CN1071359C - 具有耐久的色彩和/或荧光性能的制品 - Google Patents
具有耐久的色彩和/或荧光性能的制品 Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
一种表现出耐久的荧光性能的制品，包括聚合物基质、染料和位阻胺光稳定剂，其中聚合物基质由聚碳酸酯组成，染料主要由选自噻吨酮、苝酰亚胺和/或硫靛化合物的染料组成。本发明任选地复合有逆向反射元件使得当将得到的制品置于阳光下时它能具有耐久的荧光性能并同时能逆向反射。还披露了表现出耐久的荧光性能的制品的制造方法以及在染色的体系中增加聚碳酸酯寿命的方法。
Description
发明的领域
本发明涉及具有增强的色彩和/或荧光寿命的制品。
发明的背景
通常已知紫外光会造成着色剂的降解。这对于长期暴露在阳光辐照下的制品(如室外放置的制品)是一个特别严重的问题。着色剂降解发生在用常规着色剂着色的制品以及用荧光着色剂着色的制品中。但是，对荧光制品而言问题特别严重。荧光着色剂降解，通常比常规的着色剂更快地转变成无色。置于日常太阳光辐照中的荧光物质的有效寿命是短的，并常以天或月为计算单位。相反，常规着色剂物质的寿命通常大致较长，常以年为计算单位。
如果要求制品具有增强的可见度，则常用荧光着色剂着色该制品，尽管荧光着色剂的寿命劣于常规着色剂的寿命。荧光着色剂具有增强的可见度是因为荧光着色剂产生的与环境的光学对比度使该物质比常规的非荧光制品更明显。使用荧光着色剂受益的工业的例子有交通标志工业。荧光着色的交通标志在增加标志的可见度(从而增加驾驶员的安全)方面是有效的。尽管荧光标志增加了驾驶员的安全，但是它们的使用是有限的，因为它们的色彩稳定性差，需要频繁地换新以保持有效的性能。
在地面附近，太阳光辐射包括波长大于约290nm的电磁辐射，在约400-700nm范围内常认为是可见光范围。据信波长小于可见光的辐射会破坏常规和荧光着色剂。保持荧光制品色彩的努力包括添加能选择性地滤去低于340-380nm范围辐射的紫外屏蔽层。日本Kokai No.2-16042，申请号No.63-165914(Koshiji等)披露了包括一层屏蔽层和一个荧光着色剂层的荧光制品，其中屏蔽层仅允许一定范围的光透过。欧洲专利申请91311189.4也披露了一种逆向反射制品，包括紫外屏蔽层和含有规定聚合物基体的色彩层。该制品具有耐久的日光荧光和抗日光降解性。
需要即使暴露在紫外光辐照下也具有增强的荧光和色彩寿命的制品。具体地说，需要保留其色彩和/或其荧光性能而无需使用保护性表层的荧光制品。
发明的概述
简单地说，本发明提供具有增强的色彩寿命和荧光性能、带有或不带有保护性表层的制品。即本发明制品即使置于直射的阳光下也能在比通常所要求的时间更长的时期内保持其色彩并能发出荧光。本发明还包括这种耐久荧光制品的制造方法。还包括增强聚碳酸酯在染色的体系中的寿命的方法。
本发明制品包括(1)聚合物基质，(2)染料，以及(3)位阻胺光稳定剂，其中聚合物基质由聚碳酸酯组成，染料含有至少一种选自噻吨酮、苝酰亚胺和硫靛染料的化合物。在较好实例中位阻胺光稳定剂由来自2,2,6,6-四烷基哌啶类化合物组成。
在一个实例中，本发明制品还包括逆向反射元件。形成的制品具有逆向反射性和耐久的色彩和/或耐久的荧光性能。在长期的室外放置中这种材料表现出增强的白天和晚间可见度。
附图简述
将参照附图对本发明进行进一步说明，其中：
图1是本发明含有逆向反射元件的实例的横截面图，
图2是本发明含有逆向反射元件的另一个实例的横截面图，
图3是本发明含有逆向反射元件的另一个实例的横截面图，
图4是本发明含有紫外保护表层和逆向反射元件的另一个实例的横截面图。
这些想象化的图不是按比例绘制的，仅用于说明而非限制性的。
定义
在本文中，术语“着色剂”指用于使制品具有色彩、色度和色调的颜料、染料或其它物质。
在本文中，术语“常规着色剂”是指不发出可肉眼观察到荧光的着色剂。
在本文中，术语“耐久的”是指气候老化时增强的色彩或荧光保留性。
在本文中，术语“位阻胺光稳定剂”是指通常由2,2,6,6-四烷基哌啶这类化合物代表的空间位阻的胺。
在本文中，术语“气候老化”是指将制品置于天然的或人造的环境中，所述环境包括加热、光照、湿气和紫外辐照。
本发明说明性实例的详细描述
本发明合成含有染料和位阻胺光稳定剂的聚合物基质制造具有增强的色彩寿命和/或更耐久的荧光性能的制品。首先讨论本发明聚合物基质，然后讨论合适的染料和合适的位阻胺光稳定剂。
聚合物基质
聚碳酸酯是较好的本发明聚合物基质，因为它基本透明，容易用荧光染料和常规染料着色。另外，聚碳酸酯具有良好的光学性能，如对本发明是重要的良好的透光性。尽管聚碳酸酯具有这些要求的特性，但是本发明选用聚碳酸酯作为聚合物基质是令人惊讶的。正如本领域中已知的那样，当聚碳酸酯被置于紫外辐照下时，它是光敏的并发生降解。
染料
在一个较好的实例中，本发明荧光染料是来自噻吨酮、苝酰亚胺和硫靛染料类化合物的染料。本发明预期可使用单种荧光着色剂或染料着色本发明制品，或可以组合使用一种或多种荧光着色剂和一种或多种常规着色剂。
在本发明制品中常含有约0.01-2.00重量％，较好含有约0.05-0.70重量％，最好含有约0.1-0.5重量％荧光染料。应该理解根据本发明可使用染料含量超出该范围的制品。尽管染料的含量随最终应用的不同而不同，但是该含量常用于约0.075-0.25mm厚的膜。但是如果染料被加至较厚的膜中，较低的染料含量可给出相同的视觉效果，正如本领域中的技术人员所知的那样，与含有较低量的同种染料的制品相比，具有较高染料含量的制品具有较明亮的荧光和/或较深的色彩。但是，具有很高荧光染料含量的制品会发生自淬灭现象，这是荧光染料分子吸收相邻荧光染料分子发出的能量造成的。这种自淬灭不合要求地减小了荧光亮度。
在一些实例中，本发明制品中的着色剂主要由一种或多种选自苝酰亚胺、硫靛染料和噻吨酮类化合物的染料组成。在其它情况下，除了用所述染料以外，制品也可含有其它着色剂，如颜料或其它染料以调节制品的色彩和外观。例如，聚碳酸酯常具有黄色的色调。可掺混微量的(如约0.01重量％或更少)颜料(有时称之为蓝色漂白剂)以中和黄色的外观。还可向本发明制品中加入其它非荧光或常规染料或颜料，但是在选择这种染料和染料含量时应注意这种染料不应明显地影响荧光染料的性能。如果本发明制品中包括逆向反射元件，则任何染料或颜料都不应不合要求地损害制品的透明性，因为这会损害制品的逆向反射性能。
位阻胺光稳定剂
本发明制品中含有位阻胺光稳定剂(HALS)。这是一种有些奇怪的组合，因为如本领域中的熟练技术人员所知的那样，胺和聚碳酸酯的组合是不可取的。在传统观念上已知胺会进攻聚碳酸酯的羰基，从而使聚碳酸酯降解(例如参见Schnell,Chemistry and Physics of Polycarbonates,Page183,1964)。
不受理论的束缚，相信本发明中空间位阻胺、聚碳酸酯基质和染料的组合阻止了至今未搞清楚的降解和/或其它情况下会发生的染料和聚碳酸酯之间的反应。在我们已知的范围内，本发明的优点是通过组合本文所述的染料、聚合物基质和位阻胺光稳定剂而获得的。在本发明中染料被认为是作为单态氧敏化剂。能量转移剂(通常产生于三重态(triplet state)染料)被基态分子氧淬灭，产生活性的单态氧。随后单态氧不受约束地与染料反应，使染料降解。或者，单态氧与聚合物反应，使聚碳酸酯降解。但是，存在于本发明中的位阻胺光稳定剂能直接淬灭形成的单态氧，阻止引发降解反应。位阻胺光稳定剂也可阻止由聚合物氧化引发的次级反应的进行。这些反应包括一系列据认为在会导致聚合物和染料降解的聚碳酸酯光氧化中发生的自由基或基于过氧化物的链反应。在染色的体系中阻止这些反应增加了聚碳酸酯和染料的寿命。
任何位阻胺光稳定剂(如2,2,6,6-四烷基哌啶)都适用于本发明，但较好的是使用2,2,6,6-四甲基哌啶化合物作为位阻胺光稳定剂，因为这种化合物易于获得。在本发明制品中位阻胺光稳定剂的含量约为0.05-1.00重量％，较好约为0.10-0.75重量％，最好约为0.1-0.5重量％。
逆向反射
如前面所述，在一些实例中本发明制品是逆向反射的。当使用本发明制品制造交通标志时这种逆向反射能力是重要的。图1说明了本发明怎样通过在含有聚合物基质/位阻胺/染料复合物的膜32的一侧形成逆向反射元件30获得逆向反射能力的。图2和图3显示了本发明两种逆向反射实例。通过将逆向反射基片和本发明片材机械地直接相互层压在一起或者用透明粘合剂粘合两种片材，将逆向反射基片12或40附着在本发明片材18或50上。如果使用粘合剂，则该粘合剂最好对可见光是基本透明的。如图2所示，逆向反射基片可以包括形成于片材背面上的立方角(cube-corner)逆向反射元件20。其它实例包括如图3所示的具有基于微球的逆向反射结构52的基片40。单层微球71嵌入带有间隔层72、镜面反射层74和任选的粘合剂76的粘合剂层70。逆向反射元件的例子可参见美国专利4,896,943和5,069,964(均描述基于微球的结构)和4,938,563(立方角反射器结构)。
紫外保护表层
尽管不是必需的，但是本发明制品可任选地包括含有或不含有紫外吸收剂的表层。当用含有紫外吸收剂的表层覆盖的本发明制品并将其置于阳光下时，可观察到一些抗降解方面其它的改进。表层对可见光最好是基本透明的，并具有一种手段屏蔽大部分入射的紫外辐射。图4是相似于图2所示的本发明逆向反射实例，它还包括表层56。聚合物基质/染料/位阻胺光稳定剂复合物表示为膜60并层压在立体角逆向反射片64上。表层56最好与复合物膜60共延伸以便向本发明膜60提供最大的保护。
实施例
将通过下列说明性而非限制性的实施例对本发明进行进一步的说明。除非另有说明，所有量都以重量份表示。
在实施例中使用下列缩写：缩写 含义PC 聚碳酸酯PMMA 聚甲基丙烯酸甲酯SO63 HOSTASOL RED GGTM-购自Hoechst Celanese的Solvent
Orange63噻吨酮染料RED41 HOSTASOL RED 5BTM-购自Hoechst Celanese的Vat Red41
硫靛染料PI240 LUMOGEN F240TM购自BASF的橙色苝酰亚胺染料SY160:1 购自Mobay Corp.的MACROLEX 10GNTM Solvent Yellow
160:1苯并噁唑香豆素染料SG5 购自BASF的FLUOROL GREEN GOLD 084TM Solvent
Green5苝染料HALS1 购自Ciba-Geigy Corp,Hawthorne,NY名为TINUVIN622的
带有4-羟基-2,2,6,6,-四甲基-1-哌啶乙醇的丁二酸二甲酯聚
合物HALS2 购自Ciba-Geigy Corp名为CHIMASORB 944FL的聚
[6[(1,1,3,3-四甲基丁基)氨基]-s-三嗪-2,4-二基][2,2,6,6-四甲
基-4-哌啶基)亚氨基]六亚甲基[(2,2,6,6-四甲基-4-哌啶基)亚
氨基]HALS3 购自Ciba-Geigy Corp名为TINUVIN770的癸二酸二
(2,2,6,6-四甲基-4-哌啶基)酯
除非另有说明，否则使用下列试验方法。
加速的气候老化
为了以加速的方法模仿室外阳光环境，根据ASTM G26-B型，方法A，将实施例1-6和8中的试样用一水冷却的带硼硅酸盐内衬(inner)外过滤器的氙弧光装置在约63℃ Black Panel温度下照射102分钟，随后在去离子水喷射试样的同时再照射18分钟。据信这种循环的1000小时照射相当于室外阳光直射下至少几个月的照射。
色彩
用下列技术测定色彩。
使用购自Hunter、具有如下设置和条件的Labscan6000分光光度计：
光源D65，
0/45几何形状(Geometry)，
25mm入口(port)，
CIE2°标准观察器，
在400-700nm范围内每隔10nm测量一次。
初始的峰值全光谱发光系数(Peak Total Spectral Radiance Factor)的百分数(％PTSR)是通过在初始的峰值全光谱发光波长处经过指定时间(时间t)照射后试样的峰值全光谱发光系数与未经照射试样的峰值全光谱发光系数之比(百分比)算得的。算式最好用下式表示：
峰值全光谱发光系数是荧光含量的相对尺度。荧光含量直接与荧光染料的量相关，因此，峰值反射率是保留的荧光染料含量的相对尺度。通常认为约5或更小的％PTSR的差异对结构测量不是显著的。
测量经指定时间照射后的试样和未经照射的试样之间的CIELAB颜色差异(或DE*)。DE*是几种颜色媒介组分的函数。仅出于参考的目的，约2个单位的DE*或颜色变化才能被肉眼所分辨，而20或更大的DE*代表实际的颜色变化。
保留的荧光
用带有150瓦连续氙灯的SLM AS2荧光分光光度计(SLM Instruments,Rochester,NY)测量荧光。
在未照射试样的峰值发射波长处，以经指定时间照射的试样的荧光强度与未经照射试样的荧光强度之比(百分比)算得保留的荧光。
分子量
分子量是使用凝胶渗透色谱法(GPC)用一套MICROSTYRAGEL牌色谱柱(购自Waters Division of Millipore Corp,Milford,MA)测定的，并使用聚苯乙烯标准进行刻度。试样溶解在四氢呋喃中并用四氢呋喃在30℃以1.0ml/分钟的流速流动。使用设置在266nm的UV检测器检测聚碳酸酯。
室外气候老化
在约7×12厘米大小的试样上进行室外气候老化。将试样粘合在铝片上，铝片固定在涂成黑色、面朝上与垂直成45°角并朝南放置的板上。试样在Wittmann,Arizona放置12个月。
测定染料损失50％所需时间
将膜固定在铝滑动棚架(slide frames)上，用UV透明的聚烯烃膜(2mil(0.005cm)厚由购自Dow Corporation of Mldland,MI的Primacor3440制成的乙烯-丙烯酸共聚物膜)覆盖之，根据前面所述ASTM G26,B型，方法A进行照射。
测量每个试样的初始染料浓度和每经500小时照射后的染料浓度。试样总计经2000小时的照射。从染料浓度-总照射时间曲线(即[SO63]-小时图)图解内插得到每个试样的染料损失50％所需的时间。
根据Beer-Lambert定律用紫外-可见分光光度计测量染料浓度。所有测量都是在Beckman DU-70型紫外-可见分光光度计上进行的。
实施例1
实施例1说明带位阻胺光稳定剂的荧光染料SO63的荧光性能和色彩的改进的寿命，并对试样和带紫外保护表层的试样的寿命进行了比较。
如下制得实施例1的试样。将荧光染料和HALS(如有的话)与聚碳酸酯树脂颗粒一起掺混。将荧光染料以0.2重量％的含量加入聚碳酸酯树脂颗粒中。将位阻胺光稳定剂(如有的话)以0.26重量％的含量加入混合物中。所使用的树脂颗粒为Makrolon FCR-2407，购自Miles Inc.of Pittsburgh,PA.将染料/树脂/HALS混合物干燥过夜以除去水分。干燥过夜后，使用三个加热区设置在260℃、260℃和304℃，薄膜模头设置在304℃的单螺杆挤出机将混合物挤出成约4-6mils(0.1-0.15mm)厚的膜。挤出机是3/4英寸单螺杆挤出机，名为Haake Rheocord购自德国Haake of Karlsruhe。
随后使用透明的丙烯酸粘合剂将膜层压在3M牌ScotchliteTM Diamond GradeRetroreflective Sheeting3970G(3M Company of St.Paul,Minnesota制)构件上。用丙烯酸粘合剂将由聚氨酯-丙烯酸膜组成的含有或不含有UV吸收剂的表层膜(如表1所示)层压在荧光/逆向反射构件上。
用于实施例1的位阻胺光稳定剂(HALS)是HALS1(Tinuvin622)，一种叔胺低聚物。不含HALS的比较膜也如前面所述制得并层压成具有荧光/逆向反射/表层结构的试样，所有试样都在前面所述的加速的试验设备上进行气候老化。通过Hunter Labscan6000上的颜色测量评价荧光和色彩的保留。荧光寿命与％PTSR相关，由前面所述DE*计算色彩变化。
表1
| ％初始的峰值光谱发光系数加速的照射(小时) | ||||||
| 试样1 | HALS2 | UV吸收剂3 | 500 | 1000 | 1500 | 2000 |
| 1-A | 有 | 无 | 86％ | 80％ | 68％ | 61％ |
| 1-B | 无 | 无 | 80％ | 60％ | 54％ | 43％ |
| 1-C | 有 | 有 | 90％ | 84％ | 80％ | 63％ |
| 1-D | 无 | 有 | 87％ | 73％ | 63％ | 46％ |
1所有试样含有0.2重量％的染料SO63
2含量为0.26重量％的HALS1
3UV吸收剂是购自BASF的Uvinol400，含量3重量％。
表2
| 在加速的辐照下照射1000小时的试样与未照射试样比较的DE* | ||||||
| 试样1 | HALS2 | UVA3 | 500 | 1000 | 1500 | 2000 |
| 1-A | 有 | 无 | 5.7 | 12.4 | 26.6 | 38.2 |
| 1-B | 无 | 无 | 9.9 | 30.7 | 35.8 | 53.8 |
| 1-C | 有 | 有 | 4.9 | 13.1 | 17.8 | 47.2 |
| 1-D | 无 | 有 | 5.5 | 23.0 | 32.1 | 58.6 |
1所有试样含有0.2重量％的染料SO63
2含量为0.26重量％的HALS1
3在表层中具有3重量％Uvinol400(UV吸收剂)的聚氨酯-丙烯酸表层。
表1和表2的结果表明在具有或不具有紫外保护表层的情况下，HALS向SO63的荧光和色彩持久性提供了实质性的改进。与不含HALS的试样相比，含有HALS的试样在色彩和荧光寿命方面得到了改进。另外，当向试样增加UV吸收表层时，在含有HALS的试样中可观察到改进。
实施例2
实施例2说明本发明制品中染料RED41的荧光性能寿命的改进。
如实施例1所述制得实施例2的试样2E-2H，但是所使用的聚碳酸酯树脂是购自GE Plastics of Mt.Vernon,IN的Lexan123R-112。用于实施例2的位阻胺光稳定剂是HALS1。使用加速的气候老化设备在指定的时间内对试样进行气候老化，结果列于下表3。
表3
| ％初始的峰值全光谱发光系数照射(小时) | ||||
| 试样1 | HALS2 | UVA3 | 500 | 1000 |
| 2-E | 无 | 无 | 81％ | 53％ |
| 2-F | 有 | 无 | 76％ | 63％ |
| 2-G | 无 | 有 | 92％ | 62％ |
| 2-H | 有 | 有 | 91％ | 77％ |
1试样2E-2H含有0.2重量％的染料Red41
2含量为0.26重量％的HALS1
3具有3％Uvinol400的聚氨酯-丙烯酸表层。
表3的结果表明染料RED41得益于加入HALS1(试样2-F和2-H)。
实施例3
实施例3说明不同的位阻胺稳定剂以不同的用量适用于增加荧光染料SO63的寿命。
如实施例1制得膜。加入各种膜的HALS和染料的用量和类型列于下表4。如前面所述将试样在加速的气候老化设备中进行照射。
表4
| 试样 | 膜厚度(mm) | 初始SO63的重量％ | 添加剂/重量％ | 染料损失50％的时间 |
| 对照 | 0.1 | 0.2 | 无 | 420小时 |
| 3A | 0.1 | 0.2 | HALS2/0.25％ | 800小时 |
| 3B | 0.1 | 0.2 | HALS2/0.5％ | 740小时 |
| 3C | 0.1 | 0.2 | HALS1/0.5％ | 550小时 |
表4的结果表明不同的位阻胺光稳定剂(包括HALS1和HALS2)在增加SO63荧光染料的寿命方面都是有效的。
实施例4
实施例4说明适用于本发明的染料含量范围。
如实施例3所述制得试样。在制备试样时使用染料SO63和HALS1。在含有HALS的试样中，含有0.5重量％的HALS1。加入每种试样的染料的量列于下表中。将试样置于加速的气候老化设备中进行气候老化。
表5
| 试样 | 膜厚度(mm) | 初始SO63的重量％ | HALS/重量％ | 染料损失50％的时间 |
| 对照 | 0.1 | 0.2 | 无 | 420小时 |
| 3C | 0.1 | 0.2 | HALS1/0.5％ | 550小时 |
| 4A | 0.1 | 0.4 | HALS1/0.5％ | 570小时 |
表5的结果证明在不同的染料含量下HALS都是有效的。
实施例5
实施例5说明在一定含量范围内的不同的位阻胺光稳定剂都适用于本发明。
如实施例1所述制得膜。所使用的树脂是购自Miles Incorporated of Pittsburgh,PA的Makrolon FCR-2407。通过将着色的膜热层压至第二表面压印有逆向反射元件的透明层并将PMMA表层热层压至着色膜的第一表面制得试样。所有着色膜含有0.2重量％的染料SO63。如下表6所示将HALS1加入膜中。将试样在加速的气候老化设备中放置1000小时进行气候老化。结果列于表6。
表6
| 加速气候老化1000小时的％PTRSF和DE* | |||||
| 试样 | [SO63]重量％ | HALS | [HALS]重量％ | DE* | ％PTSRF |
| 5A | 0.2 | - | 0 | 17.3 | 75％ |
| 5B | 0.2 | HALS1 | 0.1 | 9.8 | 89％ |
| 5C | 0.2 | HALS1 | 0.25 | 5.9 | 89％ |
| 5D | 0.2 | HALS1 | 0.5 | 6.8 | 90％ |
结果表明各种含量的HALS1在增加染料SO63的荧光性能的寿命方面都是有效的。
比较例6
比较例6说明聚甲基丙烯酸甲酯不是合适的制造本发明制品的基质，因为这种制品没有表现出增加的荧光性能或色彩寿命。
如实施例1所述制得比较例6的膜，但是使用聚甲基丙烯酸甲酯(PMMA)代替聚碳酸酯作为聚合物基质。所使用的PMMA可以是购自ICI Acrylics(St.Louis,MO)的Perspex CP924或CP923，或者是购自杜邦(Wilmington,DE)的Lucite47K，它们都含有约0.3重量％苯并三唑型UV吸收剂。使用的HALS(如有的话)是含量为0.25重量％的HALS1。对PMMA的挤出温度为249-260℃。通过将四层3mil(0.075mm)的着色膜或两层6mil(0.15mm)的着色膜热层压在一起并将逆向反射元件压印在层压结构的第二表面制得试样。将试样在加速的气候老化设备中放置表7所列的时间进行气候老化。
表7
| 对PMMR1的％初始的峰值光谱发光系数，照射时间(小时) | ||||
| 试样 | 染料2 | HALS3 | 500小时 | 1000小时 |
| 6A | SO63 | 有 | 74％ | 72％ |
| 6A-1 | SO63 | 无 | 85％ | 78％ |
| 6B | Red41 | 有 | 66％ | 61％ |
| 6B-1 | Red41 | 无 | 70％ | 63％ |
| 6C | PI240 | 有 | 93％ | 92％ |
| 6C-1 | PI240 | 无 | 89％ | 90％ |
1聚甲基丙烯酸甲酯
2试样中染料的加入量为0.20重量％，但试样6C-1中的加入量为0.29重量％
3加入的HALS1为0.25重量％
如上所述，当向聚甲基丙烯酸甲酯中加入HALS和荧光染料时没有观察到荧光和色彩的寿命有增加的迹象(参见表7)。
实施例7
实施例7说明如果位阻胺光稳定剂与聚合物基质和荧光染料一起使用，则聚碳酸酯更具寿命。
如实施例5所述制得实施例7的试样。所使用的树脂是购自Miles Inc.的Makrolon FCR-2407。以0.2重量％的含量向试样中加入染料SO63。位阻胺光稳定剂以及向每个试样中加入的量列于表8。如上所述通过室外放置12个月进行气候老化。
表8
| 试样 | HALS | HALS的重量％ | 聚碳酸酯数均分子量 | DE*(对未 | 保留的峰值全光谱发光系数(％初始) | |
| 未放置老化 | 放置老化 | 放置老化的) | ||||
| 对照 | 无 | 0 | 17,796 | 12,058 | 62 | 55 |
| 7-A | HALS2 | 0.25 | 17,687 | 15,865 | 19 | 87 |
| 7-B | HALS2 | 0.50 | 17,836 | 15,552 | 20 | 87 |
| 7-C | HALS3 | 0.50 | 17,934 | 15,311 | 35 | 77 |
表8的分子量结果表明含有HALS的聚碳酸酯和荧光染料试样不如无HALS的对照试样那样容易降解。因此，本发明有助于增加聚碳酸酯的寿命。
表8的结果还表明含有HALS的试样的色彩和荧光性能不像无HALS的试样那样容易改变色彩。
实施例8
实施例8说明在室外放置时几种不同的位阻胺光稳定剂对荧光色彩寿命的影响。
如实施例5制得试样，但使用第二色彩层代替透明层，并且该层压印有逆向反射元件。所使用的树脂是购自Miles Inc.的Makrolon FCR-2407。所有着色的膜是含有0.25重量％SO63染料的聚碳酸酯，位阻胺光稳定剂列于表9，其用量为0.25重量％。如前面所述将试样在Arizona放置1年并测量初始峰值全光谱发光的百分数和色彩变化。色彩变化结果列于表9。
表9
| 在Arizona放置12个月 | |||
| 试样 | 加入的HALS | ％PTSRF | 色彩变化(DE*) |
| 对照 | 无 | 43 | 48 |
| 8-A | HALS1 | 70 | 21 |
| 8-B | HALS2 | 83 | 9.6 |
| 8-C | HALS3 | 89 | 14 |
实施例9
实施例9说明由分光荧光计(spectrofluorometer)测定的本发明试样的增强的荧光寿命。如实施例5制得试样，并放置进行加速的气候老化。在开始老化及老化2500小时后进行读数。HALS、染料、它们各自的含量和试验结果列于下表10。
表10
| 试样 | [HALS] | 染料[SO63] | 保留的荧光％ | DE* | ％PTSRF |
| 对照9A1 | 0 | 0.2重量％ | 31％ | 68.6 | 48％ |
| 9B1 | HALS2/0.25重量％ | 0.2重量％ | 78％ | 34.8 | 77％ |
| 对照9C2 | 0 | 0.2重量％ | 26％ | 71.3 | 42％ |
| 9D2 | HALS3/0.25重量％ | 0.2重量％ | 81％ | 32.3 | 81％ |
1聚碳酸酯由Makrolon2407组成
2聚碳酸酯由80％Makrolon2407和20％Lexan123R组成
比较例10
比较例10说明荧光染料SY160:1和SG5不是合适的用于本发明的染料。如实施例1制得膜。将两层4mil(0.1mm)着色的膜热层压在一起制得试样10A、10B和10D。将一层2mil含有1.8％Tinuvin327(购自Ciba-Geigy的UV吸收剂)的PMMA表层热层压在着色的层压物的第一表面上。通过将一层3mil含有1.2重量％Tinuvin327的PMMA表层热层压至一层12mil(0.3mm)膜的第一表面并在该膜的第二表面压印逆向反射元件制得试样10C。用于试样10A和10B的聚碳酸酯树脂是Makrolon2407，试样10C和10D使用的是Lexan 123R-112。
试样10E和10F是用于比较目的的试样。按照本发明制得试样10E和10F并证明苝酰亚胺染料适用于本发明。试样10E由聚碳酸酯树脂Lexan123R-112制成。将3mil(0.075mm)PMMA表层热层压至着色膜的第一表面上(在该着色膜的第二表面中压印有逆向反射元件)形成12mil聚碳酸酯膜。试样10-F由聚碳酸酯树脂Lexan 123R-112制成。通过将二层4mil(0.10mm)着色膜热层压在一起并将一层2mil(0.05mm)PMMA表层层压在得到的着色膜的第一表面上制得试样。在着色膜的第二表面上压印逆向反射元件。用于试样10-E和10-F的表层被制成具有相同的UV屏蔽能力。3mil(0.75mm)的表层含有1.2重量％Tinuvin327(购自Ciba Geigy Corp.),2mil(0.05mm)表层含有1.8重量％Tinuvin327。所有试样使用的HALS都是HALS1。将试样放置进行加速的气候老化。结果列于表11。
表11
| 试样 | [染料]重量％ | [HALS]重量％ | 1000 | 1500 | 2000 |
| 10A | SY160:10.2 | -- | 82％ | 79％ | 67％ |
| 10B | SY160:10.2 | 0.25 | 84％ | 80％ | 66％ |
| 10C | SG50.2 | -- | 50％ | 44％ | --1 |
| 10D | SG50.2 | 0.26 | 46％ | 42％ | --1 |
| 10E | PI2400.2 | -- | 83％ | --2 | 76％ |
| 10F | PI2400.2 | 0.26 | 94％ | --2 | 88％ |
1由于急剧的色彩降解而未测得数据
2在1500小时间隔未进行测量。
本领域中的熟练技术人员应该理解在不偏离本发明精神和权利要求范围的情况下可对上述实例的详细内容进行各种变化。
Claims (10)
1．一种表现出耐久的色彩和/或荧光性能的制品，包括聚合物基质、染料和位阻胺光稳定剂，其特征在于染料为至少一种选自噻吨酮、苝酰亚胺和硫靛化合物的染料，聚合物基质为聚碳酸酯。
2．如权利要求1所述的制品，其特征在于该制品是逆向反射的。
3．如权利要求1所述的制品，其特征在于该制品是膜。
4．如权利要求1所述的制品，其特征在于该制品含有0.01-2.00重量％的所述染料。
5．如权利要求1所述的制品，其特征在于所述制品含有0.10-0.75重量％所述位阻胺光稳定剂。
6．如权利要求1所述的制品，其特征在于所述位阻胺光稳定剂由2,2,6,6-四甲基哌啶化合物组成。
7．一种表现出耐久的色彩和/或荧光性能的制品的制造方法，包括：
挤压出含有0.01-2.0重量％至少一种选自噻吨酮、苝酰亚胺和硫靛化合物的染料，和0.05-1.00重量％位阻胺光稳定剂的聚碳酸酯基质。
8．如权利要求7所述的方法，其特征在于位阻胺光稳定剂由2,2,6,6-四甲基哌啶类化合物组成。
9．一种增加聚碳酸酯寿命的方法，包括将聚碳酸酯与位阻胺光稳定剂和染料相混合，其特征在于染料含有至少一种选自噻吨酮、苝酰亚胺和硫靛化合物的染料。
10．如权利要求9所述的方法，其特征在于位阻胺光稳定剂是2,2,6,6-四甲基哌啶化合物。
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| US08/345,608 | 1994-11-28 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311016C (zh) * | 2002-05-13 | 2007-04-18 | 通用电气公司 | 具有视觉效果的模塑塑料制品 |
Families Citing this family (88)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK0438796T3 (da) | 1990-01-22 | 1999-05-25 | Hoechst Marion Roussel Inc | Fremgangsmåde til enantioselektiv syntese af alkylerede oxindoler, som anvendes som mellemprodukter ved fremstilling af phy |
| US5816238A (en) * | 1994-11-28 | 1998-10-06 | Minnesota Mining And Manufacturing Company | Durable fluorescent solar collectors |
| WO1997001440A1 (en) | 1995-06-26 | 1997-01-16 | Minnesota Mining And Manufacturing Company | Multilayer polymer film with additional coatings or layers |
| US6737154B2 (en) | 1995-06-26 | 2004-05-18 | 3M Innovative Properties Company | Multilayer polymer film with additional coatings or layers |
| WO1997001677A1 (en) * | 1995-06-29 | 1997-01-16 | Minnesota Mining And Manufacturing Company | Wet retroreflective marking material |
| US6451408B1 (en) | 1995-06-29 | 2002-09-17 | 3M Innovative Properties Company | Retroreflective article |
| US6703108B1 (en) | 1995-06-29 | 2004-03-09 | 3M Innovative Properties Company | Wet retroreflective marking material |
| JPH11511592A (ja) * | 1995-08-28 | 1999-10-05 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | 持続性のある蛍光ソーラコレクタ |
| US5674622A (en) * | 1995-09-29 | 1997-10-07 | Minnesota Mining And Manufacturing Company | Fluorescent dye blends |
| US5920429A (en) * | 1995-09-29 | 1999-07-06 | Minnesota Mining And Manufacturing Company | Fluorescent dye blends |
| US6303058B1 (en) | 1996-06-27 | 2001-10-16 | 3M Innovative Properties Company | Method of making profiled retroreflective marking material |
| US5783307A (en) * | 1996-11-04 | 1998-07-21 | Eastman Chemical Company | UV stabilized multi-layer structures with detectable UV protective layers and a method of detection |
| AT409306B (de) * | 1997-10-03 | 2002-07-25 | Hoffmann La Roche | Optisch chemischer sensor |
| US6110566A (en) * | 1997-10-23 | 2000-08-29 | 3M Innovative Properties Company | Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers |
| US6001936A (en) | 1997-10-24 | 1999-12-14 | 3M Innovative Properties Company | Dye enhanced durability through controlled dye environment |
| JP2001522047A (ja) * | 1997-10-31 | 2001-11-13 | サーノフ コーポレイション | 蛍光を増強する方法 |
| US6191200B1 (en) | 1998-01-21 | 2001-02-20 | Reflexite Corporation | Extended life fluorescence polyvinyl chloride sheeting |
| DE19839669C1 (de) * | 1998-09-01 | 2000-08-03 | Leo Baumann | Verfahren und Vorrichtung zur Simulation der Belastung von Materialien durch solare ultraviolette Strahlung |
| GB9824314D0 (en) * | 1998-11-06 | 1998-12-30 | Clariant Int Ltd | New hetercyclic compounds |
| WO2000047407A1 (en) * | 1999-02-12 | 2000-08-17 | Reflexite Corporation | Extended life fluorescence polyvinyl chloride sheeting |
| US6958179B2 (en) * | 1999-12-30 | 2005-10-25 | 3M Innovative Properties Company | Segmented sheeting and methods of making and using same |
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| JP4028155B2 (ja) | 2000-04-11 | 2007-12-26 | 日本カーバイド工業株式会社 | 蛍光性再帰反射シート |
| US6552787B1 (en) | 2000-09-29 | 2003-04-22 | General Electric Company | Rapid non-destructive screening methods for polymeric coatings and materials |
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| AU2003224896B2 (en) | 2002-04-30 | 2009-01-15 | Avery Dennison Corporation | Fluorescent articles having multiple film layers |
| US7618709B2 (en) * | 2002-04-30 | 2009-11-17 | Avery Dennison Corporation | Fluorescent articles having multiple film layers |
| MXPA05000126A (es) * | 2002-07-08 | 2005-04-11 | Nippon Carbide Kogyo Kk | Senal iluminada internamente. |
| US20040146677A1 (en) | 2003-01-24 | 2004-07-29 | 3M Innovative Properties Company | Flexible reflective sleeve |
| US8617004B2 (en) * | 2007-02-16 | 2013-12-31 | Acushnet Company | Golf ball with translucent cover |
| US20040176184A1 (en) * | 2003-03-07 | 2004-09-09 | Morgan William E. | Multi-layer golf ball with translucent cover |
| US6949595B2 (en) * | 2003-03-07 | 2005-09-27 | Acushnet Company | Multi-layer golf ball with translucent cover |
| US20040176188A1 (en) | 2003-03-07 | 2004-09-09 | Morgan William E. | Multi-layer golf ball with translucent cover |
| US20040180734A1 (en) * | 2003-03-07 | 2004-09-16 | Puniello Paul A. | Co-injection nozzle, method of its use, and resulting golf ball |
| US7862760B2 (en) * | 2003-03-07 | 2011-01-04 | Acushnet Company | Co-injection nozzle, method of its use, and resulting golf ball |
| US20040176185A1 (en) * | 2003-03-07 | 2004-09-09 | Morgan William E. | Multi-layer golf ball with translucent cover |
| US20070006493A1 (en) * | 2003-05-12 | 2007-01-11 | Arnold Eberwein | Illuminated license plate for vehicles and vehicle provided with the same |
| US20070031641A1 (en) * | 2003-09-05 | 2007-02-08 | 3M Innovative Properties Company | License plate for back illumination and method for making same |
| US7261535B2 (en) * | 2003-12-31 | 2007-08-28 | Acushnet Company | Co-injection nozzle |
| US20050154098A1 (en) * | 2004-01-09 | 2005-07-14 | Reflexite Corporation | Fade-resistant fluorescent retroreflective articles |
| EP2757197A3 (en) | 2004-01-21 | 2014-11-19 | 3M Innovative Properties Company | Retroreflective elements and articles |
| US7329447B2 (en) * | 2004-04-01 | 2008-02-12 | 3M Innovative Properties Company | Retroreflective sheeting with controlled cap-Y |
| PL1584518T3 (pl) * | 2004-04-07 | 2008-03-31 | 3M Innovative Properties Co | Zespół tablicy rejestracyjnej zawierający źródło światła i podświetloną tablicę rejestracyjną |
| US7625501B2 (en) * | 2004-05-18 | 2009-12-01 | Ifire Ip Corporation | Color-converting photoluminescent film |
| US20060026731A1 (en) * | 2004-08-04 | 2006-02-09 | Reemay, Inc. | High visibility fabric and safety vest |
| DE102005043572A1 (de) * | 2005-09-12 | 2007-03-15 | Basf Ag | Fluoreszenzkonversionssolarzellen auf Basis von Terrylenfluoreszenzfarbstoffen |
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| GB2433637A (en) * | 2005-12-21 | 2007-06-27 | 3M Innovative Properties Co | Semi-transparent retroreflective material |
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| US7374297B2 (en) * | 2006-03-31 | 2008-05-20 | Reflexite Corporation | Conformable retroreflective film structure |
| US7842374B2 (en) * | 2006-07-28 | 2010-11-30 | 3M Innovative Properties Company | Retroreflective article comprising a copolyester ether composition layer and method of making same |
| US7674515B2 (en) * | 2006-10-23 | 2010-03-09 | Avery Dennison Corporation | Fluorescent polycarbonate articles |
| US8070626B2 (en) | 2007-02-16 | 2011-12-06 | Acushnet Company | Golf ball with a translucent layer comprising composite material |
| US7901301B2 (en) | 2007-02-16 | 2011-03-08 | Acushnet Company | Golf ball having visually enhanced non-uniform thickness intermediate layer |
| US7922607B2 (en) | 2007-02-16 | 2011-04-12 | Acushnet Company | Noncontact printing on subsurface layers of translucent cover golf balls |
| US9295882B2 (en) | 2007-02-16 | 2016-03-29 | Acushnet Company | Golf ball having a translucent layer containing fiber flock |
| DE102007052325A1 (de) * | 2007-03-29 | 2009-05-07 | Erk Eckrohrkessel Gmbh | Verfahren zum gleitenden Temperieren chemischer Substanzen mit definierten Ein- und Ausgangstemperaturen in einem Erhitzer und Einrichtung zur Durchführung des Verfahrens |
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| US20090286049A1 (en) * | 2008-05-15 | 2009-11-19 | 3M Innovative Properties Company | Methods of applying uv-curable inks to retroreflective sheeting |
| JP2012511177A (ja) | 2008-12-08 | 2012-05-17 | スリーエム イノベイティブ プロパティズ カンパニー | 図形を有するプリズム状再帰反射性物品及びその作製方法 |
| KR20110098781A (ko) * | 2008-12-08 | 2011-09-01 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | 그래픽을 갖는 보호 오버레이 및 오버레이를 포함하는 재귀반사성 물품 |
| EP2292972B1 (en) | 2009-09-02 | 2013-03-27 | 3M Innovative Properties Company | Light device and vehicle including light device |
| KR101741863B1 (ko) | 2009-10-16 | 2017-05-30 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | 적외광의 재귀반사도가 감소된 프리즘형 재귀반사성 시트류 |
| US9339843B2 (en) | 2010-10-14 | 2016-05-17 | Acushnet Company | Multi-colored golf ball and method for visually enhancing dimple arrangement |
| US9199127B2 (en) | 2012-03-26 | 2015-12-01 | Acushnet Company | Color golf ball |
| US9056223B2 (en) | 2012-03-26 | 2015-06-16 | Acushnet Company | Color golf ball |
| JP6305063B2 (ja) * | 2011-02-24 | 2018-04-04 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | 新規な照明装置 |
| DE102012104688A1 (de) | 2012-05-30 | 2013-12-05 | Hamilton Bonaduz Ag | Optisches Sensorelement |
| DE102012111686A1 (de) * | 2012-11-30 | 2014-06-05 | Hamilton Bonaduz Ag | Chemisch stabiler Sensor |
| US9187034B2 (en) | 2013-03-15 | 2015-11-17 | International Automotive Components Group North America, Inc. | Luminescent, ultraviolet protected automotive interior members |
| US9204598B2 (en) | 2013-05-27 | 2015-12-08 | Saudi Basic Indsutries Corporation | Solar energy funneling using thermoplastics for agricultural applications |
| US9333396B2 (en) | 2014-03-06 | 2016-05-10 | Acushnet Company | Color golf ball constructions incorporating durable and light-stable compositions |
| JP6346305B2 (ja) * | 2014-12-05 | 2018-06-20 | 大日精化工業株式会社 | 顆粒状樹脂用添加剤の製造方法、その製造方法により得られる顆粒状樹脂用添加剤、熱可塑性樹脂組成物、及び成形品 |
| JP2016118584A (ja) | 2014-12-18 | 2016-06-30 | スリーエム イノベイティブ プロパティズ カンパニー | 再帰性反射シート及びライセンスプレート、並びにそれらの製造方法 |
| US11925219B2 (en) * | 2015-06-18 | 2024-03-12 | Jeffrey Garre Barkshire | Fashionable high-visibility safety apparel |
| JP6698400B2 (ja) * | 2016-03-29 | 2020-05-27 | 帝人株式会社 | 赤外線遮蔽透明部材用樹脂組成物及び成形品 |
| US11542384B2 (en) * | 2017-03-28 | 2023-01-03 | Ford Global Technologies, Llc | Stabilized additive manufacturing articles |
| WO2023189049A1 (ja) * | 2022-03-30 | 2023-10-05 | 三菱ケミカル株式会社 | 樹脂組成物、フィルム、フィルムの製造方法および積層体 |
| CN116084174A (zh) * | 2023-03-03 | 2023-05-09 | 西安工程大学 | 同时掺杂荧光染料和光稳定剂的聚合物光纤及其制备方法 |
Family Cites Families (43)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3116256A (en) * | 1961-08-24 | 1963-12-31 | Lawter Chem Inc | Daylight fluorescent compositions |
| US3830682A (en) * | 1972-11-06 | 1974-08-20 | Rowland Dev Corp | Retroreflecting signs and the like with novel day-night coloration |
| JPS5147738B2 (zh) * | 1973-11-27 | 1976-12-16 | ||
| JPS57119941A (en) * | 1981-07-13 | 1982-07-26 | Sumitomo Chem Co Ltd | Polymeric material composition containing pigment and stabilizer |
| JPS5898357A (ja) * | 1981-12-08 | 1983-06-11 | Teijin Chem Ltd | 樹脂組成物 |
| IT1151544B (it) * | 1982-04-15 | 1986-12-24 | Anic Spa | Composizione a base di policarbonati alifatici contenente grupi uretanici e terminazioni acriliche o metacriliche reticolabile in presenza di iniziatori radicalici |
| DE3382687D1 (de) * | 1982-09-30 | 1993-07-01 | Ciba Geigy Ag | Mit bis-(polyalkylpiperidinyl-amino)-1,3,5-triazinen stabilisierte polyolefine. |
| US4691015A (en) * | 1984-07-23 | 1987-09-01 | Ciba-Geigy Corporation | Hydroxylamines derived from hindered amines |
| US4778837A (en) * | 1985-05-03 | 1988-10-18 | American Cyanamid Company | Low basicity hindered amine light stabilizers |
| US4863981A (en) * | 1986-06-30 | 1989-09-05 | Ciba-Geigy Corporation | Synergistic mixture of stabilizers |
| US4839405A (en) * | 1986-07-08 | 1989-06-13 | Plasticolors, Inc. | Ultraviolet stabilizer compositions, stabilized organic materials, and methods |
| US4743642A (en) * | 1986-09-08 | 1988-05-10 | The Dow Chemical Company | Color balanced rubber-reinforced plastic |
| US4938563A (en) * | 1986-11-21 | 1990-07-03 | Minnesota Mining And Manufacturing Company | High efficiency cube corner retroflective material |
| JPS63199248A (ja) * | 1987-02-13 | 1988-08-17 | Fuji Photo Film Co Ltd | 有機基体物質を光に対して安定化する方法 |
| US5073404A (en) * | 1987-03-09 | 1991-12-17 | Minnesota Mining And Manufacturing Company | Silica coating composition for reflective sheeting |
| US4896943A (en) * | 1987-05-13 | 1990-01-30 | Minnesota Mining And Manufacturing Company | Encapsulated-lens retroreflective sheeting having improved cover film |
| US4857595A (en) * | 1987-08-12 | 1989-08-15 | Pennwalt Corporation | Polymer bound hindered amine light stabilizers |
| US5096977A (en) * | 1987-08-12 | 1992-03-17 | Atochem North America, Inc. | Process for preparing polymer bound UV stabilizers |
| JPS6474272A (en) * | 1987-09-14 | 1989-03-20 | Fuji Photo Film Co Ltd | Stabilization of organic base substance against light |
| US5162405A (en) * | 1987-12-24 | 1992-11-10 | Elf Atochem North America, Inc. | Single-functional and mixtures of multi-functional oligomeric performance additive compositions and their uses |
| ES2050274T3 (es) * | 1988-06-14 | 1994-05-16 | Ciba Geigy Ag | Procedimiento para la estabilizacion fotoquimica de fibras de polipropileno sin teñir y teñidas. |
| JP2844339B2 (ja) * | 1988-07-05 | 1999-01-06 | 日本カーバイド工業株式会社 | 蛍光発色シート |
| JP2989610B2 (ja) * | 1988-08-22 | 1999-12-13 | ポリプラスチックス株式会社 | 耐候性ポリアセタール樹脂組成物 |
| US5004770A (en) * | 1988-10-19 | 1991-04-02 | Ciba-Geigy Corporation | Polymeric substrates stabilized with N-substituted hindered amines |
| US5140081A (en) * | 1989-03-21 | 1992-08-18 | Ciba-Geigy Corporation | Peroxide free radical initiators containing hindered amine moieties with low basicity |
| US5145893A (en) * | 1989-03-21 | 1992-09-08 | Ciba-Geigy Corporation | Non-migrating 1-hydrocarbyloxy hindered amine derivatives as polymer stabilizers |
| US5069964A (en) * | 1989-05-23 | 1991-12-03 | Minnesota Mining And Manufacturing Company | Flexible, substrate-insular retroreflective sheeting |
| JPH0364350A (ja) * | 1989-08-01 | 1991-03-19 | Polyplastics Co | 耐候性ポリアセタール樹脂組成物 |
| JP2731601B2 (ja) * | 1989-09-06 | 1998-03-25 | 旭電化工業株式会社 | ポリカーボネート樹脂組成物 |
| US5177246A (en) * | 1989-10-02 | 1993-01-05 | Ciba-Geigy Corporation | Hydroxphenylcarboxylic acid esters as stabilizers |
| FR2652578B1 (fr) * | 1989-10-02 | 1994-04-29 | Rhone Poulenc Chimie | Nouvelles dihydropyridines a groupements amine encombree. |
| US5302497A (en) * | 1989-12-21 | 1994-04-12 | Ciba-Geigy Corporation | Photosensitive organic polymeric material containing UV absorbers |
| US5068356A (en) * | 1990-02-20 | 1991-11-26 | Atochem North America, Inc. | Hindered phenolic n-(amido)imides |
| SE468856B (sv) * | 1990-07-11 | 1993-03-29 | Ultralux Ab | Fluorescerande vaegmarkering |
| ZA918849B (en) * | 1990-12-06 | 1992-08-26 | Minnesota Mining & Mfg | Articles exhibiting durable fluorescence |
| US5132387A (en) * | 1991-01-07 | 1992-07-21 | Elf Atochem North America, Inc. | Hindered amine light stabilizer hydrazides for stabilizing polyurethane, polyurea and polyurethane-polyurea polymers |
| US5334699A (en) * | 1992-06-29 | 1994-08-02 | Xerox Corporation | Polymeric initiator compounds |
| US5234888A (en) * | 1992-07-29 | 1993-08-10 | Agfa-Gevaert, N.V. | Dye-donor element for use according to thermal dye sublimation transfer |
| TW237471B (zh) * | 1992-09-03 | 1995-01-01 | Ciba Geigy | |
| EP0612796A1 (en) * | 1993-02-23 | 1994-08-31 | Ciba-Geigy Ag | Stabilisation of organic pigments |
| US5306456A (en) * | 1993-03-10 | 1994-04-26 | Ciba-Geigy Corporation | Preparing laminated thermoplastics stabilized with bisbenzophenones |
| DE4313519C2 (de) * | 1993-04-24 | 1996-07-11 | Kurz Leonhard Fa | Heißprägefolie zur Herstellung von Kraftfahrzeug-Nummernschilder |
| IT1266113B1 (it) * | 1993-08-02 | 1996-12-20 | Nordica Spa | Procedimento per l'ottenimento di elementi iniettati presentanti opacita' o trasparenza predeterminabile |
-
1995
- 1995-10-11 DE DE69515062T patent/DE69515062T2/de not_active Expired - Lifetime
- 1995-10-11 AU AU38341/95A patent/AU700888B2/en not_active Expired
- 1995-10-11 EP EP95936357A patent/EP0794975B1/en not_active Expired - Lifetime
- 1995-10-11 CA CA002205805A patent/CA2205805C/en not_active Expired - Lifetime
- 1995-10-11 WO PCT/US1995/013340 patent/WO1996017012A1/en active IP Right Grant
- 1995-10-11 JP JP51876596A patent/JP3447744B2/ja not_active Expired - Lifetime
- 1995-10-11 CN CN95196453A patent/CN1071359C/zh not_active Expired - Lifetime
- 1995-10-11 KR KR1019970703526A patent/KR100431164B1/ko not_active IP Right Cessation
-
1996
- 1996-05-21 US US08/650,964 patent/US5605761A/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311016C (zh) * | 2002-05-13 | 2007-04-18 | 通用电气公司 | 具有视觉效果的模塑塑料制品 |
Also Published As
| Publication number | Publication date |
|---|---|
| US5605761A (en) | 1997-02-25 |
| DE69515062T2 (de) | 2000-09-14 |
| AU700888B2 (en) | 1999-01-14 |
| EP0794975B1 (en) | 2000-02-09 |
| DE69515062D1 (de) | 2000-03-16 |
| CA2205805A1 (en) | 1996-06-06 |
| AU3834195A (en) | 1996-06-19 |
| MX9703689A (es) | 1997-10-31 |
| KR100431164B1 (ko) | 2004-09-16 |
| CA2205805C (en) | 2005-08-09 |
| EP0794975A1 (en) | 1997-09-17 |
| JP3447744B2 (ja) | 2003-09-16 |
| WO1996017012A1 (en) | 1996-06-06 |
| JPH10510313A (ja) | 1998-10-06 |
| CN1168684A (zh) | 1997-12-24 |
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