公开(公告)号：US4754056A

公开(公告)日：1988-06-28

申请号：US938452

申请日：1986-12-05

申请人： Robert E. Ansel ,  Kevin P. Murray

发明人： Robert E. Ansel ,  Kevin P. Murray

IPC分类号： C08G18/83 ,  C09D4/00 ,  G11B5/702 ,  C07C69/54 ,  C07C102/06 ,  C07C103/14 ,  C07C103/24

CPC分类号： C08G18/833 ,  C09D4/00 ,  G11B5/7026

摘要： Liquid coating compositions adapted to be cured by exposure to ionizing radiation are disclosed in which a liquid vehicle of coating viscosity having an ethylenically unsaturated portion comprising one or more polyethylenically unsaturated materials adapted to cure on radiation exposure, pigment dispersed in the vehicle, and an acrylate-functional radiation-curable dispersant having free carboxyl group for wetting the pigment and assisting in the stable dispersion of the pigment in the vehicle. This dispersant is an acrylate-functional carboxylic acid amide carrying free carboxyl groups, especially an adduct of a polyacrylate and a stoichiometric deficiency of a primary amine to provide a secondary amine having acrylate functionality, the secondary amine functionality being reacted with a polycarboxylic acid anhydride to form amide groups therewith.

摘要翻译： 公开了适于通过暴露于电离辐射而固化的液体涂料组合物，其中具有烯属不饱和部分的涂料粘度的液体载体包含适于在辐射照射下固化的一种或多种多烯属不饱和物质，分散在载体中的颜料和丙烯酸酯 具有游离羧基的功能性可辐射固化分散剂，用于润湿颜料并有助于颜料在车辆中的稳定分散。 该分散剂是带有游离羧基的丙烯酸酯官能羧酸酰胺，特别是聚丙烯酸酯与伯胺的化学计量不足的加合物，以提供具有丙烯酸酯官能团的仲胺，仲胺官能团与多元羧酸酐反应生成 与其形成酰胺基。

公开(公告)号：US5011635A

公开(公告)日：1991-04-30

申请号：US353538

申请日：1989-05-18

申请人： Edward J. Murphy ,  John J. Krajewski ,  Robert E. Ansel

发明人： Edward J. Murphy ,  John J. Krajewski ,  Robert E. Ansel

IPC分类号： B29C67/00

CPC分类号： B29C67/0066

摘要： The present invention contemplates a stereolithographic apparatus and method having a liquid organic phase and a fluid phase separated by a membrane that inhibits contact between the phases.

摘要翻译： 本发明考虑了一种立体光刻设备和方法，其具有液体有机相和通过膜分离的流体相，其抑制相之间的接触。

公开(公告)号：US4945032A

公开(公告)日：1990-07-31

申请号：US429561

申请日：1989-10-31

申请人： Edward J. Murphy ,  Robert E. Ansel ,  John J. Krajewski

发明人： Edward J. Murphy ,  Robert E. Ansel ,  John J. Krajewski

IPC分类号： B29C67/00 ,  G03F7/00

CPC分类号： B29C67/0066 ,  G03F7/0037 ,  Y10S430/146

摘要： An improved stereolithographic process is provided in which the formation of a thin walled three-dimensional object in a reservoir of liquid ultraviolet-curable ethylenically unsaturated material using a support is positioned immediately beneath the upper surface of the liquid reservoir with that upper surface being exposed to ultraviolet light in a pattern to solidify the liquid at and near the upper surface in a series of cross-sections of the desired three-dimensional object, one atop the other. In this way there is formed a series of superposed layers which adhere to one another to build the desired three-dimensional object within the liquid reservoir. The improvement comprises, stopping the exposure at any portion of the surface in the formation of said layers and then repeating the exposure at least once again in the production of each surface layer so that the strength and solvent resistance of the formed object are increased and its distortion is minimized. The ultraviolet exposure of each surface layer is preferably carried out as a series of rapid repeated scans of a computer-directed focused laser.

摘要翻译： 提供了一种改进的立体光刻方法，其中使用支撑体在液体紫外线固化的烯属不饱和材料的储存器中形成薄壁三维物体位于液体储存器的上表面的正下方，该上表面暴露于 紫外光以图案的方式固化所需三维物体的一系列横截面中的上表面上和附近的液体，一个在另一个之上。 以这种方式形成一系列重叠的层，其彼此粘附以在液体储存器内构建所需的三维物体。 改进之处在于，在形成所述层的表面的任何部分处停止曝光，然后在每个表面层的制造中至少再次重复曝光，使得所形成的物体的强度和耐溶剂性增加， 失真最小化。 每个表面层的紫外线暴露优选作为计算机引导的聚焦激光器的一系列快速重复扫描进行。

公开(公告)号：US4942001A

公开(公告)日：1990-07-17

申请号：US429568

申请日：1989-10-31

申请人： Edward J. Murphy ,  Robert E. Ansel ,  John J. Krajewski

发明人： Edward J. Murphy ,  Robert E. Ansel ,  John J. Krajewski

IPC分类号： B29C35/08 ,  B29C39/00 ,  B29C67/00 ,  G03F7/00

CPC分类号： B29C67/0062 ,  B29C35/08 ,  B29C39/006 ,  G03F7/0037 ,  B29K2025/00 ,  B29K2033/04 ,  B29K2055/00

摘要： A stereolithographic method which employs an ultraviolet-curable liquid composition adapted to cure rapidly to a lightly cross-linked solvent-swellable three-dimensional complexly-shaped polymeric thin-walled element constituted by heat-softenable solid polymer upon exposure to ultraviolet dosage in the range of about 0.1 to about 10 Joules per square centimeter and which possesses reduced distortion comprises, from 20 to 80 weight percent, of a resinous polyacrylate or polymethacrylate dissolved in a combination of 10 to 45 weight percent of a liquid polyacrylate or polymethacrylate, which is preferably trifunctional, and 10 to 45 weight percent of liquid N-vinyl monomer, preferably N-vinyl pyrrolidone. Thus, the weight ratio of polyacrylate: polymethacrylate: N-vinyl monomer is about 1:2:2 to about 8:1:1. One of the foregoing polyacrylates or polymethacrylates is a polyacrylate and the other is a polymethacrylate so that good cure speed is accompanied by good distortion resistance. In the method, a reservoir of the liquid composition is established and its exposed surface is irradiated to solidify the surface and build up a thin-walled element which is removed from the reservoir, drained of liquid adhering thereto and cured.

摘要翻译： 一种立体光刻方法，其采用可紫外线固化的液体组合物，其适于快速固化至在可暴露于范围内的紫外线剂量下由可热软化的固体聚合物构成的轻度交联的溶剂可膨胀的三维复合形状的聚合物薄壁元件 约0.1至约10焦耳每平方厘米并且具有减小的变形的组合包含20至80重量％的以10至45重量％的液体聚丙烯酸酯或聚甲基丙烯酸甲酯的组合溶解的树脂聚丙烯酸酯或聚甲基丙烯酸酯，其优选 三官能和10至45重量％的液体N-乙烯基单体，优选N-乙烯基吡咯烷酮。 因此，聚丙烯酸酯：聚甲基丙烯酸酯：N-乙烯基单体的重量比为约1:2:2至约8:1:1。 上述聚丙烯酸酯或聚甲基丙烯酸酯之一是聚丙烯酸酯，另一种是聚甲基丙烯酸酯，因此良好的固化速度伴随着良好的抗变形性。 在该方法中，建立了液体组合物的储存器，并且照射其暴露的表面以固化表面并且形成从储存器中取出的薄壁元件，排出附着在其上并固化的液体。

公开(公告)号：US4932750A

公开(公告)日：1990-06-12

申请号：US448252

申请日：1982-12-09

申请人： Robert E. Ansel ,  Orvid R. Cutler, Jr.

发明人： Robert E. Ansel ,  Orvid R. Cutler, Jr.

IPC分类号： C03C25/10 ,  C08F299/06 ,  C08G18/10 ,  C08G18/67

CPC分类号： C08G18/671 ,  C03C25/106 ,  C08F299/065 ,  C08G18/10

摘要： Radiation-curable coating compositions particularly adapted for the single coat coating of optical fibers are disclosed. These comprise (1) from 65% to 85% of a diethylenic-terminated polyurethane, which may contain urea groups, the polyurethane being based on a diisocyanate having an average molecular weight of from 400 to 5000; and (2) from 5% to 25% of an ether of a C.sub.2 -C.sub.4 alkylene glycol monoester of a monoethylenically unsaturated monocarboxylic acid, the ether being selected from the group consisting of ethoxyethyl, dicyclopentenyl, phenyl, and mixtures thereof. Ethoxyethoxyethyl acrylate is particularly preferred. A triacrylate ester, such as trimethylol propane triacrylate, is also desirably present.

摘要翻译： 公开了特别适用于光纤的单涂层涂层的可辐射固化涂料组合物。 这些包括（1）65％至85％的可含有尿素基团的二亚乙基封端的聚氨酯，所述聚氨酯基于平均分子量为400至5000的二异氰酸酯; 和（2）5％至25％的单烯属不饱和一元羧酸的C 2 -C 4亚烷基二醇单酯的醚，所述醚选自乙氧基乙基，二环戊烯基，苯基及其混合物。 特别优选丙烯酸乙氧基乙氧基乙酯。 还希望存在三丙烯酸酯，如三羟甲基丙烷三丙烯酸酯。

公开(公告)号：US4496210A

公开(公告)日：1985-01-29

申请号：US398161

申请日：1982-07-19

申请人： Robert E. Ansel ,  Orvid R. Cutler ,  Elias P. Moschovis

发明人： Robert E. Ansel ,  Orvid R. Cutler ,  Elias P. Moschovis

IPC分类号： C08L83/04 ,  C03C25/10 ,  C03C25/24 ,  C08F290/00 ,  C08F299/00 ,  C08F299/08 ,  C08G18/61 ,  C08G18/81 ,  C08G77/388 ,  C08G77/392 ,  C08L83/08 ,  C09D183/04 ,  G02B6/44 ,  B05D5/06 ,  G02B5/172

CPC分类号： C08L83/08 ,  C03C25/106 ,  C08G18/61 ,  C08G18/8175 ,  C08G77/388 ,  C08G77/392 ,  Y10T428/31612

摘要： Optical fibers are coated with a radiation-curable liquid, polyethylenically unsaturated coating composition consisting essentially of an organic polysiloxane having from 2 to 6 reactive side chains each of which carry a functional group providing one reactive site which has been reached to provide a single radiation-curable monoethylenically unsaturated side chain. There are about one such side chain for every 500 to 5,000 units of molecular weight. This provides a prime coating which has a modulus of elasticity at room temperature and at -60.degree. C. below 3000.

摘要翻译： 用可辐射固化液体，多烯属不饱和涂层组合物涂覆光纤，该组合物基本上由具有2-6个反应性侧链的有机聚硅氧烷组成，每个反应性侧链带有提供一个反应部位的官能团， 可固化单烯属不饱和侧链。 每500-5,000个分子量单位有约一个侧链。 这提供了一种初始涂层，其在室温和-60℃以下在3000以下具有弹性模量。

公开(公告)号：US4818780A

公开(公告)日：1989-04-04

申请号：US185538

申请日：1988-04-25

申请人： Kevin P. Murray ,  William E. Hoffman ,  Robert E. Ansel

发明人： Kevin P. Murray ,  William E. Hoffman ,  Robert E. Ansel

IPC分类号： C08G18/08 ,  C08G18/00 ,  C08G18/48 ,  C08G18/64 ,  C08G18/67 ,  C08G18/72 ,  C08G18/81 ,  C08G18/04

CPC分类号： C08G18/6407 ,  C08G18/4879 ,  C08G18/8158

摘要： The reaction product of an adduct of an ethylenically unsaturated monohydric alcohol, such as 2-hydroxyethyl acrylate, with an organic diisocyanate in which one of the two isocyanate groups is more strongly reactive than the other, such as isophorone diisocyanate, is reacted with a phenoxy resin in solvent solution. The alcohol is used in a molar excess of at least about 3% up to 30% to insure the absence of any significant proportion of unreacted diisocyanate. The phenoxy resin which is reacted with is a high molecular weight hydroxy functional polyether having a number average molecular weight above 10,000 and an hydroxy functionality in the range of from about 20 to about 300. The adduct is used in an amount to introduce about 1.5 to about 20 ethylenically unsaturated groups per molecule of the polyether, and the reaction is continued to substantially eliminate unreacted isocyanate functionality. These unsaturated products are useful in electron beam coating compositions, especially in combination with unsaturated liquids which lower the glass transition temperature. They can also be used in combination with acrylate-terminated polyurethanes to provide films having greater handleability prior to cure.

摘要翻译： 烯丙基不饱和一元醇如丙烯酸2-羟乙酯与有机二异氰酸酯的加成物的反应产物，其中两个异氰酸酯基中的一个比另一个异氰酸酯反应性更强，例如异佛尔酮二异氰酸酯，与苯氧基 树脂在溶剂溶液中。 醇的摩尔过量使用至少约3％至30％，以确保不存在任何显着比例的未反应的二异氰酸酯。 与之反应的苯氧基树脂是数均分子量大于10,000且羟基官能度在约20至约300范围内的高分子量羟基官能聚醚。加合物的用量为约1.5至 每分子聚醚约20个烯属不饱和基团，继续反应基本上消除未反应的异氰酸酯官能度。 这些不饱和产物可用于电子束涂料组合物，特别是与降低玻璃化转变温度的不饱和液体组合使用。 它们也可以与丙烯酸酯封端的聚氨酯组合使用，以提供在固化前具有更高可操作性的膜。

公开(公告)号：US4716209A

公开(公告)日：1987-12-29

申请号：US824547

申请日：1986-01-23

申请人： Steven R. Schmid ,  Robert E. Ansel ,  Kevin P. Murray

发明人： Steven R. Schmid ,  Robert E. Ansel ,  Kevin P. Murray

IPC分类号： C08F2/54 ,  C08F299/06 ,  C08G18/12 ,  C08G18/66 ,  C08G18/67 ,  C08F26/02 ,  C08F226/02

CPC分类号： C08G18/671 ,  C08F299/065 ,  C08G18/12 ,  C08G18/6607 ,  C08G18/6618

摘要： An essentially isocyanate-free polyurethane polyurea polyethylenic oligomer is disclosed which is unusually strong and elastic. This oligomer is the reaction product of: (1) organic diisocyanate; (2) a stoichiometric deficiency of difunctional materials reactive therewith and consisting essentially of: (A) diol component selected from polycarbonate diol and polyoxyalkylene glycol, this diol component having a molecular weight of from 200 to 2000; (B) dihydric bisphenol-based alkylene oxide adduct containing from 2-10 alkylene groups per molecule; and (C) a diprimary diamine component selected from alkylene diamine and polyoxyalkylene diamine, this diamine component having a molecular weight of from about 70 to 800. Components (A) and (B) are present in a weight ratio of from 1:4 to 9:1 and component (C) is present to supply from 30 to 60 equivalent percent of the total equivalents of component (2). The polyurethane polyurea so-constituted is capped with monohydric ethylenic compound, such as 2-hydroxyethyl acrylate, to provide a molecular weight in the range of about 5,000 to about 30,000.This polyethylenic oligomer is cured by radiation exposure, such as an electron beam, using from 5% to 25%, based on total polymer solids, of a polyethylenic cross-linking agent.

摘要翻译： 公开了一种基本上不含异氰酸酯的聚脲聚乙烯低聚物，其具有非常强的和有弹性的。 该低聚物是以下物质的反应产物：（1）有机二异氰酸酯; （2）与其反应的二官能材料的化学计量不足，基本上由以下组成：（A）选自聚碳酸酯二醇和聚氧化亚烷基二醇的二醇组分，该二醇组分的分子量为200-2000; （B）每分子含有2-10个亚烷基的二元双酚类环氧烷加成物; 和（C）选自亚烷基二胺和聚氧化烯二胺的二元二胺组分，该二胺组分的分子量为约70至800.组分（A）和（B）的重量比为1:4至 9：1，组分（C）的存在量为组分（2）的总当量的30至60当量。 如此构成的聚氨酯聚脲用一元乙烯化合物如丙烯酸2-羟乙酯封端，以提供约5,000至约30,000的分子量。 该聚烯烃低聚物通过辐射暴露（例如电子束）固化，使用基于聚合物固体总量的5％至25％的聚乙烯交联剂。

公开(公告)号：US4682851A

公开(公告)日：1987-07-28

申请号：US582705

申请日：1984-02-23

申请人： Robert E. Ansel

发明人： Robert E. Ansel

IPC分类号： C08F283/00 ,  C08G18/10 ,  C08G18/60 ,  C08G18/67 ,  C08G18/81 ,  C09D4/00 ,  G02B6/00

CPC分类号： C08G18/10 ,  C08F283/00 ,  C08G18/603 ,  C08G18/672 ,  C08G18/8175 ,  C09D4/00

摘要： A radiation-curable liquid coating composition which cures on radiation exposure to form a soft and tough coating and which is adapted for coating optical fiber is disclosed. This composition comprises a polyurethane, polyamide or polyurea oligomer having (1) a molecular weight in the range of about 2000 to about 8000; (2) amide, urea or urethane groups in an amount of one such group for every 300 to 900 units of weight; and (3) polyalkylene polyether, polyalkylene polysulfide or polyalkylene polyester groups in which the alkylene moiety contains 2-6 carbon atoms. The polyether, polysulfide or polyester constitutes about 40% to about 90% by weight of the oligomer, and each end of the oligomer is terminated with a monoethylenically unsaturated addition polymerizable group. From 20% to 50% of the weight of the composition is a radiation-curable monoethylenically unsaturated monomer having a T.sub.g below about 10.degree. C., and from 2% to 20% of the composition is a monoethylenically unsaturated monomer having a strong capacity for hydrogen bonding, such as vinyl pyrrolidone.

摘要翻译： 公开了一种可辐射固化的液体涂料组合物，其在辐射暴露下固化以形成柔软且坚韧的涂层，并且适用于涂覆光纤。 该组合物包含具有（1）分子量在约2000至约8000范围内的聚氨酯，聚酰胺或聚脲低聚物; （2）每300至900单位重量的酰胺，脲或氨基甲酸酯基团; 和（3）聚亚烷基聚醚，聚亚烷基多硫化物或其中亚烷基部分含有2-6个碳原子的聚亚烷基聚酯基团。 聚醚，多硫化物或聚酯构成低聚物的约40重量％至约90重量％，低聚物的每个末端用单烯属不饱和加成聚合基团封端。 组合物重量的20％至50％是Tg低于约10℃的可辐射固化的单烯属不饱和单体，组合物的2％至20％是单烯属不饱和单体，其具有强的 氢键，如乙烯基吡咯烷酮。

公开(公告)号：US4590250A

公开(公告)日：1986-05-20

申请号：US754409

申请日：1985-07-12

申请人： Robert E. Ansel

发明人： Robert E. Ansel

IPC分类号： C08F2/46 ,  C08G18/67 ,  C09D5/23 ,  G11B5/702 ,  C08F26/02 ,  C08F126/02 ,  C08F226/02

CPC分类号： G11B5/7026 ,  C08G18/672

摘要： Radiation curable coating compositions, and especially electron beam-curable coating compositions, are disclosed in which magnetizable particles are dispersed in a liquid vehicle comprising an hydroxy functional polyethylenically unsaturated polyurethane having the following structural formula: ##STR1## in which X is an ethylenically unsaturated monomer initially carrying a single hydroxy group, R' is the residue of an at least trifunctional polyol or amino alcohol linking compound, s is a number of 0.8 to 10, t is a number from 1 to 15, and Z is a diisocyanate terminated polycarbonate diol polyurethane oligomer having the following structure: ##STR2## in which R is alkylene having from 1-20 carbon atoms, Q is the residue of an organic diisocyanate; y is at least 1, and R and y are selected to provide a molecular weight for the polycarbonate diol reactant of from 300 to 3000.

摘要翻译： 公开了可辐射固化涂料组合物，特别是电子束可固化涂料组合物，其中可磁化颗粒分散在包含具有以下结构式的羟基官能多烯属不饱和聚氨酯的液体载体中：其中X是烯属不饱和单体 最初携带单个羟基，R'是至少三官能多元醇或氨基醇连接化合物的残基，s为0.8至10的数，t为1至15的数，Z为二异氰酸酯封端的聚碳酸酯二醇 具有以下结构的聚氨酯低聚物：其中R是具有1-20个碳原子的亚烷基，其中Q是有机二异氰酸酯的残基; y至少为1，选择R和y以提供300至3000的聚碳酸酯二醇反应物的分子量。