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1.发明授权Actinic radiation-curable stereolithographic resin composition having improved stability 有权光稳定的可辐射固化的立体光刻树脂组合物具有改进的稳定性公开(公告)号：US08338074B2
公开(公告)日：2012-12-25
申请号：US10562098
申请日：2004-06-24
申请人： Takashi Ito , Tsuneo Hagiwara , Hideki Kimura , Masashi Date , Jiro Yamamoto
发明人： Takashi Ito , Tsuneo Hagiwara , Hideki Kimura , Masashi Date , Jiro Yamamoto
CPC分类号： C08G59/687 , B33Y70/00 , C08F2/50 , C08F2/56 , G03F7/0045 , G03F7/027 , G03F7/038
摘要： It is intended to provide the following resin composition for stereolithography which is superior in storage stability and aging stability during operation, shows no increase in viscosity upon prolonged storage, has a high light-curing sensitivity and, therefore, makes it possible to produce, upon photo irradiation, an object by stereolithography, which is superior in dimensional accuracy, fabricating accuracy, water resistance, moisture resistance and mechanical properties at a high fabricating speed and a high productivity. A resin composition for stereolithography which is an actinic radiation-curable resin composition containing a cationic-polymerizable organic compound, a radical-polymerizable organic compound, a photo cationic polymerization initiator and a photo radical polymerization initiator, in which the photo cationic polymerization initiator contains a compound represented by the following formula (I) and having a purity of 80% or higher: wherein M represents an antimony atom or a phosphorus atom; and the broken line between S+ and MF6− represents an ionic bond.
摘要翻译： 旨在提供以下用于立体光刻的树脂组合物，其在操作中的储存稳定性和老化稳定性优异，在长时间保存时不显示粘度增加，具有高的光固化灵敏度，因此可以在 照相照射，通过立体光刻法，在高制造速度和高生产率下尺寸精度，制造精度，耐水性，耐湿性和机械性能都优异。 一种用于立体光刻的树脂组合物，其是含有阳离子可聚合有机化合物，自由基可聚合有机化合物，光阳离子聚合引发剂和光自由基聚合引发剂的光化辐射固化树脂组合物，其中光阳离子聚合引发剂包含 由下式（I）表示的并且纯度为80％以上的化合物：其中M表示锑原子或磷原子; S +和MF6-之间的虚线表示离子键。
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2.发明申请Actinic radiation-curable stereolithographic resin composition having improved stability 有权光稳定的可辐射固化的立体光刻树脂组合物具有改进的稳定性公开(公告)号：US20070060682A1
公开(公告)日：2007-03-15
申请号：US10562098
申请日：2004-06-24
申请人： Takashi Ito , Tsuneo Hagiwara , Hideki Kimura , Masashi Date , Jiro Yamamoto
发明人： Takashi Ito , Tsuneo Hagiwara , Hideki Kimura , Masashi Date , Jiro Yamamoto
IPC分类号： C08C1/14
CPC分类号： C08G59/687 , B33Y70/00 , C08F2/50 , C08F2/56 , G03F7/0045 , G03F7/027 , G03F7/038
摘要： It is intended to provide the following resin composition for stereolithography which is superior in storage stability and aging stability during operation, shows no increase in viscosity upon prolonged storage, has a high light-curing sensitivity and, therefore, makes it possible to produce, upon photo irradiation, an object by stereolithography, which is superior in dimensional accuracy, fabricating accuracy, water resistance, moisture resistance and mechanical properties at a high fabricating speed and a high productivity. A resin composition for stereolithography which is an actinic radiation-curable resin composition containing a cationic-polymerizable organic compound, a radical-polymerizable organic compound, a photo cationic polymerization inhibitor and a photo radical polymerization inhibitor, in which the photo cationic polymerization inhibitor contains a compound represented by the following formula (I) and having a purity of 80% or higher: wherein M represents an antimony atom or a phosphorus atom; and the broken line between S+ and MF6− represents an ionic bond.
摘要翻译： 旨在提供以下用于立体光刻的树脂组合物，其在操作中的储存稳定性和老化稳定性优异，在长时间保存时不显示粘度增加，具有高的光固化灵敏度，因此可以在 照相照射，通过立体光刻法，在高制造速度和高生产率下尺寸精度，制造精度，耐水性，耐湿性和机械性能都优异。 一种用于立体光刻的树脂组合物，其是含有阳离子可聚合有机化合物，可自由基聚合的有机化合物，光阳离子聚合抑制剂和光自由基聚合抑制剂的光化辐射固化树脂组合物，其中光阳离子聚合抑制剂含有 由下式（I）表示的并且纯度为80％以上的化合物：其中M表示锑原子或磷原子; 并且S SUP + +和/或MF 6之间的虚线表示离子键。
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公开(公告)号：US20060141276A1
公开(公告)日：2006-06-29
申请号：US10561673
申请日：2004-06-23
申请人： Takashi Ito , Tsuneo Hagiwara
发明人： Takashi Ito , Tsuneo Hagiwara
IPC分类号： B32B27/00
CPC分类号： B29C64/135 , B33Y70/00 , Y10T428/24942 , Y10T428/254 , Y10T428/26 , Y10T428/31855
摘要： It is intended to provide an optical three-dimensional object as will be described below which has a high impact resistance and is superior in dimensional accuracy, mechanical properties such as tensile strength, and other properties such as water resistance, moisture resistance and heat resistance, and a method of producing the same. An optical three-dimensional object includes multiple cured resin layers containing at least cured resin layer that has a sea-island microstructure in which fine island components of a polymer differing from a cured resin constituting the sea component and have a particle diameter of 20 to 2,000 nm are dispersed in the sea component made of the cured polymer; and a method of producing this optical three-dimensional object by stereolithographic molding method with the use of a photo curable resin composition containing a homogeneous mixture of a curable resin component for forming the sea component with a component (preferably a polyalkylene ether compound) for forming the polymeric island components.
摘要翻译： 旨在提供具有高耐冲击性并且尺寸精度优异，拉伸强度等机械性能，耐水性，耐湿性，耐热性等其他性能的光学三维物体， 及其制造方法。 光学三维物体包括多个固化树脂层，其至少包含具有海岛微结构的固化树脂层，其中聚合物的细小岛成分与构成海成分的固化树脂不同，粒径为20至2,000 nm分散在由固化的聚合物制成的海组分中; 以及通过使用含有用于形成海成分的固化性树脂成分的均匀混合物与成分（优选为聚亚烷基醚化合物）形成的光固化性树脂组合物的立体成像法来制造该光学三维物体的方法 聚合物岛组分。
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公开(公告)号：US07354643B2
公开(公告)日：2008-04-08
申请号：US10561673
申请日：2004-06-23
申请人： Takashi Ito , Tsuneo Hagiwara
发明人： Takashi Ito , Tsuneo Hagiwara
CPC分类号： B29C64/135 , B33Y70/00 , Y10T428/24942 , Y10T428/254 , Y10T428/26 , Y10T428/31855
摘要： It is intended to provide an optical three-dimensional object as will be described below which has a high impact resistance and is superior in dimensional accuracy, mechanical properties such as tensile strength, and other properties such as water resistance, moisture resistance and heat resistance, and a method of producing the same. An optical three-dimensional object includes multiple cured resin layers containing at least one cured resin layer that has a sea-island microstructure in which fine island components of a polymer differing from a cured resin constituting the sea component and have a particle diameter of 20 to 2,000 nm are dispersed in the sea component made of the cured polymer; and a method of producing this optical three-dimensional object by stereolithographic molding method with the use of a photo curable resin composition containing a homogeneous mixture of a curable resin component for forming the sea component with a component (preferably a polyalkylene ether compound) for forming the polymeric island components.
摘要翻译： 旨在提供具有高耐冲击性并且尺寸精度优异，拉伸强度等机械性能，耐水性，耐湿性，耐热性等其他性能的光学三维物体， 及其制造方法。 光学三维物体包括多个固化树脂层，其含有至少一个具有海岛微结构的固化树脂层，其中聚合物的细小岛成分与构成海成分的固化树脂不同，粒径为20〜 2,000nm分散在由固化的聚合物制成的海组分中; 以及通过使用含有用于形成海成分的固化性树脂成分的均匀混合物与成分（优选为聚亚烷基醚化合物）形成的光固化性树脂组合物的立体成像法制造该光学立体物的方法 聚合物岛组分。
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公开(公告)号：US08361376B2
公开(公告)日：2013-01-29
申请号：US11993355
申请日：2006-06-15
申请人： Takashi Ito , Tsuneo Hagiwara
发明人： Takashi Ito , Tsuneo Hagiwara
CPC分类号： G03F7/0037 , B29C64/106 , B33Y10/00 , B33Y70/00 , C08L63/00 , C08L67/07 , Y10T428/24355 , Y10T428/24777 , C08L2666/18
摘要： An optical three-dimensional shaped item excelling in the smoothness of molding end face. There is provided a three-dimensional shaped item composed of, superimposed one upon another, multiple cured resin layers having a given configurational pattern formed by irradiating with actinic energy rays a molding face consisting of an actinic energy ray curable resin composition, wherein at least part of an uneven region of molding end face of the three-dimensional shaped item, the degree of unevenness thereof is reduced to smoothness by segregation of a component contained in the actinic energy ray curable resin composition and/or a substance derived from the component. Also, there is provided an actinic energy ray curable resin composition for the three-dimensional shaped item.
摘要翻译： 成型端面平滑度优异的光学立体成型件。 提供一种三维成形物品，它们由多个固化树脂层组成，具有通过用光化能射线照射由光化能量射线固化树脂组合物构成的成型面而形成的给定结构图案，其中至少部分 在三维成形品的成型端面的不均匀区域中，通过使光活性能量射线固化型树脂组合物中所含的成分和/或来自该成分的物质的偏析分离，其不均匀度降低到平滑度。 此外，提供了一种用于三维成形物品的光化学能量射线固化树脂组合物。
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公开(公告)号：US08293810B2
公开(公告)日：2012-10-23
申请号：US11212711
申请日：2005-08-29
申请人： Takashi Ito , Tsuneo Hagiwara , Toshiyuki Ozai , Takeshi Miyao
发明人： Takashi Ito , Tsuneo Hagiwara , Toshiyuki Ozai , Takeshi Miyao
CPC分类号： C08F283/12 , B33Y70/00 , C08L83/08 , C08L83/00
摘要： A resin composition suited for rapid prototyping is provided comprising (I) an actinic energy radiation-curable silicone composition, (II) an actinic energy radiation-sensitive polymerization initiator, and (III) an actinic energy radiation absorber. The resin composition experiences little viscosity buildup and maintains fluidity during long-term storage at elevated temperature, and is effective in rapid prototyping or shaping by stereolithography using any actinic energy radiation.
摘要翻译： 提供了适用于快速成型的树脂组合物，其包括（I）光化能辐射可固化硅氧烷组合物，（II）光化能辐射敏感聚合引发剂，和（III）光化能辐射吸收剂。 树脂组合物在高温下长时间储存期间几乎不产生粘度增加并保持流动性，并且通过使用任何光化能量辐射的立体光刻技术在快速成型或成型中是有效的。
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公开(公告)号：US08293448B2
公开(公告)日：2012-10-23
申请号：US12304962
申请日：2007-06-15
申请人： Takashi Ito , Tsuneo Hagiwara , Kenji Hirotsu , Tadashi Murakami
发明人： Takashi Ito , Tsuneo Hagiwara , Kenji Hirotsu , Tadashi Murakami
摘要： Provided is a resin composition for stereolithography that absorbs little water and moisture over time in uncured state, maintains a low moisture absorption rate even under high humidity, and has high curing sensitivity, from which a stereolithography product excellent in the properties, such as dimensional accuracy, mechanical properties, and dimensional stability can be smoothly produced for reduced light irradiation time. The resin composition for stereolithography comprising an oxetane compound expressed by the general formula (I) below: wherein R1 denotes an alkyl group having 1 to 5 carbon atoms, and R2 denotes an alkylene group having 2 to 10 carbon atoms that may contain an ether bond, in the proportion of from 3 to 60 mass % based on the total mass of the resin composition for stereolithography.
摘要翻译： 提供一种用于立体光刻的树脂组合物，其在未固化状态下随时间吸收几乎没有水分和水分，即使在高湿度下也保持低吸湿率，并且具有高固化灵敏度，由此可以获得诸如尺寸精度的性能优异的立体光刻产品 ，可以平滑地产生机械性能和尺寸稳定性，以减少光照射时间。 用于立体光刻的树脂组合物，其包含由以下通式（I）表示的氧杂环丁烷化合物：其中R 1表示具有1至5个碳原子的烷基，R 2表示可含有醚键的具有2至10个碳原子的亚烷基 ，以用于立体光刻的树脂组合物的总质量为3〜60质量％的比例。
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公开(公告)号：US20100152314A1
公开(公告)日：2010-06-17
申请号：US12088522
申请日：2006-09-29
申请人： Takashi Ito , Tsuneo Hagiwara
发明人： Takashi Ito , Tsuneo Hagiwara
IPC分类号： C08F2/46
CPC分类号： C08F283/10 , B33Y70/00 , C08F290/144 , C08G59/24 , C08G65/18 , G03F7/0037 , G03F7/027 , G03F7/038
摘要： The invention provides a resin composition for stereolithography, which is low in absorption of water and moisture even when the composition is preserved for a long time, which is capable of maintaining high curing sensitivity for long, which is capable of fabricating a three-dimensional object in a shortened molding time, smoothly and in high productivity, the three-dimensional object being excellent in molding accuracy, dimensional accuracy, water resistance, moisture resistance, and mechanical characteristics.A resin composition for stereolithography (i) includes: an epoxy compound (A); an ethylenic unsaturated compound (B); a photo initiator for cationic polymerization (C); a photo initiator for radical polymerization (D); and an oxetane compound (E), (ii) an epoxy compound containing an alicyclic diglycidyl ether compound is included as the epoxy compound (A) in a proportion of 20 to 100 weight % with respect to a total weight of the epoxy compound (A), the alicyclic diglycidyl ether compound being represented by formula (I): in which R1 represents a hydrogenated bisphenol A residue, a hydrogenated bisphenol F residue, a hydrogenated bisphenol Z residue, a cyclohexanedimethanol residue, or a tricyclodecanedimethanol residue, and (iii) an oxetane compound containing: a monooxetane compound (E1) having one oxetane group in a molecule thereof; and a polyoxetane compound (E2) having two or more oxetane groups in a molecule thereof is included as the oxetane compound (E) in a weight ratio of the monooxetane compound (E1) to the polyoxetane compound (E2) of 95:5 to 5:95.
摘要翻译： 本发明提供一种用于立体光刻的树脂组合物，即使组合物长时间保存，水分和水分的吸收性也低，其能够长时间保持高的固化灵敏度，其能够制造三维物体 在缩短的成型时间内，平滑且高生产率，三维物体的成型精度，尺寸精度，耐水性，耐湿性和机械特性均优异。 用于立体光刻（I）的树脂组合物包括：环氧化合物（A）; 烯属不饱和化合物（B）; 阳离子聚合用光引发剂（C）; 用于自由基聚合的光引发剂（D）; 和氧杂环丁烷化合物（E），（ii）含有脂环族二缩水甘油醚化合物的环氧化合物作为环氧化合物（A）的比例相对于环氧化合物（A）的总重量为20〜100重量％ ），脂肪族二缩水甘油醚化合物由式（I）表示：其中R1表示氢化双酚A残基，氢化双酚F残基，氢化双酚Z残基，环己烷二甲醇残基或三环癸烷二甲醇残基，（iii） 一种氧杂环丁烷化合物，其分子中含有一个氧杂环丁烷基的单氧杂环丁烷化合物（E1） 并且分子中具有2个以上的氧杂环丁烷基的聚氧杂环丁烷化合物（E2）作为氧杂环丁烷化合物（E），以单氧杂环丁烷化合物（E1）与聚氧杂环丁烷化合物（E2）的重量比为95:5〜5 ：95。
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公开(公告)号：US20100104804A1
公开(公告)日：2010-04-29
申请号：US11993355
申请日：2006-06-15
申请人： Takashi Ito , Tsuneo Hagiwara
发明人： Takashi Ito , Tsuneo Hagiwara
CPC分类号： G03F7/0037 , B29C64/106 , B33Y10/00 , B33Y70/00 , C08L63/00 , C08L67/07 , Y10T428/24355 , Y10T428/24777 , C08L2666/18
摘要： An optical three-dimensional shaped item excelling in the smoothness of molding end face. There is provided a three-dimensional shaped item composed of, superimposed one upon another, multiple cured resin layers having a given configurational pattern formed by irradiating with actinic energy rays a molding face consisting of an actinic energy ray curable resin composition, wherein at at least part of an uneven region of molding end face of the three-dimensional shaped item, the degree of unevenness thereof is reduced to smoothness by segregation of a component contained in the actinic energy ray curable resin composition and/or a substance derived from the component. Also, there is provided an actinic energy ray curable resin composition for the three-dimensional shaped item.
摘要翻译： 成型端面平滑度优异的光学立体成型件。 提供一种三维形状的物品，其叠加在一起，具有通过用光化能量射线照射由光化学能量射线固化树脂组合物组成的成型面而形成的给定构型图案的多个固化树脂层，其中至少 三维成形品的成型端面的不均匀区域的一部分，通过使光活性能量射线固化性树脂组合物中所含的成分和/或来自该成分的物质偏析而使其不均匀度降低到平滑度。 此外，提供了一种用于三维成形物品的光化学能量射线固化树脂组合物。
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公开(公告)号：US20090209674A1
公开(公告)日：2009-08-20
申请号：US12304962
申请日：2007-06-15
申请人： Takashi Ito , Tsuneo Hagiwara , Kenji Hirotsu , Tadashi Murakami
发明人： Takashi Ito , Tsuneo Hagiwara , Kenji Hirotsu , Tadashi Murakami
IPC分类号： C08F2/46
摘要： Provided is a resin composition for stereolithography that absorbs little water and moisture over time in uncured state, maintains a low moisture absorption rate even under high humidity, and has high curing sensitivity, from which a stereolithography product excellent in the properties, such as dimensional accuracy, mechanical properties, and dimensional stability can be smoothly produced for reduced light irradiation time.The resin composition for stereolithography comprising an oxetane compound expressed by the general formula (I) below; (wherein R1 denotes an alkyl group having 1 to 5 carbon atoms, and R2 denotes an alkylene group having 2 to 10 carbon atoms that may contain an ether bond) in the proportion of from 3 to 60 mass % based on the total mass of the resin composition for stereolithography.
摘要翻译： 提供一种用于立体光刻的树脂组合物，其在未固化状态下随时间吸收几乎没有水分和水分，即使在高湿度下也保持低吸湿率，并且具有高固化灵敏度，由此可以获得诸如尺寸精度的性能优异的立体光刻产品 ，可以平滑地产生机械性能和尺寸稳定性，以减少光照射时间。 用于立体光刻的树脂组合物，其包含由下述通式（I）表示的氧杂环丁烷化合物; （其中R1表示具有1至5个碳原子的烷基，R2表示可含有醚键的具有2至10个碳原子的亚烷基），基于总重量的3至60质量％ 用于立体光刻的树脂组合物。
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