6-二硫杂-1,8-辛二硫醇23g,引发剂二甲基二氯化锡0.06g,紫外线吸收剂2-(2'-羟基5'-叔辛基苯基)苯并三唑0.03g。
该步骤中的固化曲线为:
一次固化:20℃保温4小时;5小时升温度到60℃;3小时升温到90℃,0.5小时升温度100℃;1小时升温度到120℃,并保温4小时后,1小时降温到80℃;所述升温及降温过程均为匀速;
二次固化:120℃保温2小时。
上述制备完成后,按照染色镜片最终的样品片颜色调整好染色槽颜料配比,把上述的镜片进行染色,染色温度为85℃,浸泡时间为1小时;然后再进行固色,固色温度90℃,维持时间3.5h。
实施例2
一种可染色1.74树脂镜片,包括折射率为1.74的模块层,所述模块层的上表面浇注一层折射率为1.60的可染色层,所述可染色层的上弯弯度与模块层的上弯弯度相等,所述可染色层的中心厚度为1.0mm。
本实施例所述可染色1.74树脂镜片的制备方法,包括以下步骤:
(1)制备折射率为1.74的模块层树脂镜片;
该模块层树脂镜片的原料为:双(2,3-环硫丙基)二硫化物100g,双(巯甲基)-3,6,9-三硫杂十一烷-1,11-二硫醇10g,引发剂N,N-二已基甲胺0.03g,N,N-二甲基环已胺0.07g,紫外吸收剂2'-(2'-羟基-3'-叔丁基-5'-甲基苯基)-5-氯苯并三唑0.3g,蓝色补色剂0.002g,红色补色剂0.014g。
该制备过程中的固化曲线为:
一次固化:15℃保温12小时;1小时升温度到30℃,并保温5小时;10小时升温到110℃,并保温2小时后,1.5小时冷却到40℃;所述升温及降温过程均为匀速;
二次固化:120℃保温3小时。
(2)将制备得到的模块层在比重为1.2的NaOH溶液中浸泡处理12分钟,处理温度70℃,浸泡同时超声处理,超声波强度是8w/cm2,然后清洗、烘干;
(3)以上述处理过的模块层为下模,玻璃模具为上模,进行合模;
(4)在合模后的模具中注入折射率为1.60的可染色层的原料,然后固化,制得;
该可染色层的原料为:树脂单体2,5(或2,6)-双(异氰酸酯基甲基)双环[2.2.1]庚烷30g,六亚甲基二异氰酸酯20g,四(3-巯基丙酸)季戊四醇酯27g,4-巯甲基-3,6-二硫杂-1,8-辛二硫醇23g,引发剂二甲基二氯化锡0.05g,紫外线吸收剂2'-(2'-羟基-3'-叔丁基-5'-甲基苯基)-5-氯苯并三唑0.02g。
该步骤中的固化曲线为:
一次固化:22℃保温5小时;6小时升温度到60℃;4小时升温到90℃,0.5小时升温度100℃;2小时升温度到120℃,并保温5小时后,1小时降温到80℃;所述升温及降温过程均为匀速;
二次固化:120℃保温2小时。
上述制备完成后,按照染色镜片最终的样品片颜色调整好染色槽颜料配比,把上述的镜片进行染色,染色温度为95℃,浸泡时间为1.5小时;然后再进行固色,固色温度100℃,维持时间3.5h。
实施例3
一种可染色1.74树脂镜片,包括折射率为1.74的模块层,所述模块层的上表面浇注一层折射率为1.60的可染色层,所述可染色层的上弯弯度与模块层的上弯弯度相等,所述可染色层的中心厚度为1.2mm。
本实施例所述可染色1.74树脂镜片的制备方法,包括以下步骤:
(1)制备折射率为1.74的模块层树脂镜片;
该模块层树脂镜片的原料为:双(2,3-环硫丙基)二硫化物100g,双(巯甲基)-3,6,9-三硫杂十一烷-1,11-二硫醇10g,引发剂N,N-二已基甲胺0.01g,N,N-二甲基环已胺0.05g,紫外吸收剂2-(2'-羟基5'-叔辛基苯基)苯并三唑0.25g,蓝色补色剂0.002g,红色补色剂0.014g。
该制备过程中的固化曲线为:
一次固化:16℃保温10小时;1小时升温度到30℃,并保温4小时;9小时升温到110℃,并保温2小时后,1.5小时冷却到40℃;所述升温及降温过程均为匀速;
二次固化:120℃保温3小时。
(2)将制备得到的模块层在比重为1.25的NaOH溶液中浸泡处理10分钟,处理温度65℃,浸泡同时超声处理,超声波强度是15w/cm2,然后清洗、烘干;
(3)以上述处理过的模块层为下模,玻璃模具为上模,进行合模;
(4)在合模后的模具中注入折射率为1.60的可染色层的原料,然后固化,制得;
该可染色层的原料为:树脂单体100重量份2,5(或2,6)-双(异氰酸酯基甲基)双环[2.2.1]庚烷30g,六亚甲基二异氰酸酯20g,四(3-巯基丙酸)季戊四醇酯27g,4-巯甲基-3,6-二硫杂-1,8-辛二硫醇23g,引发剂二甲基二氯化锡0.04g,紫外线吸收剂2-(2H-苯并三唑-2-基)-6-(1-甲基-1-苯乙基)-4-(1,1,3,3-四甲基丁基)苯酚0.03g。
该步骤中的固化曲线为:
一次固化:20℃保温5小时;6小时升温度到60℃;4小时升温到90℃,0.5小时升温度100℃;1小时升温度到120℃,并保温4小时后,1小时降温到80℃;所述升温及降温过程均为匀速;
二次固化:120℃保温2小时。
上述制备完成后,按照染色镜片最终的样品片颜色调整好染色槽颜料配比,把上述的镜片进行染色,染色温度为90℃,浸泡时间为1小时;然后再进行固色,固色温度120℃,维持时间3.5h。
对比例1
现有的折射率1.74的树脂镜片。
对比例2
按照实施例1所述方法制备可染色1.74树脂镜片,其中可染色层中心厚度为1.5mm,其余步骤相同。
对比例3
按照实施例1所述方法制备可染色1.74树脂镜片,其中可染色层的上弯弯度与模块层不同。
对比例4
按照实施例1所述方法制备可染色1.74树脂镜片,其中模块层不进行碱处理,其余步骤相同。
对比例5
按照实施例1所述方法制备可染色1.74树脂镜片,其中折射率为1.60的树脂镜片层采用常规的1.60亚克力树脂镜片的原料。
分别将上述实施例和对比例所述镜片进行染色测试和粘结力测试,结果见表1
表1实施例及对比例所述镜片性能对比
Figure BDA0003003892590000091
注:可见光透过率测试仪器是TM-3;粘结力测试纯水煮30min是否脱落,加工过程问题是会不会磨穿或者光度不准等。
从上表中可以看出,本发明所制备的可染色1.74树脂镜片的染色效果好,可染色层与模块层粘结力好,不易脱落,不影响镜片光度且不影响后续加工。
以上已经描述了本发明的各实施例,上述说明是示例性的,并非穷尽性的,并且也不限于所披露的各实施例。在不偏离所说明的各实施例的范围和技术原理的情况下,对于本技术领域的普通技术人员来说许多修改和变更都是显而易见的,这些修改和变更也应视为本发明的保护范围。

Claims (10)

1.一种可染色1.74树脂镜片,其特征在于该树脂镜片包括折射率为1.74的模块层,所述模块层的上表面浇注一层折射率为1.60的可染色层,所述可染色层的上弯弯度与模块层的上弯弯度一致,所述可染色层的中心厚度为0.5~1.2mm。
2.根据权利要求1所述的可染色1.74树脂镜片,其特征在于所述可染色层的中心厚度为0.6~1.0mm。
3.根据权利要求1所述的可染色1.74树脂镜片,其特征在于所述模块层的表面经过碱处理。
4.一种权利要求1~3中任意一项所述的可染色1.74树脂镜片的制备方法,其特征在于包括以下步骤:
(1)制备折射率为1.74的模块层树脂镜片;
(2)将制备得到的模块层在NaOH溶液中浸泡表面处理,然后清洗、烘干;
(3)以上述处理过的模块层为下模,玻璃模具为上模,进行合模;
(4)在合模后的模具中注入折射率为1.60的可染色层的原料,然后固化,制得。
5.根据权利要求4所述的可染色1.74树脂镜片的制备方法,其特征在于所述折射率为1.74的模块层包括以下组分:
树脂单体A料100重量份,树脂单体B料10重量份,引发剂0.06~0.11重量份,紫外吸收剂0.2~0.3重量份,蓝色补色剂0.002重量份,红色补色剂0.014重量份,所述树脂单体A料为双(2,3-环硫丙基)二硫化物,树脂单体B料为双(巯甲基)-3,6,9-三硫杂十一烷-1,11-二硫醇。
6.根据权利要求5所述的可染色1.74树脂镜片的制备方法,其特征在于所述引发剂为N,N-二已基甲胺和N,N-二甲基环已胺的混合物,其质量比为0.01~0.03:0.05~0.08。
7.根据权利要求5所述的可染色1.74树脂镜片的制备方法,其特征在于所述模块层树脂镜片的制备中固化曲线为:
一次固化:15~18℃保温10~15小时;1小时升温度到30℃,并保温3~5小时;8~10小时升温到110℃,并保温2小时后,1.5小时冷却到40℃;
二次固化:120℃保温3小时。
8.根据权利要求4所述的可染色1.74树脂镜片的制备方法,其特征在于所述折射率为1.60的可染色层包括以下组分:
树脂单体100重量份,引发剂0.03~0.06重量份,紫外线吸收剂0.01~0.03重量份,所述树脂单体为2,5(或2,6)-双(异氰酸酯基甲基)双环[2.2.1]庚烷、六亚甲基二异氰酸酯、四(3-巯基丙酸)季戊四醇酯和4-巯甲基-3,6-二硫杂-1,8-辛二硫醇的混合物,其质量比为30:20:27:23。
9.根据权利要求4所述的可染色1.74树脂镜片的制备方法,其特征在于所述步骤(2)中NaOH溶液的比重为1.15~1.25,浸泡时间为3~15分钟,温度60~80℃,浸泡的同时超声处理,超声波的强度是5~15w/cm2
10.根据权利要求4所述的可染色1.74树脂镜片的制备方法,其特征在于所述步骤(4)中固化的固化曲线为:
一次固化:20~22℃保温4~5小时;5~6小时升温度到60℃;3~4小时升温到90℃,0.5小时升温度100℃;1~2小时升温度到120℃,并保温4~5小时后,1小时降温到80℃;
二次固化:120℃保温2小时。
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