CN1723106A - 复制品的制造方法,以及通过进行紫外光引发或热固化处理反应性混合物获得的复制品 - Google Patents

复制品的制造方法,以及通过进行紫外光引发或热固化处理反应性混合物获得的复制品 Download PDF

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CN1723106A
CN1723106A CNA2003801056729A CN200380105672A CN1723106A CN 1723106 A CN1723106 A CN 1723106A CN A2003801056729 A CNA2003801056729 A CN A2003801056729A CN 200380105672 A CN200380105672 A CN 200380105672A CN 1723106 A CN1723106 A CN 1723106A
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H·范桑坦
H·R·斯塔佩特
J·G·克鲁斯特博尔
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C39/026—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles characterised by the shape of the surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/003—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor characterised by the choice of material
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D17/00—Producing carriers of records containing fine grooves or impressions, e.g. disc records for needle playback, cylinder records; Producing record discs from master stencils
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    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • 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

本发明涉及一种生产复制品的方法，该方法包括在模具和基材或空白物之间提供一种可固化的树脂组合物，对其进行紫外光引发或热固化处理，并将由此方法生产的复制品从模具移出，所述复制品含有基材和提供在其上的模具的复制品。本发明也涉及由对反应性化合物进行紫外光引发或热固化处理而获得的复制品，特别是对短波长(即190－400nm)具有高透光性的复制品。

Description

复制品的制造方法，以及通过进行紫外光引发或 热固化处理反应性混合物获得的复制品
本发明涉及一种生产复制品的方法，该方法包括在模具和基材或空白物(blank)之间提供一种可固化的树脂组合物，对其进行紫外光引发或热固化处理，并将由此方法生产的复制品从模具移出，所述复制品含有基材和提供在其上的模具复制品。本发明也涉及由进行紫外光引发或热固化处理反应性混合物或组合物而获得的复制品，特别是对短波长(如190-400nm)具有高透光性的复制品。
模具复制技术已广为人知。在该项技术中，复制品模具的表面为最终产品的表面的负像拷贝，该复制品模具先由主模制备。最终产品接着按复制品模具的负像表面塑造，按此方法复制出主模的表面构造。
这种方法本身在以本申请人的名义申请的美国专利4,890,905中是已知的。复制工艺采用了具有精确限定的表面的模具或模型，该表面是复制品的所需光学轮廓的负像。精确确定模具或模型的表面限定时，必须考虑到复制品的合成树脂的收缩。少量的液态、可固化合成树脂组合物设置在模具表面。接着将可或不可透过紫外光的基材以所需的一面对着模具进行模压，或将模具对着基材进行模压，结果使合成树脂在基材的表面和模具的表面间展开。所述液态合成树脂组合物可以设置在基材上，而不是在模具上。使合成树脂混合物固化，并将其上粘合了经固化的合成树脂层的基材从模具脱出。合成树脂层的自由表面是相应的模具表面的负像。这种复制工艺的优点在于具有复杂的折射表面(例如非球面表面)的光学元件(例如透镜)可以通过相对简单的工艺进行生产，而无需对基材进行复杂的抛光处理。这种通过聚合进行复制的缺点是会发生收缩。特别是可粘合树脂组合物的流动被由聚合带来的凝胶化或粘性的大幅度增加而阻止的话，进一步的聚合将导致应力的产生甚至过早剥离。如果产品随后从模具上移出，尤其在复制工艺的情况下，特别是如果所得产品由致密粘合的聚合物网络组成时，应力只是部分得到释放。然而对于所形成产品的内聚而言，这种粘合的聚合物网络是理想的。
用于形成复制品模具的聚合组合物的临界状态已经通过多次失败的尝试得到确认，这些尝试采用了众多商业上可获得的树脂来形成复制品模具以试图获得玻璃表面的精确复制品。
例如，低熔点聚乙烯在复制在最终的塑料透镜中的模具表面中表现出形成微小的缺陷。同样，这些材料难以具有足够的刚度和硬度以防止固化塑料透镜的变形。另一方面，如线型聚甲基丙烯酸甲酯等材料生产的复制品模具，其表面被原来用于形成塑料透镜的材料之一进行溶剂侵害。这种溶剂侵害导致了最终塑料透镜的粗糙抛光，难以令人满意。
使得某些聚合物材料不受欢迎的另一性质是它们由塑造时的塑料透镜脱模时的脱模特征。
几何光学透镜要求例如高透光性、高折射率、塑造后低残余双折射等的基本光学品质，这些透镜用于各种照相机例如普通照相机、一次性照相机、摄录机等，光学记录设备例如CD、CD-ROM、CD-Video、MO、CD-R、DVD、蓝光光盘等，以及办公自动化设备例如复印机、打印机等。另外还要求具有如高热稳定性、高机械强度和硬度、低水吸收性、高耐候性、高耐溶剂性等基本性质。还要求其生产具有低费用和优异的可塑性。
一种具有上面提及的基本光学品质的光学元件本身由美国专利6,285,513可知，其含有：
满足下面条件公式的硅基树脂：
(硅基树脂中以R1SiO3/2形式存在的硅原子数)/(硅基树脂中硅原子总数)≥0，
(硅基树脂中以SiO4/2形式存在的硅原子数)/(硅基树脂中硅原子总数)≥0，
(硅基树脂中以R1SiO3/2形式存在的硅原子数)+(硅基树脂中以SiO4/2形式存在的硅原子数)×100/(硅基树脂中硅原子总数)≥10％
其中R1指的是氢原子、羟基基团、氨基基团、卤原子或有机基团。
含有上述可固化硅树脂的光学元件可用如注射塑模法、挤出塑模法、浇铸塑模法等塑模方式塑造。为获得所需的低双折射，如果可能，优选采用不施加压力成型。如实施例中揭示的所得的有机硅树脂组合物在40大气压下注入到透镜模塑染料中并加热到约150℃。应用紫外光和深紫外光时，由上述方法制造的光学元件的不利之处可能在于通过元件的长光程导致的透光度太低。
本发明的目的是提供一种生产光学元件的方法，所述方法通过复制紫外光或深紫外光透过性的玻璃，极大地提高对紫外光和深紫外光的透光度。
本发明的一个目的是提供一种生产复制品的方法，其中施用对紫外光和深紫外光具有足够透光度的反应性材料。
本发明的另一目的是提供一种生产复制品的方法，其中采用的材料易于被复制并且对(深)紫外光相对不敏感。
本发明的另一目的还在于提供一种通过对反应性化合物进行紫外光引发或热固化处理而获得的复制品，其中获得足够好的非球面元件。
依据本发明，开始段落中提及的方法的特征在于所用的树脂组合物为硅基反应性材料。
依据本发明，树脂组合物含有：
Figure A20038010567200071
和
Figure A20038010567200072
其中R1、R2、R3、R4＝氢、C1-C10烷基、乙烯基、苯基、羟基、氨基、卤原子，且R1、R2、R3和R4中至少一种为氢。
在本发明的优选实施方案中，树脂组合物还含有：
其中R1、R2、R3和R4具有与前述相同的含义。另外，树脂组合物还优选含有：
其中R1、R2、R3和R4具有与上述相同的含义。
应注意所述树脂组合物也含有金属催化剂，例如铂含量为5-10ppm的铂基催化剂。
优选组分(1)以含量为40-70重量％(基于可固化树脂组合物的总重量)存在。
另外，优选组分(2)以含量为15-40重量％(基于可固化树脂组合物的总重量)存在。
另外，优选组分(3)以含量为10-30重量％(基于可固化树脂组合物的总重量)存在。
优选组分(4)以含量为1.0-5.0重量％(基于可固化树脂组合物的总重量)存在。
本发明还涉及一种通过进行紫外光引发或热固化处理含硅基反应性材料的混合物而获得的复制品，其中的树脂组合物含有上述组分(1)和(2)。本发明的其他实施方案在所附的权利要求中揭示。
为实现本发明的上述目的，所获得的复制品的透光度至少为20％，当复制在对所施加的波长透明的玻璃材料上时进行测定，测定厚度为100μm、强度为100μW/cm2、波长为190-400nm、测定期至少为50小时。
在本发明的优选实施方案中复制品的透光度至少为90％，当复制在对所施加的波长透明的玻璃材料上时进行测定，测定厚度为100m、强度为0.5mW/cm2、波长为190-400nm、测定期为至少5000小时。
依据本发明获得的光学元件是(非)球面透镜、透镜阵列、棱镜、光栅或其他用于光学领域的凹凸结构或其组合，其复制品的特征在于所述复制品不是双折射的。
本发明的这些和其他方面可以通过参考下面所述的优选实施方案变得明显和得以解释。
实施例
一种由Sylgard 184(Dow Chemicals商标，组分(1)-(4)的混合物)制造的半径为4mm的半球圆柱体透镜，具有在257nm和500微瓦/平方厘米时仅为5％的初始透光度并在几个小时内降低到低于1％。在紫外光透过性的石英透镜上复制得到的100微米的相同材料层产生了一种光学元件，其在相同剂量和波长下在几天期内具有80％的透光度。

Claims (17)

1.一种生产复制品的方法，该方法包括在模具和基材或空白物之间提供一种可固化的树脂组合物，对其进行紫外光引发或热固化处理，并将以此方法生产的复制品由模具移出，所述复制品含有基材和提供在其上的模具的复制品，其特征在于，所用树脂组合物是硅基反应性材料。
2.权利要求1的方法，其特征在于树脂组合物中包含：
(1)
和
Figure A2003801056720002C2
(2)
其中
R1、R2、R3、R4＝氢、C1-C10烷基、乙烯基、苯基、羟基、氨基、卤原子，且R1、R2、R3和R4中至少一种为氢。
3.权利要求2的方法，其特征在于树脂组合物中还包含：
Figure A2003801056720002C3
(3)
其中R1、R2、R3和R4具有与权利要求中相同的含义。
4.依据权利要求2和3的方法，其特征在于树脂组合物还含有：
Figure A2003801056720003C1
(4)
其中R1、R2、R3和R4具有与权利要求2中相同的含义。
5.依据权利要求2-4的方法，其特征在于组分(1)以40-70重量％的含量存在，基于可固化树脂组合物的总重量计。
6.依据权利要求2-5的方法，其特征在于组分(2)以15-40重量％的含量存在，基于可固化树脂组合物的总重量计。
7.依据权利要求2-6的方法，其特征在于组分(3)以10-30重量％的含量存在，基于可固化树脂组合物的总重量计。
8.依据权利要求2-7的方法，其特征在于组分(4)以1.0-5.0重量％的含量存在，基于可固化树脂组合物的总重量计。
9.一种通过对含硅基反应性材料的混合物进行紫外光引发或热固化处理而获得的复制品。
10.权利要求9的复制品，其特征在于硅基反应性材料含有：
(1)
和
Figure A2003801056720003C3
(2)
其中R1、R2、R3、R4＝氢、C1-C10烷基、乙烯基、苯基、羟基、氨基、卤原子，且R1、R2、R3和R4中至少一种为氢。
11.权利要求10的复制品，其特征在于硅基反应性材料还含有：
(3)
其中R1、R2、R3和R4具有与权利要求10中相同的含义。
12.权利要求10和11的复制品，其特征在于硅基反应性材料还含有：
(4)
其中R1、R2、R3和R4具有与权利要求10中相同的含义。
13.权利要求9-12的复制品，其特征在于当复制在对所施加的波长透明的玻璃材料上时，在100μm厚度、100μW/cm2强度、190-400nm波长、至少50小时期间测得其透光度至少为20％。
14.权利要求9-13的复制品，其特征在于当复制在对所施加的波长透明的玻璃材料上时，在100μm厚度、0.5mW/cm2强度、190-400nm波长、至少500小时期间测得其透光度至少为90％。
15.权利要求9-14的复制品，其特征在于所述复制品不是双折射的。
16.权利要求9-15的复制品，其特征在于所得到的复制品是光学元件。
17.权利要求16的复制品，其特征在于所得到的光学元件是(非)球面透镜、透镜阵列、棱镜、光栅或其他用于光学领域的凹凸结构，或它们的组合。
CNB2003801056729A 2002-12-13 2003-11-26 复制品光学元件的制造方法以及通过该方法获得的复制品光学元件 Expired - Fee Related CN100528517C (zh)

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EP1572430A1 (en) 2005-09-14
US20060157875A1 (en) 2006-07-20
JP2006509870A (ja) 2006-03-23
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