WO2003037530A1 - Use of a metal halide lamp in curing photocurable composition - Google Patents
Use of a metal halide lamp in curing photocurable composition Download PDFInfo
- Publication number
- WO2003037530A1 WO2003037530A1 PCT/CN2002/000778 CN0200778W WO03037530A1 WO 2003037530 A1 WO2003037530 A1 WO 2003037530A1 CN 0200778 W CN0200778 W CN 0200778W WO 03037530 A1 WO03037530 A1 WO 03037530A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lamp
- metal halide
- indium
- curing
- photocurable composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J61/00—Gas-discharge or vapour-discharge lamps
- H01J61/82—Lamps with high-pressure unconstricted discharge having a cold pressure > 400 Torr
- H01J61/827—Metal halide arc lamps
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J61/00—Gas-discharge or vapour-discharge lamps
- H01J61/02—Details
- H01J61/12—Selection of substances for gas fillings; Specified operating pressure or temperature
- H01J61/125—Selection of substances for gas fillings; Specified operating pressure or temperature having an halogenide as principal component
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/065—After-treatment
- B05D3/067—Curing or cross-linking the coating
Definitions
- the present invention relates to the use of a metal halide lamp as a visible light source for the curing of photocurable compositions. Background technique
- UV curing technology has been used in many fields, such as printing cover for wood, paper, metal and plastic, for decoration and protection; for optical fiber, optical disk, electronic circuit board manufacturing in the field of electronic information. Wait.
- ultraviolet light has two disadvantages: First, short-wave radiation is harmful to the human body and needs to be well shielded when used. In particular, ultraviolet rays in the 200-315 nm band act quickly, and inadvertent contact can cause redness, inflammation, and burns to the cornea. Sometimes blindness sometimes occurs. Second, the ultraviolet rays cause ozone generated by the air to cause headache and fatigue, and are irritating to the eyes and lungs, and are harmful to operators who have long been in this environment.
- the visible light source does not contain short-wave ultraviolet light, does not produce ozone, has no burn effect on the skin, and is safe to use and safe to operate; the movable light source is applied on a larger area coating, and can be applied in a place where people are active; the visible wavelength is long, wear Strong penetration, more favorable for the underlying curing.
- US 6,106,999 discloses a visible light curable resin composition in which an organic boron compound is used as a photoinitiator, and Ar or YAG laser vibrating light is used as a light source;
- CN1215421A discloses a visible light polymerizable combination.
- indoor fluorescent lamps, spotlights, and halogen work lamps are disclosed as light sources.
- these visible light sources are not satisfactory when applied to a photopolymerizable composition.
- the substance that participates in luminescence is a metal. It can be atomic luminescence or molecular luminescence. But what is charged into the lamp is not just metal, but metal halide.
- the luminescent material in a metal halide lamp is a more complex chemical system than other lamp types.
- the metal halide will continuously generate decomposition and complicated cycle.
- the process of this cycle is the principle of light emission: the metal halide is evaporated in a large amount at the working temperature of the pipe wall (about 1000K), and the arc center is concentrated due to the concentration gradient. diffusion.
- the metal halide decomposes into a metal atom and a halogen atom, and the metal atom participates in the discharge, generates thermal excitation thermal ionization, and radiates outward. Spectra of different energy distributions.
- the desired metal halides and combinations thereof are typically selected based on the spectral characteristics required for the particular application.
- 535nm produces green light to make a cesium iodide-mercury lamp.
- the molecular light-emitting lamp usually has a band spectrum, and the continuous component is sometimes strong.
- the lamp that emits light by the metal halide molecule is tin chloride or aluminum halide.
- the metal vapor discharge lamp is broadened under high pressure or ultra high pressure, the continuous background is strengthened, the color rendering is improved, and the brightness is increased.
- the metal halide lamp made by using this characteristic has an ultrahigh pressure indium lamp, a gallium lamp, etc. . Disclosure of invention
- An object of the present invention is to provide a visible light source-metal halide lamp for use in a photocurable composition, particularly a xenon lamp or an indium lamp for use in curing a photocurable composition.
- the main spectrum of the xenon lamp and the indium lamp is in the range of 350_650 nm, and the spectral response curve of the 400 W xenon lamp and the indium lamp is shown in Fig. 1. '
- the luminescent material in the xenon lamp is a cerium-containing metal halide.
- the ruthenium-containing metal halide is selected from the group consisting of ruthenium iodide and/or ruthenium bromide, a complex of a ruthenium-containing metal halide.
- the complex of the ruthenium containing metal halide in the xenon lamp is Nal ⁇ Dyl 3 .
- the luminescent substance in the indium lamp is a metal halide containing indium.
- the metal halide of indium is selected from one of a complex of indium iodide and/or indium bromide and an indium containing metal halide. kind.
- the spectrum of the xenon lamp and the indium lamp is in the range of 350-650 nm.
- metal halide lamps are doped with other metals or halides to improve light efficiency, balance color temperature and extend life.
- xenon lamp and indium lamp The spectrum of xenon lamp and indium lamp is similar to daylight. Its ultraviolet light content is very small, which is a very safe light source. The following is the energy distribution of 400W xenon lamp and indium lamp.
- the above-mentioned xenon lamp and indium lamp can be used as a light source to initiate curing of the photocurable composition.
- the photocurable composition will generally be comprised of a prepolymer, a monomer, a photoinitiator, and a suitable adjuvant.
- prepolymer examples include urethane (meth) acrylate, poly (meth) acrylate, epoxy (meth) acrylate, and polyether (meth) acrylate.
- the monomers include styrenes, (meth) acrylates, vinyl ethers, and the like.
- photoinitiators include benzoin and its alkyl ethers, such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenones, such as phenylethyl Ketone, 2,2-dimethoxy-2-phenylacetophenone (BDK), 2,2-diethoxy-2-phenylacetophenone, 1, 1-dichloroacetophenone, 1 -hydroxyacetophenone, 1-hydroxychlorohexylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one
- acetophenones such as phenylethyl Ketone, 2,2-dimethoxy-2-phenylacetophenone (BDK), 2,2-diethoxy-2-phenylacetophenone, 1, 1-dichloroacetophenone, 1 -hydroxyacetophenone, 1-hydroxychlorohexylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one
- DETX 2 (or 4)-isopropylthioxanthone (ITX), 2-chlorothioxanthone (CTX) and 2,4-diisopropylthioxanthone
- ketals such as acetophenone II Methyl ketal, and benzoyl dimethyl ketal
- benzophenones such as benzophenone and 4-benzoyl-4 '-methyldiphenyl sulfide (DMS);
- Acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TP0), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (819) , bis(2,6-dimethylbenzoyl)-2, 4, 4- Trimethylpentylphosphine oxide (BAP0), 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide (TPO-L).
- Additives mainly help initiators, pigments, fillers, polymerization inhibitors, filming aids, thickeners, leveling agents and defoamers. The best way to implement the invention
- the illuminant in the xenon lamp provided by the present invention is a cerium-containing metal halide
- the cerium-containing metal halide is selected from the group consisting of cerium iodide and/or cerium bromide and cerium-containing metal.
- One of the halide complexes is one of the halide complexes.
- metals or halides are doped in the metal halide containing cerium to improve light efficiency, balance color temperature and extend life.
- the rhodium-containing metal halide complex in the xenon lamp is Nal ⁇ Dyl 3 .
- the luminescent material in the indium lamp provided by the present invention is an indium-containing metal halide
- the indium-containing metal halide is selected from the group consisting of indium iodide and/or indium bromide and indium.
- the metal halide complexes are one of the metal halide complexes.
- the embodiment uses a 400 W xenon lamp as a light source, and the test piece is separated from the filament by 20 cm, but the present application is not limited thereto.
- a 500 W ultraviolet lamp, a 40 WX 5 medium wave lamp, and a 250 WX 2 infrared lamp were used as the light source, and the distance between the test piece and the filament was 20 cm.
- the abbreviations in the examples have the following meanings:
- TP0-L 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide
- TP0 2,4,6-trimethylbenzoyldiphenylphosphine oxide
- ITX 2 (or 4) - Isopropylthioxanthone (ITX)
- BDK 2,2-dimethoxy-2-phenylacetophenone
- TMPTA Trimethylolpropane triacrylate
- Example 1 The formulation sample of Example 1 was slightly viscous under a 40W X 5 wave lamp for 6 minutes.
- Example 1 The formulation sample of Example 1 was not fixed under the 250W X 2 infrared lamp for 6 minutes.
- TMPTA Trimethylolpropane triacrylate
- Example 2 The formulation sample of Example 2 was cured under a wave lamp at 40 WX 5 for 6 min. Comparative Example 6
- Example 3 The formulation sample of Example 2 was not solidified under a 250 W X 2 infrared lamp for 6 minutes.
- Example 3
- TMPTA Trimethylolpropane triacrylate
- HDDA Hexanediol diacrylate
- TMPTA Trimethylolpropane triacrylate
- TMPTA Trimethylolpropane triacrylate
- TMPTA Trimethylolpropane triacrylate
- the amount of the raw material added in the above examples is “parts" in parts by weight.
- 4265 is a mixture of 50% by weight of 1173 and 50% TP0.
- Xenon lamp and indium lamp can be used not only as an alternative to UV lamp in existing curing equipment, but also widely used in the curing of photocurable coatings in home painting and large-area indoor and outdoor coating projects.
- the invention will bring great convenience to the popularization and application of photocurable coatings and inks.
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
一种金属卤化物灯在光固化组合物固化中的应用 技术领域 Application of metal halide lamp in curing of photocurable composition
本发明涉及一种作为可见光光源的金属卤化物灯在可光固化组合物固 化中的应用。 背景技术 The present invention relates to the use of a metal halide lamp as a visible light source for the curing of photocurable compositions. Background technique
以前的紫外光固化技术已在众多领域得到应用， 如印刷罩光用在木器、 纸张、 金属和塑料上， 起到装饰和保护作用； 在电子信息领域中用于光纤、 光盘、 电子线路板制造等。 但紫外线有两方面不利之处： 一是短波射线对人 体有伤害， 使用时需要很好屏蔽。 尤其是 200-315nm波段紫外线作用快， 不 慎接触会使皮肤发红、 发炎、 使眼角膜灼伤。 有时会发生短暂失明。 二是紫 外线使空气产生的臭氧能引起头痛、 疲劳， 对眼睛和肺有刺激性， 对长期在 此环境的操作者有一定危害。 这些问题在一定程度上限制了紫外光固化技术 在更广泛领域的应用和更大程度的发展。 而可见光光源中不含短波紫外线， 不产生臭氧， 对皮肤无灼伤作用， 使用安全操作方便； 可移动光源在更大面 积涂装上应用， 更可以在有人活动的场所应用； 可见光波长长， 穿透力强， 对底层固化更有利。 Previous UV curing technology has been used in many fields, such as printing cover for wood, paper, metal and plastic, for decoration and protection; for optical fiber, optical disk, electronic circuit board manufacturing in the field of electronic information. Wait. However, ultraviolet light has two disadvantages: First, short-wave radiation is harmful to the human body and needs to be well shielded when used. In particular, ultraviolet rays in the 200-315 nm band act quickly, and inadvertent contact can cause redness, inflammation, and burns to the cornea. Sometimes blindness sometimes occurs. Second, the ultraviolet rays cause ozone generated by the air to cause headache and fatigue, and are irritating to the eyes and lungs, and are harmful to operators who have long been in this environment. These problems have limited the application of UV curing technology in a wider range of areas and to a greater extent. The visible light source does not contain short-wave ultraviolet light, does not produce ozone, has no burn effect on the skin, and is safe to use and safe to operate; the movable light source is applied on a larger area coating, and can be applied in a place where people are active; the visible wavelength is long, wear Strong penetration, more favorable for the underlying curing.
在现有技术中， 例如， US6106999公开了一种可见光固化树脂组合物， 其 中采用有机硼化合物作为光引发剂， 釆用 Ar或 YAG激光振动光作为光源； CN1215421A公开了一种可见光可聚合的组合物， 其中公开了采用例如室内荧 光灯、 聚光灯、 卤素工作灯作为光源。 但这些可见光源在应用于光可聚合组 合物时效果并不能令人满意。 In the prior art, for example, US 6,106,999 discloses a visible light curable resin composition in which an organic boron compound is used as a photoinitiator, and Ar or YAG laser vibrating light is used as a light source; CN1215421A discloses a visible light polymerizable combination. For example, indoor fluorescent lamps, spotlights, and halogen work lamps are disclosed as light sources. However, these visible light sources are not satisfactory when applied to a photopolymerizable composition.
在金属卤化物灯内， 参与发光的物质是金属。 它可以是原子发光， 也可 以是分子发光。 但充入灯内的并不是单是金属， 而是金属卤化物。 In a metal halide lamp, the substance that participates in luminescence is a metal. It can be atomic luminescence or molecular luminescence. But what is charged into the lamp is not just metal, but metal halide.
金属卤化物灯内发光物质是一个较其它灯种更复杂的化学体系。 在灯工 作时金属卤化物会不断地产生分解和复杂的循环， 这个循环的过程即灯的发 光原理： 金属卤化物在管壁工作温度 （1000K左右） 下大量蒸发， 因浓度梯 度而向电弧中心扩散。 在电弧中心高温区 （约 4000— 6000K) 金属卤化物分 解为金属原子和卤原子， 金属原子参与放电，产生热激发热电离， 并向外辐射 不同能量分布的光谱。 由于电弧中心金属原子和卤素原子的浓度较高， 它们 又会向管壁扩散， 在接近管壁的低温区域又重新复合形成金属卤化物分子。 正是依靠这种往复循环， 不断向电弧提供足够浓度的金属原子参与发光， 同 时又避免了金属在管壁的沉积。 The luminescent material in a metal halide lamp is a more complex chemical system than other lamp types. When the lamp is in operation, the metal halide will continuously generate decomposition and complicated cycle. The process of this cycle is the principle of light emission: the metal halide is evaporated in a large amount at the working temperature of the pipe wall (about 1000K), and the arc center is concentrated due to the concentration gradient. diffusion. In the high temperature region of the arc center (about 4000-6000K), the metal halide decomposes into a metal atom and a halogen atom, and the metal atom participates in the discharge, generates thermal excitation thermal ionization, and radiates outward. Spectra of different energy distributions. Due to the higher concentration of metal atoms and halogen atoms in the arc center, they diffuse toward the tube wall and recombine to form metal halide molecules near the low temperature region of the tube wall. It is this reciprocating cycle that continuously supplies a sufficient concentration of metal atoms to the arc to participate in the luminescence, while avoiding the deposition of metal on the tube wall.
金属卤化物灯中， 一般根据不同用途所要求的光谱特性， 选择所需的金 属卤化物及它们的组合。 In metal halide lamps, the desired metal halides and combinations thereof are typically selected based on the spectral characteristics required for the particular application.
按照金属卤化物灯的光谱特性大致可分为五类。 According to the spectral characteristics of metal halide lamps, they can be roughly classified into five categories.
( 1 )利用金属具有很强的共振辐射做成色度很纯的灯； 例如， 利用铊在 (1) using a metal with strong resonant radiation to make a lamp of very pure color; for example, using
535nm产生绿光做成碘化铊一汞灯。利用铟在 410. 2nm的蓝光和钠在 589. 0nm、 589. 6nm 的黄光， 分别做成铟灯、 钠灯等， 这类灯主要作为装饰或光谱分析 用。 535nm produces green light to make a cesium iodide-mercury lamp. Using indium in 410. 2nm of blue light and sodium in 589. 0nm, 58. 6nm yellow light, respectively, made into indium lamps, sodium lamps, etc., these lamps are mainly used for decoration or spectral analysis.
( 2 )选择几种可见光区发出强光谱线的金属碘化物按一定比例组合， 做 成白光或其他色彩的灯， 例如钠一铊一铟灯。 (2) Selecting several kinds of metal iodides that emit strong spectral lines in the visible region to be combined in a certain proportion to make white or other color lamps, such as sodium-indium-indium lamps.
( 3 )利用某些金属（如稀土金属）在可见光区能发射大量密集的线光谱， 得到类似日光的白光， 其显色性和光效往往都很高， 例如碘化镝一碘化铊灯、 碘化钪一碘化钠灯。 (3) The use of certain metals (such as rare earth metals) can emit a large number of dense line spectra in the visible light region, and obtain white light similar to sunlight, which is often high in color rendering and light efficiency, such as xenon iodide xenon iodide lamp, Sodium iodide iodide lamp.
(4)分子发光灯通常为带状光谱， 连续成分有时很强， 利用金属卤化物 分子发光的灯有氯化锡、 卤化铝等。 (4) The molecular light-emitting lamp usually has a band spectrum, and the continuous component is sometimes strong. The lamp that emits light by the metal halide molecule is tin chloride or aluminum halide.
( 5 )金属蒸气放电灯在高压或超高压下谱线展宽， 连续背景加强， 显色 性改善， 亮度增大， 利用这一特性做成的金属卤化物灯有超高压铟灯、 镓灯 等。 发明的公开 (5) The metal vapor discharge lamp is broadened under high pressure or ultra high pressure, the continuous background is strengthened, the color rendering is improved, and the brightness is increased. The metal halide lamp made by using this characteristic has an ultrahigh pressure indium lamp, a gallium lamp, etc. . Disclosure of invention
本发明的目的是为了提供一种用于光固化组合物的可见光光源一金属 卤化物灯， 特别是镝灯、 铟灯在光固化组合物固化中的应用。 SUMMARY OF THE INVENTION An object of the present invention is to provide a visible light source-metal halide lamp for use in a photocurable composition, particularly a xenon lamp or an indium lamp for use in curing a photocurable composition.
该镝灯、铟灯的主要的光谱在 350_650nm范围内，400W镝灯、铟灯光谱响 应曲线见图 1。 ' The main spectrum of the xenon lamp and the indium lamp is in the range of 350_650 nm, and the spectral response curve of the 400 W xenon lamp and the indium lamp is shown in Fig. 1. '
所述的镝灯中的发光物质为含镝的金属卤化物。 所述的含镝的金属卤化 物选自碘化镝和 /或溴化镝、 含镝的金属卤化物的络合物中的一种。 The luminescent material in the xenon lamp is a cerium-containing metal halide. The ruthenium-containing metal halide is selected from the group consisting of ruthenium iodide and/or ruthenium bromide, a complex of a ruthenium-containing metal halide.
所述的镝灯中的含镝的金属卤化物的络合物是 Nal · Dyl3。 所述的铟灯中的发光物质为含铟的金属卤化物 a 所述的铟的金属卤化物 选自碘化铟和 /或溴化铟、 含铟的金属卤化物的络合物中的一种。 The complex of the ruthenium containing metal halide in the xenon lamp is Nal · Dyl 3 . The luminescent substance in the indium lamp is a metal halide containing indium. The metal halide of indium is selected from one of a complex of indium iodide and/or indium bromide and an indium containing metal halide. Kind.
其中镝灯、 铟灯的光谱在 350-650nm范围内。 The spectrum of the xenon lamp and the indium lamp is in the range of 350-650 nm.
同时在金属卤化物灯中还掺杂其它金属或卤化物用来提高光效、 平衡色 温和延长寿命。 At the same time, metal halide lamps are doped with other metals or halides to improve light efficiency, balance color temperature and extend life.
镝灯、 铟灯的光谱类似日光， 它的紫外光含量很小， 是一种很安全的光 源； 下面是 400W镝灯、 铟灯的能量分配。 The spectrum of xenon lamp and indium lamp is similar to daylight. Its ultraviolet light content is very small, which is a very safe light source. The following is the energy distribution of 400W xenon lamp and indium lamp.
上述镝灯、 铟灯作为光源可引发光固化组合物的固化。 The above-mentioned xenon lamp and indium lamp can be used as a light source to initiate curing of the photocurable composition.
例如， 光固化组合物一般可由预聚物、 单体、 光引发剂和适当的助剂组 成。 For example, the photocurable composition will generally be comprised of a prepolymer, a monomer, a photoinitiator, and a suitable adjuvant.
预聚物的例子包括聚氨酯（甲基）丙烯酸酯、 聚酯（甲基）丙烯酸酯、 环氧 （甲基） 丙烯酸酯和聚醚 （甲基） 丙烯酸酯。 Examples of the prepolymer include urethane (meth) acrylate, poly (meth) acrylate, epoxy (meth) acrylate, and polyether (meth) acrylate.
单体包括苯乙烯类、 （甲基） 丙烯酸酯、 乙烯基醚等。 The monomers include styrenes, (meth) acrylates, vinyl ethers, and the like.
光引发剂的例子包括苯偶姻及其烷基醚，例如苯偶姻、苯偶姻甲基醚、 苯偶姻乙基醚和苯偶姻异丙基醚； 苯乙酮类， 例如苯乙酮、 2， 2-二甲氧基 -2 -苯基苯乙酮 （BDK)、 2， 2 -二乙氧基 -2-苯基苯乙酮、 1， 1-二氯苯乙酮、 1-羟基苯乙酮、 1-羟基氯己基苯乙酮、 2-羟基 -2-甲基- 1-苯基丙 -1-酮 Examples of photoinitiators include benzoin and its alkyl ethers, such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenones, such as phenylethyl Ketone, 2,2-dimethoxy-2-phenylacetophenone (BDK), 2,2-diethoxy-2-phenylacetophenone, 1, 1-dichloroacetophenone, 1 -hydroxyacetophenone, 1-hydroxychlorohexylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one
( 1173 )、 1- (4-异丙基苯基) -2-羟基- 2-甲基丙 -1 -酮 ( 1116)、 1- [4- (2- 羟基乙氧基） 苯基] -2-羟基- 2-甲基丙 -1-酮 （2959 )、 2-甲基- 1- [4- (甲基 巯基） 苯基] -2-吗啉基 -丙烷 -1-酮 （907 ) 和 2-苄基- 2-二甲基氨基 -1- (4- 吗啉基苯基） -丁 -1-酮 （369); 蒽醌， 例如 2-叔丁基蒽醌、 1-氯蒽醌和 2 - 戊基蒽醌； 噻吨酮， 例如 2， 4-二甲基噻吨酮 （DMTX)、 2， 4-二乙基噻吨酮(1173), 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one (1116), 1-[4-(2-hydroxyethoxy)phenyl]- 2-hydroxy-2-methylpropan-1-one (2959), 2-methyl-1- [4-(methylindenyl)phenyl]-2-morpholinyl-propan-1-one (907) And 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one (369); hydrazine, for example 2-tert-butylhydrazine, 1-chloroindole醌 and 2 - pentyl hydrazine; thioxanthone, such as 2, 4-dimethylthioxanthone (DMTX), 2, 4-diethylthioxanthone
( DETX)、 2 (或 4) -异丙基噻吨酮 （ITX)、 2-氯噻吨酮 ( CTX) 和 2， 4-二 异丙基噻吨酮； 縮酮， 例如苯乙酮二甲基縮酮， 和偶苯酰二甲基縮酮； 二 苯酮类，例如二苯酮和 4-苯甲酰基 -4 ' -甲基二苯基硫醚（DMS); 和 Ρ占吨酮； 酰基膦氧化合物如 2, 4， 6-三甲基苯甲酰基二苯基氧化膦（TP0)、双（2， 4， 6- 三甲基苯甲酰基） -苯基氧化膦 （819 )、 二（2， 6 -二甲基苯甲酰基） -2， 4， 4- 三甲基戊基氧化膦 （BAP0 )、 2， 4， 6-三甲基苯甲酰基苯基乙氧基氧化膦 ( TPO- L)。 (DETX), 2 (or 4)-isopropylthioxanthone (ITX), 2-chlorothioxanthone (CTX) and 2,4-diisopropylthioxanthone; ketals, such as acetophenone II Methyl ketal, and benzoyl dimethyl ketal; benzophenones such as benzophenone and 4-benzoyl-4 '-methyldiphenyl sulfide (DMS); Acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TP0), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (819) , bis(2,6-dimethylbenzoyl)-2, 4, 4- Trimethylpentylphosphine oxide (BAP0), 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide (TPO-L).
助剂主要有助引发剂、 颜料、 填料、 阻聚剂、 成膜助剂、 增稠剂、 流 平剂和消泡剂等。 实现本发明的最佳方式 Additives mainly help initiators, pigments, fillers, polymerization inhibitors, filming aids, thickeners, leveling agents and defoamers. The best way to implement the invention
实施例 Example
在优选的实施方案中， 本发明提供的镝灯中的发光物质为含镝的金属卤 化物， 所述的含镝的金属卤化物选自碘化镝和 /或溴化镝、含镝的金属卤化物 的络合物中的一种。 In a preferred embodiment, the illuminant in the xenon lamp provided by the present invention is a cerium-containing metal halide, and the cerium-containing metal halide is selected from the group consisting of cerium iodide and/or cerium bromide and cerium-containing metal. One of the halide complexes.
同时在含镝的金属卤化物中还掺杂其它金属或卤化物用来提高光效、 平 衡色温和延长寿命。 At the same time, other metals or halides are doped in the metal halide containing cerium to improve light efficiency, balance color temperature and extend life.
在更优选的实施方案中， 所述的镝灯中的含镝的金属卤化物的络合物为 Nal · Dyl3。 In a more preferred embodiment, the rhodium-containing metal halide complex in the xenon lamp is Nal · Dyl 3 .
在另一优选的实施方案中， 本发明提供的铟灯中的发光物质为含铟的金 属卤化物， 所述的含铟的金属卤化物选自碘化铟和 /或溴化铟、含铟的金属卤 化物的络合物中的一种。 In another preferred embodiment, the luminescent material in the indium lamp provided by the present invention is an indium-containing metal halide, and the indium-containing metal halide is selected from the group consisting of indium iodide and/or indium bromide and indium. One of the metal halide complexes.
同时在含铟的金属卤化物中还惨杂其它金属或卤化物用来提高光效、 平 衡色温和延长寿命。 At the same time, other metals or halides are also used in the indium-containing metal halides to improve light efficiency, balance color temperature and extend life.
下述实施例和对照例可以更进一步说明本发明中的镝灯、 铟灯特点， 但并不受这些例子的限制。 The following examples and comparative examples can further illustrate the characteristics of the xenon lamp and the indium lamp in the present invention, but are not limited by these examples.
本发明的实施例中所涉及到的测试方法见下表： The test methods involved in the embodiments of the present invention are as follows:
实施例使用 400W镝灯作为光源， 试片与灯丝距离 20cm ， 但本申请 并不局限于此。 The embodiment uses a 400 W xenon lamp as a light source, and the test piece is separated from the filament by 20 cm, but the present application is not limited thereto.
对照例使用 500W紫外灯、 40WX 5中波灯、 250WX 2红外灯作为光源， 试片与灯丝距离 20cm。 实施例中的缩写具有下列含意： In the comparative example, a 500 W ultraviolet lamp, a 40 WX 5 medium wave lamp, and a 250 WX 2 infrared lamp were used as the light source, and the distance between the test piece and the filament was 20 cm. The abbreviations in the examples have the following meanings:
TP0-L: 2 , 4， 6-三甲基苯甲酰基苯基乙氧基氧化膦（TP0-L) TP0: 2 , 4， 6-三甲基苯甲酰基二苯基氧化膦（TP0) TP0-L: 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide (TP0-L) TP0: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TP0)
1173： 2-羟基- 2-甲基- 1-苯基丙 -1-酮 (1173) 1173: 2-Hydroxy-2-methyl-1-phenylpropan-1-one (1173)
ITX: 2 (或 4) -异丙基噻吨酮（ITX) ITX: 2 (or 4) - Isopropylthioxanthone (ITX)
907： 2 -甲基 -1- [4- (甲基巯基）苯基] -2 -吗啉基-丙烷 -1-酮 (907) 907: 2 -Methyl-1-[4-(methylindenyl)phenyl]-2 morpholinyl-propan-1-one (907)
184： 1 -羟基环己基苯基酮（184) 184: 1 -Hydroxycyclohexyl phenyl ketone (184)
BDK: 2， 2 -二甲氧基- 2-苯基苯乙酮（BDK) BDK: 2,2-dimethoxy-2-phenylacetophenone (BDK)
CN972: 丙烯酸氨基酯， SART0MER的产品 CN972: Amino acrylate, products of SART0MER
CN120: 环氧丙烯酸酯， SART0MER的产品 CN120: Epoxy acrylate, SART0MER products
CN292: 聚酯丙烯酸酯， SART0MER的产品 CN292: Polyester acrylate, products of SART0MER
实施例 1 Example 1
双酚 A环氧丙烯酸酯 60份 Bisphenol A epoxy acrylate 60 parts
三羟甲基丙垸三丙烯酸酯 （TMPTA) 25份 Trimethylolpropane triacrylate (TMPTA) 25 parts
己二醇二丙烯酸酯 （HDDA) 12. 5份 Hexanediol diacrylate (HDDA) 12. 5 parts
TP0-L 2. 5份 TP0-L 2. 5 parts
三乙醇胺 0. 85份 Triethanolamine 0. 85 parts
固化时间 20s Curing time 20s
对照例 1 Comparative example 1
实施例 1的配方样品在 UV灯固化时间 20s Formulation sample of Example 1 at UV lamp curing time 20s
对照例 2 Comparative example 2
实施例 1的配方样品在 40W X 5中波灯下 6min表面微粘 The formulation sample of Example 1 was slightly viscous under a 40W X 5 wave lamp for 6 minutes.
对照例 3 Comparative Example 3
实施例 1的配方样品在 250W X 2红外灯下 6min不固 The formulation sample of Example 1 was not fixed under the 250W X 2 infrared lamp for 6 minutes.
实施例 2 Example 2
双酚 A环氧丙烯酸酯 60份 Bisphenol A epoxy acrylate 60 parts
三羟甲基丙烷三丙烯酸酯 （TMPTA) 25份 Trimethylolpropane triacrylate (TMPTA) 25 parts
己二醇二丙烯酸酯 （HDDA) 12. 5份 Hexanediol diacrylate (HDDA) 12. 5 parts
TP0 0. 63份 TP0 0. 63 copies
1173 1. 90份 三乙醇胺 0. 85份 固化时间 20s 1173 1. 90 copies Triethanolamine 0. 85 parts curing time 20s
对照例 4 Comparative Example 4
实施例 2的配方样品在 UV灯固化时间 10s Formulation sample of Example 2 at UV lamp curing time 10s
对照例 5 Comparative Example 5
实施例 2的配方样品在 40WX 5中波灯下固化时间 6min 对照例 6 The formulation sample of Example 2 was cured under a wave lamp at 40 WX 5 for 6 min. Comparative Example 6
实施例 2的配方样品在 250W X 2红外灯下 6min不固 实施例 3 The formulation sample of Example 2 was not solidified under a 250 W X 2 infrared lamp for 6 minutes. Example 3
CN972 (SART0MER) 9. 6份 CN972 (SART0MER) 9. 6 copies
CN120 (SARTOMER) 29份 CN120 (SARTOMER) 29 copies
CN292 (SART0MER) 19份 三羟甲基丙烷三丙烯酸酯 （TMPTA) 29份 己二醇二丙烯酸酯 （HDDA) 9. 6份 CN292 (SART0MER) 19 parts Trimethylolpropane triacrylate (TMPTA) 29 parts Hexanediol diacrylate (HDDA) 9. 6 parts
ITX 2. 9份 三乙醇胺 0. 96份 固化时间 30s ITX 2. 9 parts Triethanolamine 0. 96 parts Curing time 30s
对照例 7 Comparative Example 7
实施例 3的配方样品在 UV灯固化时间 30s Formulation sample of Example 3 at UV lamp curing time 30s
实施例 4 Example 4
CN120 (SART0MER) 48份 CN120 (SART0MER) 48 copies
CN292 (SART0MER) 19份 CN292 (SART0MER) 19 copies
三羟甲基丙垸三丙烯酸酯 （TMPTA) 29份 Trimethylolpropane triacrylate (TMPTA) 29 parts
BDK 2. 9份 BDK 2. 9 copies
对二甲氨基苯甲酸乙酯 0. 96份 固化时间 60s Ethyl p-dimethylaminobenzoate 0. 96 parts Curing time 60s
柔韧性 15mm Flexibility 15mm
60°光泽 131 60° gloss 131
硬度 0. 67 对照例 8 实施例 4的配方样品在 UV灯固化时间 20s 柔韧性 15讓Hardness 0. 67 Comparative Example 8 Formulation sample of Example 4 in UV lamp curing time 20s flexibility 15 let
60'光泽 132 硬度 0. 69 实施例 5 60' gloss 132 hardness 0. 69 Example 5
CN120 CSARTOMER) 48份 CN120 CSARTOMER) 48 copies
CN292 (SART0MER) 19份 三羟甲基丙垸三丙烯酸酯 （ TMPTA) 29份CN292 (SART0MER) 19 parts Trimethylolpropane triacrylate (TMPTA) 29 parts
907 2. 9份907 2. 9 copies
ITX 0. 48份 三乙醇胺 0. 96份 固化时间 20s 柔韧性 15mmITX 0. 48 parts Triethanolamine 0. 96 parts Curing time 20s Flexibility 15mm
60·光泽 131 硬度 0. 67 对照例 9 60·Gloss 131 Hardness 0. 67 Comparative Example 9
实施例 5的配方样品在 UV灯固化时间 10s 柔韧性 15腿Formulation sample of Example 5 in UV lamp curing time 10s flexibility 15 legs
60°光泽 132 硬度 0. 72 实施例 6 60° gloss 132 hardness 0. 72 Example 6
CN120 (SART0MER) 48份 CN120 (SART0MER) 48 copies
CN292 (SART0MER) 19份 三羟甲基丙烷三丙烯酸酯 （TMPTA) 29份CN292 (SART0MER) 19 parts Trimethylolpropane triacrylate (TMPTA) 29 parts
Ti02. 5份Ti02. 5 parts
TP0 4份4 copies of TP0
ITX 0. 48份ITX 0. 48 copies
907 0. 8份 三乙醇胺 0. 96份 固化时间 20s 对照例 10 907 0. 8 parts of triethanolamine 0. 96 parts curing time 20s Comparative Example 10
实施例 6的配方样品在 UV灯固化时间 20s Formulation sample of Example 6 at UV lamp curing time 20s
上述实施例中的原料的添加量 "份" 为重量份。 The amount of the raw material added in the above examples is "parts" in parts by weight.
实施例 7 - 12 Example 7 - 12
预聚物和单体共 8g， 三乙醇胺 0. lg混合物中加入引发剂， 涂布在相应 试板上， 固化后， 固化膜性能测试结果 Prepolymer and monomer a total of 8g, triethanolamine 0. lg mixture was added to the initiator, coated on the corresponding test plate, after curing, cured film performance test results
注： 1 ) 1000为 80 % (重量） 1173和 20 % 184的混合物; Note: 1) 1000 is a mixture of 80% by weight of 1173 and 20% 184;
2 ) 4265为 50% (重量) 1173和 50 %TP0的混合物。 工业实用性 2) 4265 is a mixture of 50% by weight of 1173 and 50% TP0. Industrial applicability
镝灯、 铟灯不但可替代紫外灯在现有固化设备上使用， 更可广泛用于家 具涂装和大面积室内外涂装工程中光固化涂料的固化。 本发明将为光固化涂 料和油墨的推广应用带来极大方便。 Xenon lamp and indium lamp can be used not only as an alternative to UV lamp in existing curing equipment, but also widely used in the curing of photocurable coatings in home painting and large-area indoor and outdoor coating projects. The invention will bring great convenience to the popularization and application of photocurable coatings and inks.
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01134383 CN1416966A (en) | 2001-11-02 | 2001-11-02 | Visible light source for photocured compostion |
| CN01134383.4 | 2001-11-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2003037530A1 true WO2003037530A1 (en) | 2003-05-08 |
Family
ID=4672458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2002/000778 Ceased WO2003037530A1 (en) | 2001-11-02 | 2002-11-01 | Use of a metal halide lamp in curing photocurable composition |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1416966A (en) |
| WO (1) | WO2003037530A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530816A (en) * | 2014-12-12 | 2015-04-22 | 惠州市至上新材料有限公司 | Bendable UV colored silk-screen printing ink for polished aluminum plates of suspended ceilings |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5184044A (en) * | 1990-08-13 | 1993-02-02 | Welch Allyn, Inc. | Dental curing lamp |
| JPH05104543A (en) * | 1991-10-18 | 1993-04-27 | Asahi Glass Co Ltd | Method for curing photo-setting resin and light source device for photo-setting resin |
-
2001
- 2001-11-02 CN CN 01134383 patent/CN1416966A/en active Pending
-
2002
- 2002-11-01 WO PCT/CN2002/000778 patent/WO2003037530A1/en not_active Ceased
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5184044A (en) * | 1990-08-13 | 1993-02-02 | Welch Allyn, Inc. | Dental curing lamp |
| JPH05104543A (en) * | 1991-10-18 | 1993-04-27 | Asahi Glass Co Ltd | Method for curing photo-setting resin and light source device for photo-setting resin |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530816A (en) * | 2014-12-12 | 2015-04-22 | 惠州市至上新材料有限公司 | Bendable UV colored silk-screen printing ink for polished aluminum plates of suspended ceilings |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1416966A (en) | 2003-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3353020B2 (en) | Method for producing polymer | |
| CA1233931A (en) | Photosensitive hydroxyalkylphenones | |
| JP2005514476A5 (en) | ||
| CN1175058C (en) | UV curable compositions for producing electroluminescent coatings | |
| WO2003037936A1 (en) | Visible-light curable composition | |
| JP2002500670A (en) | Aromatic maleimides and methods of using the same | |
| Kirschner et al. | A new phosphine for efficient free radical polymerization under air | |
| Burget et al. | Photopolymerization of thiol–allyl ether and thiol–acrylate coatings with visible light photosensitive systems | |
| WO2003037530A1 (en) | Use of a metal halide lamp in curing photocurable composition | |
| JPWO2019188353A1 (en) | Antibacterial composition, antibacterial membrane, substrate with antibacterial membrane | |
| US6265458B1 (en) | Photoinitiators and applications therefor | |
| JP2003533548A6 (en) | Chelates containing quinoid groups as photopolymerization initiators | |
| CN108948243B (en) | Preparation method of polymethyl methacrylate with high molecular weight and narrow distribution | |
| JPH0299585A (en) | Fluorescent paste composition | |
| CN110156728A (en) | 2-Phenylthiofuran or thienyl ketoxime ester compound and preparation method and application thereof | |
| JP6475131B2 (en) | Curable composition, cured product | |
| JPH06348013A (en) | Photosensitive resin composition | |
| GB2180245A (en) | Light curing compositions for dental restoration | |
| WO2006100825A1 (en) | Photocurable resin composition for forming black matrix, photosensitive film using the same, method for forming black matrix, black matrix and plasma display panel having the black matrix | |
| US6277897B1 (en) | Photoinitiators and applications therefor | |
| RU2006107216A (en) | COMPOSITIONS FOR APPLICATION OF SELF-OXIDIZING ARCHITECTURAL COATINGS | |
| JPH0473448B2 (en) | ||
| JPH11133596A (en) | Photopolymerizable composition, pattern forming method using the same, and method for manufacturing cathode ray tube | |
| JPH04132710A (en) | Resin composition and cured material thereof | |
| TW583509B (en) | Photopolymerizable composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LU MC NL PT SE SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| 122 | Ep: pct application non-entry in european phase | ||
| NENP | Non-entry into the national phase |
Ref country code: JP |
|
| WWW | Wipo information: withdrawn in national office |
Country of ref document: JP |