CN1612909A - 制造复制品的方法以及通过进行uv光引发阳离子聚合反应而得到的复制品 - Google Patents
制造复制品的方法以及通过进行uv光引发阳离子聚合反应而得到的复制品 Download PDFInfo
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- B44C3/00—Processes, not specifically provided for elsewhere, for producing ornamental structures
- B44C3/04—Modelling plastic materials, e.g. clay
- B44C3/042—Modelling plastic materials, e.g. clay producing a copy from an original structure
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29D11/00009—Production of simple or compound lenses
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29D11/00009—Production of simple or compound lenses
- B29D11/00432—Auxiliary operations, e.g. machines for filling the moulds
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- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
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- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
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Abstract
本发明涉及一种制造复制品的方法，该方法包括在具有预成型表面的前模具和具有预成型表面的后模具之间提供可聚合树脂组合物，进行固化处理和将如此制成的复制品从模具中取出。本发明进一步涉及一种通过进行UV光－引发的阳离子聚合反应而得到的复制品。
Description
本发明涉及一种制造复制品的方法，该方法包括在具有预成型表面的前模具，和具有预成型表面的后模具之间提供可聚合树脂，进行固化处理和从模具中取出如此制成的复制品，所述复制品包括一个其上复制有前模具的表面形状和后模具的表面形状的固体。本发明还涉及一种通过进行UV光-引发阳离子聚合反应而得到的复制品。
这种方法本身得知于以本申请人名义递交的美国专利说明书4,890,905。复制工艺采用具有精确确定的表面的模具或基质，该表面是复制品的所需光学轮廓的负像。在精确确定模具或基质的表面的清晰度时，必须考虑到复制品的合成树脂的收缩。将一定量的液体，可固化合成树脂组合物提供在模具中。关闭包含前部分和后部分的模具，这样合成树脂模具部分的预成型表面之间铺展。合成树脂混合物固化和形成复制品。随后复制品从模具中取出。合成树脂复制品的自由表面是模具部分的相应表面的负像。复制工艺的优点在于，具有复杂折射表面，例如球形表面的光学元件，如透镜可以一种相对简单的方式制成而不必将基材，如玻璃进行复杂的抛光处理以得到所需表面形状。利用聚合反应的这种复制的缺陷在于出现收缩。尤其是，如果可键接树脂组合物的流动因为胶凝或粘度显著增加而受阻，进一步聚合反应会导致产生应力或甚至导致过早脱层。如果产品随后从模具中取出，尤其是在复制工艺的情况下，仅发生部分应力松弛，尤其当所形成的产品由密集交联聚合物网状结构构成时。但这种键接聚合物网状结构对于所形成的产品的内聚是理想的。
因此，本发明的目的是提供一种可聚合树脂组合物，如果该组合物在模具内固化，那么在它从模具中取出之后具有尽可能小的松弛和因此尽可能精确地呈现模具的形状。
本发明的另一目的是提供一种制造复制品的方法，该方法采用一种还特征在于高反应速率和可通过UV辐射控制反应的可聚合树脂组合物。
本发明的另一目的是提供一种制造复制品的方法，其中可聚合树脂在固化过程中基本上对氧不敏感，这样不完全被模具包封的那部分树脂仍可在环境空气中固化，这样避免了对用惰性气体覆盖所述模具的需求。
本发明的另一目的是提供一种制造复制品的方法，该方法采用一种其最终产物对应于有关透明度和硬度的目前适用的质量要求的可聚合树脂组合物。
本发明进一步的目的是提供一种制造复制品的方法，其中采用一种其粘度低至使得它可精确在复制品工艺中计量而没有任何问题的可聚合树脂组合物。
按照本发明，在开头段落中提及的方法的特征在于，固化处理是UV光-引发阳离子聚合反应，所用的树脂组合物是一种包含至少两个阳离子可聚合环状醚基团的化合物，它仅在已经发生至少30％的在适当固化条件下可在模具中实现的转化率时表现出胶凝迹象。
通过使用这种可键接树脂组合物，最终产品由于晚胶凝和相对小的收缩而基本上没有收缩应力。根据申请人的理解，相当小的收缩度可归因于以下事实：目前固化处理所基于的开环工艺不造成化学键数目的显著变化，而是起始产品和键接产品中的键的数目或多或少地相互对应，这样仅发生低程度的收缩。相反，在例如从上述美国专利说明书4,890,905中得知的已知的(甲基)丙烯酸酯化合物中，出现化学键数目的增加，这解释了较高的收缩度。另外，在按照本发明的化合物中，胶凝和玻璃化在达到高转化百分数之前不会发生，这样应力的产生在明显较后的阶段开始。根据本申请人的理解，这种惊人的作用由惊人地高程度的链转移所带来，这样在键接反应开始时，主要形成相当小的在达到高转化百分数之前不形成凝胶的分子。如果按照本发明的方法应用于复制例如，CD播放机的球形透镜，按照本发明的可键接组合物的应用可使得模具的形状基本上精确地对应于最终形成的产品，这样需要明显较小的收缩校正。另外，因为在产品从模具中取出之后需要较少的松弛，复制透镜在形状上的扩展预期会明显低于上述生产工艺。按照本发明的方法可尤其适用于复制需要精确(亚微米)形状复制的浮雕结构。
可适用于本发明的制造复制品的方法的化合物包括具有以下通式的可键接树脂组合物：
其中：
Y＝-O-，-SO2-，-CH2-，-C(CF3)2-，-C(CH3)2-，-C(＝O)-，-O-C(＝O)-，-O-C(＝O)-O-，
X＝卤素或CH3，
R1＝-CH2-，-C(CH3)2-，
R2＝-OCH2CH2-，-OCCH3HCH2-，-OCH2CCH3H-，-OCH2CHOHCH2-，
R3＝H，CnH2n+1，
n＝＞1的整数，
p＝1-4，
m，a，b，c分别是0-4的整数。
对于可键接树脂组合物，也可使用选自1，2，7，8-二环氧辛烷、3，4-环氧环-己基甲基-3′，4′-环氧环己烷羧酸酯、己二酸二(3，4-环氧环己基甲基)酯、己二酸二(3，4-环氧-6-甲基环己基甲基)酯和C12-C14-烷基缩水甘油基醚和其相应的氧杂环丁烷化合物的化合物。特别适用的氧杂环丁烷化合物是1，4-二[(3-乙基-3-氧杂环丁烷基甲氧基)甲基]苯。
根据所选可键接树脂组合物的粘度，在某些实施方案中可优选的是，可键接树脂组合物另外包含反应性稀释剂，优选选自丁基缩水甘油基醚，庚基缩水甘油基醚，辛基缩水甘油基醚，烯丙基缩水甘油基醚，p-t-丁基苯基缩水甘油基醚，苯基缩水甘油基醚，甲酚基缩水甘油基醚，1，4-丁烷二醇的二缩水甘油基醚，新戊基二醇的二缩水甘油基醚，聚丙二醇的二缩水甘油基醚，乙烯基环己烷二氧化物，间苯二酚的二缩水甘油基醚，聚丙二醇的二缩水甘油基醚和亚油酸二聚体的二缩水甘油基酯和其相应的氧杂环丁烷化合物。
本发明进一步涉及一种通过使包含至少两个阳离子可聚合环状醚基团的化合物进行UV光-引发阳离子聚合反应而得到的复制品，所述化合物不会在已经发生至少30％的可在适当固化条件下(如果需要在反应性稀释剂存在下)在模具中实现的转化率之前表现出胶凝。
合适的复制品是需要精确(亚微米)复制的任何浮雕结构。合适的复制品的其它例子是光学元件，尤其是球形透镜，透镜阵列，棱镜，光栅或用于光学场合的另一浮雕结构，或其组合。
本发明的这些和其它方面根据以下描述的实施方案变得显然和可理解。
对比例
球形透镜利用通常已知的光复制方法而制成，其中将包含单体，光引发剂和，如果需要，敏化剂的反应性混合物提供到球形模具中和压制使得液体在前模具的预成型表面和后模具的预成型表面之间铺展而不夹杂气泡。随后，反应性混合物暴露于穿过所述前和后模具中的至少一个并源自配有仅传输320-390nm光谱范围的滤光片的高压汞灯的UV光。如果需要，曝光工艺可进行使得UV光经过前模具和后模具，前提是两个模具被合并成透明的。在曝光工艺之后，透镜从模具中取出并进行光学和机械检查。
上述光复制方法使用包含4％2，2-二甲基氧基-1，2-二苯基乙烷-1-酮在2，2-二(4-(2-甲基丙烯酰氧基乙-1-氧基)苯基)丙烷中的溶液的反应性混合物进行。该混合物在室温下在强度40mW/cm2下暴露7秒和随后取出，然后它在10mW/cm2下在室温下再暴露1小时和在140摄氏度下在黑暗中稳定16小时。将如此得到的透镜进行光学和机械表征。
在聚合反应工艺过程中，混合物具有约7％的收缩率。通过使用这种反应性混合物，球形模具必须在迭代工艺中校正以得到所需形状的透镜。
按照本发明的实施例
使用描述于以上对比例的通常已知的光复制方法，只是所用的反应性混合物是4.75％二苯基六氟砷酸碘鎓和0.25％蒽在2，2-二(4-(缩水甘油基氧基)苯基)丙烷中的溶液。该混合物随后在室温下在强度100mW/cm2下暴露7秒和随后取出，然后它在10mW/cm2下在室温下再暴露1小时，和在110摄氏度下在黑暗中稳定8小时。将如此得到的透镜进行光学和机械表征。
在聚合反应工艺过程中，混合物具有约2.3％的收缩率。通过使用这种包含包括至少两个阳离子可聚合环状醚基团的化合物的反应性混合物，无需或几乎无需为了得到所需形状的透镜而校正球形模具，这不同于用于对比例的反应性混合物。该有利结果归因于以下事实：在从模具中取出之后，几乎不发生任何松弛。根据本申请人的理解，这种与用于对比例的反应性混合物相比非常小的松弛程度可归因于收缩下降和胶凝延迟的组合。
用于制造透镜的设备应该优选包括例如公开于美国专利US4,477,328的用于使至少一个模具在轴方向上在固化工艺过程中移动的装置或例如公开于美国专利US 4,812,346的用于在固化过程中补偿单体的装置。
Claims (12)
1.一种制造复制品的方法，该方法包括在具有预成型表面的前模具，和具有预成型表面的后模具之间提供可聚合树脂组合物，进行固化处理和从模具中取出如此制成的复制品，所述复制品包括一个其上复制有前模具的表面形状和后模具的表面形状的固体，特征在于固化处理是UV光-引发的阳离子聚合反应，所用的树脂组合物是一种包含至少两个阳离子可聚合环状醚基团的化合物，它仅在已经发生至少30％的在适当固化条件下可在模具中实现的转化率时表现出胶凝迹象。
2.权利要求1所要求的方法，特征在于树脂组合物进一步包含反应性稀释剂。
3.权利要求1-2所要求的方法，特征在于所述化合物表示为以下通式：
其中：
Y＝-O-，-SO2-，-CH2-，-C(CF3)2-，-C(CH3)2-，-C(＝O)-，-O-C(＝O)-，-O-C(＝O)-O-，
X＝卤素或CH3，
R1＝-CH2-，-C(CH3)2-，
R2＝-OCH2CH2-，-OCCH3HCH2-，-OCH2CCH3H-，-OCH2CHOHCH2-，
R3＝H，CnH2n+1，
n＝＞1的整数，
p＝1-4，
m，a，b，c分别为0-4的整数。
4.权利要求1-2所要求的方法，特征在于所述化合物选自1，2，7，8-二环氧辛烷、3，4-环氧环己基甲基-3′，4′-环氧环己烷羧酸酯、己二酸二(3，4-环氧环己基甲基)酯、己二酸二(3，4-环氧-6-甲基环己基甲基)酯和C12-C14-烷基缩水甘油基醚和其相应的氧杂环丁烷化合物，尤其是1，4-二[(3-乙基-3-氧杂环丁烷基甲氧基)甲基]苯。
5.权利要求1-4所要求的方法，特征在于对于反应性稀释剂，使用选自丁基缩水甘油基醚，庚基缩水甘油基醚，辛基缩水甘油基醚，烯丙基缩水甘油基醚，p-t-丁基苯基缩水甘油基醚，苯基缩水甘油基醚，甲酚基缩水甘油基醚，1，4-丁烷二醇的缩水甘油基醚，新戊基二醇的二缩水甘油基醚，聚丙二醇的二缩水甘油基醚，乙烯基环己烷二氧化物，间苯二酚的二缩水甘油基醚，聚丙二醇的二缩水甘油基醚和亚油酸二聚体的二缩水甘油基酯和其相应的氧杂环丁烷化合物的化合物。
6.一种通过使包含至少两个阳离子可聚合环状醚基团的化合物进行UV光-引发的阳离子聚合反应而得到的复制品，所述化合物仅在已经发生至少30％的可在适当固化条件下，如果需要在反应性稀释剂存在下，在模具中实现的转化率时表现出胶凝。
7.权利要求6所要求的复制品，特征在于该复制品在至少一面上包含浮雕结构，所述浮雕结构必须满足有关形态必要精度方面的高(亚微米)要求。
8.权利要求6-7所要求的复制品，特征在于所得复制品是光学元件。
9.权利要求8所要求的复制品，特征在于所得光学元件是(a)球形透镜，透镜排列，棱镜，光栅或用于光学场合的另一浮雕结构，或其组合。
10.权利要求6-9所要求的复制品，特征在于所述化合物表示为以下通式：
其中：
Y＝-O-，-SO2-，-CH2-，-C(CF3)2-，-C(CH3)2-，-C(＝O)-，-O-C(＝O)-，-O-C(＝O)-O-，
X＝卤素或CH3，
R1＝-CH2-，-C(CH3)2-，
R2＝-OCH2CH2-，-OCCH3HCH2-，-OCH2CCH3H-，-OCH2CHOHCH2-，
R3＝H，CnH2n+1，
n＝＞1的整数，
p＝1-4，
m，a，b，c分别为0-4的整数。
11.权利要求6-10所要求的复制品，特征在于所述化合物选自1，2，7，8-二环氧辛烷、3，4-环氧环己基甲基-3′，4′-环氧环己烷羧酸酯、己二酸二(3，4-环氧环己基甲基)酯、己二酸二(3，4-环氧-6-甲基环己基-甲基)酯和C12-C14-烷基缩水甘油基醚和其相应的氧杂环丁烷化合物，尤其是1，4-二[(3-乙基-3-氧杂环丁烷基甲氧基)甲基]苯。
12.权利要求6-11所要求的复制品，特征在于对于反应性稀释剂，使用选自丁基缩水甘油基醚，庚基缩水甘油基醚，辛基缩水甘油基醚，烯丙基缩水甘油基醚，p-t-丁基苯基缩水甘油基醚，苯基缩水甘油基醚，甲酚基缩水甘油基醚，1，4-丁烷二醇的二缩水甘油基醚，新戊基二醇的二缩水甘油基醚，聚丙二醇的二缩水甘油基醚，乙烯基环己烷二氧化物，间苯二酚的二缩水甘油基醚，聚丙二醇的二缩水甘油基醚和亚油酸二聚体的二缩水甘油基酯和其相应的氧杂环丁烷化合物的化合物。
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| DE102007018753B4 (de) | 2007-04-20 | 2012-11-08 | Airbus Operations Gmbh | Brandschutzraum für Flugzeugpassagiere mit Hilfe von Rumpfbehäutung aus Faser-Metall-Laminaten |
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| JP3140478B2 (ja) * | 1991-04-12 | 2001-03-05 | 旭電化工業株式会社 | エネルギー線を用いた注型成型方法 |
| US5807977A (en) * | 1992-07-10 | 1998-09-15 | Aerojet General Corporation | Polymers and prepolymers from mono-substituted fluorinated oxetane monomers |
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