CN105482070B - 一种运用有机和无机杂交的具有高耐冲击、耐热性和折射率的光学树脂组合物及其制备方法 - Google Patents

一种运用有机和无机杂交的具有高耐冲击、耐热性和折射率的光学树脂组合物及其制备方法 Download PDF

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CN105482070B
CN105482070B CN201510893873.4A CN201510893873A CN105482070B CN 105482070 B CN105482070 B CN 105482070B CN 201510893873 A CN201510893873 A CN 201510893873A CN 105482070 B CN105482070 B CN 105482070B
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钱建平
邹继新
柳炯圭
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Jiangsu Qianyuan New Material Technology Co Ltd
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Abstract

本发明涉及一种运用有机和无机杂交的具有高耐冲击、耐热性和折射率的光学树脂组合物及其制备方法,光学树脂组合物的组成成分按质量百分比计如下:混合物A 100%,无机材料0.1‑5%,紫外吸收剂0.05‑6%,脱模剂0.01‑5%,聚合引发剂0.01‑5%和颜色调节剂0.03‑2%;本发明制成的光学树脂组合物可用于制备光学树脂镜片,使光学树脂镜片具有质量轻、易成型、易染色、高透明性及高阿贝数的特点,同时表面经过喷涂后具有高冲击性,高耐热性及高曲折率等优点。

Description

一种运用有机和无机杂交的具有高耐冲击、耐热性和折射率 的光学树脂组合物及其制备方法
技术领域
本发明涉及一种运用有机和无机杂交的具有高耐冲击、耐热性和折射率的光学树脂组合物及其制备方法,属于光学树脂材料技术领域。
背景技术
光学树脂镜片与普通的玻璃镜片相比,因其质量轻,易染色和耐冲击性优异而被广泛应用于市场,而为了满足镜片可以阻挡散射光线和高透过率效果,在镜片的两侧表面需经过多次喷涂(SiO2 , ZrO2 等),但经喷涂后镜片的强度会显著下降,此类问题在低曲折镜片,中曲折镜片,高曲折镜片及初高曲折镜片都有发生。
现有技术中使用低曲折性能的高分子二甘醇双烯丙基碳酸酯制作的光学树脂镜片(中心厚度1.2mm)在经过多次涂层后,使用FDA标准的钢球(16.8g),于127cm的高度,进行钢球跌落试验时,镜片中心破碎。
现有技术中的高曲折镜片,主要成分是在间苯二甲酸二烷基多元醇中添加二烷基间苯二甲酸和二甘醇双烯丙基碳酸的混合物,而为增加镜片强度,向二烷基间苯二甲酸中添加乙醇, 但使用改性间苯二甲酸二烯丙酯制作中曲折树脂镜片(中心厚度 1.2mm), 在经过多次涂层试验后,最终未能通过FDA测试;同时为达到使四(3-巯基丙酸)季戊四醇酯镜片强化的目的,在异氰酸酯和氰酸酯中添加了酒精,制成了强度优秀的光学树脂镜片,但因该树脂镜片的黏度非常高,导致注入速度缓慢,同时液相流动时产生大量烟气,最终导致生产出来的光学树脂镜片不良率非常高。
现有技术中的高曲折度及初高曲折镜片,采用二异氰酸酯和1,2-二巯基及乙基-3-巯基丙烷的聚合物,并利用脂肪族异氰酸,1,2-二巯基及乙基-3-巯基丙烷及四(3-巯基丙酸)季戊四醇酯提高镜片的曲折率,此方法虽然将曲折率提高,但最终镜片经过多次喷涂后未能通过FDA测试,而注塑而成的聚碳酸酯镜片在经过多次喷涂后,虽然其强度增加,但是耐热性减弱,镜片中心变形严重。
现有技术中的耐冲击性镜片,采用异氰酸酯,氰酸酯,四(3-巯基丙酸)季戊四醇酯以及四(3-巯基丙酸)季戊四醇酯和季戊四醇四甲基丙烯酸酯的混合物研制出高强化的光学镜片,但使用此方法制得的中曲折镜片强度较高,却对高曲折镜片却没有效果,同时与注塑方法制成的树脂镜片聚碳酸酯一致,其耐热性较弱并且经过喷涂后,不良率很高。多次喷涂后镜片中心区域变形严重。
因此,制备一种具有高耐冲击、耐热性和折射率的光学树脂组合物应用于光学树脂镜片成材,对改良其性质具有重大意义。
发明内容
本发明的目的是针对现有技术的缺陷,提供一种运用有机和无机杂交的具有高耐冲击、耐热性和折射率的光学树脂组合物及其制备方法,制成的光学树脂组合物可用于制备光学树脂镜片,使光学树脂镜片具有质量轻、易成型、易染色、高透明性及高阿贝数的特点,同时表面经过喷涂后具有高冲击性,高耐热性及高曲折率等优点。
本发明是通过如下的技术方案予以实现的:
一种运用有机和无机杂交的具有高耐冲击、耐热性和折射率的光学树脂组合物,所述光学树脂组合物的组成成分按质量百分比计如下:
混合物A 100%
无机材料 0.1-5%
紫外吸收剂 0.05-6%
脱模剂 0.01-5%
聚合引发剂 0.01-5%
颜色调节剂 0.03-2%;
其中,所述混合物A由混合物B和无机材料混合而成,所述无机材料的质量百分比为混合物B的0.1-5%,所述无机材料为TiO2 ,SiO2, Zn(OH)2中的一种;
所述混合物B由按质量百分比计30-60%的混合物C和40-70%的混合物D组成;
所述混合物C为异氰酸酯,氰酸酯和氢化二苯基甲烷二异氰酸酯中的三者混合,或上述任意两者混合而成,所述异氰酸酯与氰酸酯的摩尔比为1:0.3,所述异氰酸酯与氢化二苯基甲烷二异氰酸酯的摩尔比为1:0.4,所述氢化二苯基甲烷二异氰酸酯与氰酸酯的摩尔比为1:(0.1~0.5);
所述混合物D为四(3-巯基丙酸)季戊四醇酯和2,3-二硫代(2-巯基)-1-丙烷硫醇中的混合而成,所述四(3-巯基丙酸)季戊四醇酯与2,3-二硫代(2-巯基)-1-丙烷硫醇的摩尔比为(0.3~1):1;
所述紫外吸收剂为2-(2'-羟基-5-甲基苯基)-2H-苯并三唑、2-(2'-羟基-3',5'-二叔 - 叔丁基苯基)-5-氯-2H- 苯并三唑、2-(2'-羟基-3'-叔丁基-5'-甲基苯基)-5-氯-2H-苯并三唑、2-(2'-羟基-3',5'-二叔戊基苯基-T-)-2H-苯并三唑、 2-(2'-羟基-3',5'-二叔丁基-叔苯基)-2H-苯并三唑、2(2'-羟基-5'-叔丁基苯基)-2H-苯并三唑、 2-(2'-羟基-5'-叔辛基苯酚)-2H-苯并三唑、2,4-二羟基二苯甲酮、2-羟基-4-甲氧基二苯甲酮、2-羟基-4-辛氧基二苯甲酮、 4-十二烷氧基-2-羟基二苯甲酮、 2,2’,4,4’-四羟基二苯甲酮、2,2’,4,4’-四羟基二苯甲酮和2,2’-二羟基-4,4’-二甲氧基二苯甲酮中的一种;
所述脱模剂为酸性磷酸酯,所述酸性磷酸酯包括磷酸异丙酯,磷酸二异丙酯,磷酸丁酯,磷酸辛酯,磷酸二异癸酯,十三烷醇磷酸酯和磷酸双(十三烷基)酯;
所述聚合引发剂是具有锡基和氨基的化学物,所述具有锡基的化合物包括二月桂酸二丁基锡、 二(三氯甲基) 碳酸酯、苯骈三氮唑;辛酸亚锡、二月桂酸二丁基锡、 四氟化锡、四氯化锡、 四溴化锡、 四碘化锡、甲基三氯化锡、丁基三氯化锡、二甲基二氯化锡、二丁基二氯化锡、 三甲基氯化锡、三丁基氯化锡、三苯基氯化锡和二丁基硫化锡。
上述一种运用有机和无机杂交的具有高耐冲击、耐热性和折射率的光学树脂组合物,其中,优选地,所述氢化二苯基甲烷二异氰酸酯与氰酸酯的摩尔比为1:(0.2~0.4)。
上述一种运用有机和无机杂交的具有高耐冲击、耐热性和折射率的光学树脂组合物,其中,所述光学树脂组合物20℃时的液相粘度是15~180 cps。
上述一种运用有机和无机杂交的具有高耐冲击、耐热性和折射率的光学树脂组合物的制备方法,其制备方法如下:
按质量百分比计将30-60%的混合物C与40-70%混合物D投入氮气填充的反应器中得混合物B,随后添加无机材料,所述无机材料的质量百分比为混合物B的0.1-5%,得混合物A,再添加质量百分比为混合物D的0.05-6%的紫外吸收剂,0.01-5%的脱模剂,0.01-5%的聚合引发剂和0.03-2% 颜色调节剂,减压搅拌2~5个小时后,终止反应并减压脱泡即可。
上述一种运用有机和无机杂交的具有高耐冲击、耐热性和折射率的光学树脂组合物,可应用于制备光学树脂镜片,其制备方法如下:
将光学树脂组合物注入至模具后放入到烘箱中,控制温度为33~37℃保持2h, 经5h升温至38~42℃,经12h升温至 115~130℃并在该温度下保持2h, 在经2h冷却至60~80℃,移除模具后,在105∼135℃温度下要进行1.5~3小时的热处理,并进行硬化处理和多层喷涂处理即可。
本发明的有益效果为:
本发明制得的光学树脂组合物的液相折射率为(nD) 1.430~1.635, 液相比重为1.02~1.35,光学树脂镜片的固相折射率为(nD) 1.535~1.675, 阿贝数为35~48,固相比重为1.12~1.45,光学树脂镜片具有优秀的耐冲击性和耐热性,以及优秀的轻质性,成形性,染色性,透明性及高阿贝数的性质,镜片的表面经硬质处理和多层喷涂后,可保持镜片优异的特性,并且可以利用喷涂多性能的涂层,将镜片应用到各行各业。
具体实施方式
下面结合实施例对本发明的具体实施方式作进一步说明:
实施例1
一种运用有机和无机杂交的具有高耐冲击、耐热性和折射率的光学树脂组合物,可应用于制备光学树脂镜片,其制备及应用方法如下:
(1) 将氢化二苯基甲烷二异氰酸酯(H12MDI)176.5g和氰酸酯(HDI)86.9g, 将四(3-巯基丙酸)季戊四醇酯(PETMP)150g,2,3-双(硫代(2-巯乙基))-1-正丙硫醇(MDODT)100g,0.5g SiO2,紫外吸收剂2-(2'-羟基-3',5'-二叔丁基-叔苯基)-5-氯 -2H-苯并三唑(HBCBT)20g,脱模剂磷酸丁酯(BP)0.2g, 聚合引发剂二(三氯甲基) 碳酸酯(BTC)1.2g,和1%的颜色调节剂1-羟基-4-(对甲苯胺基)-蒽醌(HTAQ )20ppm,PRD10 ppm放入反应器中,并冲入氮气保护,减压搅拌2个小时后,停止反应得组合物;
(2) 将组合物注入玻璃模具中,(折光度 -6.00)后,放入循环烘箱,在35℃维持2小时,经3小时升温至40℃,经12小时升温至130℃, 并在该温度下维持2小时, 经2小时温度降至70℃;树脂经强化后,从模具中取出得光学镜片,光学镜片的中心厚度为1.2mm,直径为75mm;
(3) 光学镜片经强碱溶液超声洗涤后,在130℃热处理2小时;
(4) 经步骤(3)中得到的光学镜片通过加硬液的侵蚀后,经热固化处理,镜片的两侧表明面需喷涂氧化硅,氧化锆,氧化硅,ITO,氧化锆,氧化硅,氧化锆,以及水膜(含氟聚合物)等即可。
实施例2
一种运用有机和无机杂交的具有高耐冲击、耐热性和折射率的光学树脂组合物,其制备及应用方法如下:
将氢化二苯基甲烷二异氰酸酯(H12MDI)176.5g和氰酸酯(HDI)86.9g, 将四(3-巯基丙酸)季戊四醇酯(PETMP)150g,2,3-双(硫代(2-巯乙基))-1-正丙硫醇(MDODT)100g,0.5g TiO2,紫外吸收剂2-(2'-羟基-3',5'-二叔丁基-叔苯基)-5-氯 -2H-苯并三唑(HBCBT)20g,脱模剂磷酸丁酯(BP)0.2g, 聚合引发剂二(三氯甲基) 碳酸酯(BTC)1.2g,和1%的颜色调节剂1-羟基-4-(对甲苯胺基)-蒽醌(HTAQ )20ppm,PRD10 ppm放入反应器中,并冲入氮气保护,减压搅拌2个小时后,停止反应得组合物。
实施例3
一种运用有机和无机杂交的具有高耐冲击、耐热性和折射率的光学树脂组合物,其制备及应用方法如下:
将氢化二苯基甲烷二异氰酸酯(H12MDI)176.5g和氰酸酯(HDI)86.9g, 将四(3-巯基丙酸)季戊四醇酯(PETMP)150g,2,3-双(硫代(2-巯乙基))-1-正丙硫醇(MDODT)100g,0.5g Zn(OH)2,紫外吸收剂2-(2'-羟基-3',5'-二叔丁基-叔苯基)-5-氯 -2H-苯并三唑(HBCBT)20g,脱模剂磷酸丁酯(BP)0.2g, 聚合引发剂二(三氯甲基) 碳酸酯(BTC)1.2g,和1%的颜色调节剂1-羟基-4-(对甲苯胺基)-蒽醌(HTAQ )20ppm,PRD10 ppm放入反应器中,并冲入氮气保护,减压搅拌2个小时后,停止反应得组合物。
实施例4
一种运用有机和无机杂交的具有高耐冲击、耐热性和折射率的光学树脂组合物,其制备及应用方法如下:
将氢化二苯基甲烷二异氰酸酯(H12MDI)181.4g和氰酸酯(HDI)89.4g, 将四(3-巯基丙酸)季戊四醇酯(PETMP)130g,2,3-双(硫代(2-巯乙基))-1-正丙硫醇(MDODT)100g,0.5g Zn(OH)2,紫外吸收剂2-(2'-羟基-5-甲基苯基)-2H-苯并三唑(HMBT)20g,脱模剂十三烷醇磷酸酯(TDP)0.2g, 聚合引发剂二(三氯甲基) 碳酸酯(BTC)1.2g,和1%的颜色调节剂1-羟基-4-(对甲苯胺基)-蒽醌(HTAQ )20ppm,PRD10 ppm放入反应器中,并冲入氮气保护,减压搅拌2个小时后,停止反应得组合物。
上述实施例2、实施例3和实施例4均可按实施例1步骤(2)、(3)、(4)制得光学树脂镜片,并进行如下的物性检测:
1. 折射率和阿贝数:使用Atacota Co 1T 德林阿贝折射仪测定;
2. 透光率:使用分光光度计测定;
3. 比重:利用排水法测定镜片的体积和质量,进而计算比重;
4. 耐热性:使用瑞士METTLER TOLEDO 测定(DSC-1和TGA温度);
5. 气泡:如实例1中所诉,树脂放入模具经热强化处理冷却后,10个镜片的中心位置处均无气泡产生记为O,若1~3个镜片存在气泡记为△,若4个以上记为X;
6. 耐冲击性:对镜片的中心部位进行钢球自由坠落实验,此镜片已经过硬化处理和多层喷涂处理。实验时,采用质量为72g钢球,高度为127cm,每个镜片反复测试3次。若10个镜片中一个都没有出现裂痕记为O,有一个以上的镜片出现裂痕记为X;
7. 耐光性:使用Q-Pannellad products QUV/Spray (5w)照射光学镜片(度数 -6.00),经过200小时的照射后,若镜片没有色变记为O,若出现变色记为X;
8. 开模性:与实例1所诉一致,将单体,添加剂,聚合引发剂混合后,经过真空脱泡注入玻璃模具。树脂在加热强化成型后,去除模具时,模具没有损伤记为O,模具出现损伤记为X。
上述实施例物性结果如下表:
物性 实施例1 实施例2 实施例3 实施例4
折射率(nD) 1.59 1.595 1.595 1.598
阿贝数 40 40 41 41
雾度
透过率(%) 81 87 98 98
比重 1.28 1.28 1.29 1.29
耐热性 O O O O
气泡 O O O O
耐冲击 O O O O
耐光性 O O O O
开模性 O O O O
由上表可知,本发明制得的光学树脂组成物和光学镜片具有优秀的轻质性,成形性,染色性,透明性及高阿贝数的性质。镜片的表明经硬质处理和多层喷涂(防反射膜喷涂)后,可保持镜片优异的特性,并且可以利用喷涂多性能的涂层,将镜片应用到各行各业。
上述化学名中:
单体:
IPDI: 异氰酸酯;HMDI: 氰酸酯;PETMP: 四(3-巯基丙酸)季戊四醇酯 ;PETMA:季戊四醇四甲基丙烯酸酯;XDI: 二异氰酸酯;DBzM: 马来酸苄;DAIP: 间苯二甲酸二烯丙酯;P-DAIPE: 间苯二甲酸乙二醇聚酯低聚物;CR-39: 二甘醇双烯丙基碳酸酯;BMEMP: 1,2-双(巯基甲基)-3-巯基丙烷。
紫外吸收剂:
HMBT: 2-(2'-羟基-5-甲基苯基)-2H-苯并三唑;HBCBT: 2-(2'-羟基-3',5'-二叔丁基-叔苯基)-5-氯 -2H-苯并三唑;HBMCBT: 2-(2'-羟基-3'-叔丁基-5'-甲基苯基)-5-氯-2H- 苯并三唑;HAPBT: 2-(2'-羟基-3',5'-二叔戊基苯基-T-)-2H-苯并三唑;HBPBT: 2-(2'-羟基-5'-叔丁基苯基)-2H-苯并三唑;HOPBT: 2-(2'-羟基-5'-叔辛基苯酚)-2H-苯并三唑;DHBP: 二羟基 - 2,4,二苯甲酮;HMBP: 2 - 羟基 - 4 - 甲氧氯二苯酮;HOOBP: 2-羟基-4-辛氧基二苯甲酮;DOHBP: 4-十二烷氧基-2-羟基二苯甲酮;BHBP: 4-苯并-2-羟基二苯甲酮;THBP: 2,2’,4,4’-四羟基二苯甲酮;DHMBP: 2,2'-二羟基-4,4'-二甲氧基二苯甲酮;BHMCBT: 2-(3'-叔丁基-2'-羟基-5'-甲基苯基)-5-氯苯三唑。
脱模剂:
IPPT :磷酸异丙酯;DIPP : 磷酸二异丙酯;BP : 磷酸丁酯;OP : 磷酸辛酯;DOP: 邻苯二甲酸二辛酯;IDP: 肌苷二磷酸;DIDP : 邻苯二甲酸二异癸酯;TDP : 十三烷醇磷酸酯;BTDP : 磷酸双(十三烷基)酯。
1%颜色调节剂:向甲苯(染料分散液)99g中添加1g有机染料制作质量分数1%颜色调节剂;
HTAQ :1-羟基-4-(对甲苯胺基)-蒽醌;PRD : 染料(紫环酮PERINONE DYE);
颜料料分散液 :日本德山公司BL-1颜料分散液。
聚合引发剂:
BTL : 二月桂酸二丁基锡;BTC : 二(三氯甲基) 碳酸酯;BTA :苯骈三氮唑;TEA: 三乙胺;IPP : 过氧化二碳酸二异丙酯;NPP : 过氧化二碳酸二正丙酯。
这里本发明的描述和应用是说明性的,并非想将本发明的范围限制在上述实施例中,因此,本发明不受本实施例的限制,任何采用等效替换取得的技术方案均在本发明保护的范围内。

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1.一种运用有机和无机杂交的具有高耐冲击、耐热性和折射率的光学树脂组合物的制备方法,其特征为制备方法如下:
将氢化二苯基甲烷二异氰酸酯176.5g,氰酸酯86.9g,四(3-巯基丙酸)季戊四醇酯150g,2,3-双(硫代(2-巯乙基))-1-正丙硫醇100g,0.5g Zn(OH)2,紫外吸收剂2-(2'-羟基-3',5'-二叔丁基-叔苯基)-5-氯 -2H-苯并三唑20g,脱模剂磷酸丁酯0.2g, 聚合引发剂二(三氯甲基) 碳酸酯1.2g,和1%的颜色调节剂1-羟基-4-(对甲苯胺基)-蒽醌20ppm,紫环酮10 ppm放入反应器中并冲入氮气保护,减压搅拌2个小时后,停止反应得所述组合物。
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