CN101320208B - Reflection holography thin film and preparation method thereof - Google Patents

Reflection holography thin film and preparation method thereof Download PDF

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CN101320208B
CN101320208B CN 200810040804 CN200810040804A CN101320208B CN 101320208 B CN101320208 B CN 101320208B CN 200810040804 CN200810040804 CN 200810040804 CN 200810040804 A CN200810040804 A CN 200810040804A CN 101320208 B CN101320208 B CN 101320208B
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film
coating
photosensitive
hologram
material
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CN101320208A (en
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徐良衡
徐雪雯
李兰芳
游仁顺
高芸
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上海复旦天臣新技术有限公司
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Abstract

The invention provides a reflection holographic thin membrane and a preparation method thereof. The reflection holography membrane comprises a basement membrane, a buffer layer which is coated at one side of the basement membrane, a photopolymer coating which is coated at the other side of the buffer layer and formed by the holographic polymer paints, and a protective membrane which is covered onthe surface of the photopolymer; wherein, hologram images or the interference fringes of double discoloration pictures are recorded on the photopolymer coating; the photopolymer coating comprises film-forming agents, a nano-composite pre-polymer, a monomer, photo initiators, chain transfer agents and photo sensitizers; the nano-composite pre-polymer is a product which is prepared by alkenyl unsaturated monomer with an unsaturated group at the terminal position and nano-particles. The invention has high sensitivity, high reflection efficiency, high refractivity modulation value, long storage life and little influence of the environment on the hologram images; the recorded images are treated by photo-curing and heat-enhancement and can reach reflected images and double discoloration images with the reflection efficiency of more than 99.9 precent, so mass production is available.

Description

反射全息薄膜及其制备方法 Reflection holographic film and preparation method

技术领域 FIELD

[0001] 本发明涉及一种反射全息薄膜及其制备方法。 [0001] The present invention relates to a film A reflective hologram and its preparation method.

背景技术 Background technique

[0002] 反射全息图的制作限于其记录的干涉条纹不同于彩虹全息,大多数平行于记录介质表面,无法通过机械方式实现复制,只能通过光学的方法实现图像复制。 Production [0002] limited in its reflection hologram recording interference fringes different from rainbow hologram, most parallel to the surface of the recording medium, copying can not be achieved by mechanical means, the image can only be achieved by an optical copying process. 而全息图的显现通常是通过干涉条纹的对比度来实现。 Show the hologram is typically accomplished by the contrast of the interference fringes. 而用于记录反射全息图的材料,种类较多,但是理想的记录材料却较少,可以用于规模化生产的材料更少。 And the material used for recording reflection holograms, more species, but it is less desirable to a recording material, can be used for large-scale production of less material. 通常较多的是,使用银盐和重铬酸明胶以及US3,658526专利中公开的一种光聚合物材料。 More generally, the use of a silver salt and an optical dichromate gelatin, and polymer material disclosed in Patent US3,658526.

[0003] 银盐记录材料具有高的灵敏度,其干涉条纹是由感光后材料的黑白对比度来实现,但是衍射效率低,即使采用稀释显影的方法衍射效率也只能达40%左右; [0003] The silver halide recording material having high sensitivity, which is achieved by the interference fringes contrast of the black and white photosensitive materials, but low diffraction efficiency, the diffraction efficiency even when diluted with the method developed only up to about 40%;

[0004] 重铬酸明胶是目前制备反射全息图的常选材料,其干涉条纹是由折射率的差异所体现,它制作的全息图具有很高的衍射效率,可达85%以上,很多全息元件都是采用此材料制成。 [0004] Preparation of dichromate gelatin is often selected from the reflection hologram material, interference fringe which is reflected by the difference in refractive index, making it hologram having a high diffraction efficiency, up to 85%, many holographic components are made of this material. 但它也有很多不足之处,如感光度偏低,储存寿命短,感光版需要随用随制作等缺憾, 同时该材料在成像后,需要湿法加工,全息图受环境的影响很大,在湿度较大的环境中很容易消像; But it also has many disadvantages, such as low sensitivity, short storage life, the photosensitive printing plate production, etc. need to be used with the defects, while the material after forming, requires wet processing, the hologram is greatly affected by the environment, in larger humidity environment easily eliminate image;

[0005] 而光致聚合物材料,如US3,658526专利公开的材料中的光聚物,是通过两种聚合物的不同折射率实现干涉条纹显示,虽然其可以克服银盐和重铬酸明胶的缺点,但他们对可见光只有有限的视觉响应,受分辨率的影响,一直局限于透射全息图,当用于反射全息图时,反射效率很低。 [0005] photopolymer material and the material, as disclosed in the patent US3,658526 photopolymer, by different refractive indices of the two polymers to achieve interference fringe display, although it can overcome gelatin dichromate and silver shortcomings, but they are visible only limited visual response, affected by the resolution, has been limited to transmission holograms, when used in a reflection hologram reflection efficiency is very low.

发明内容 SUMMARY

[0006] 本发明的目的是公开一种反射全息薄膜及其制备方法,以克服现有技术存在的上述缺陷; [0006] The object of the present invention is to disclose a method for preparing a holographic reflection film and to overcome the above drawbacks of the prior art;

[0007] 本发明的另一个目的是提供一种可以记录反射全息的感光聚合物薄膜; [0007] Another object of the present invention is to provide a photopolymer recording film is a reflection hologram;

[0008] 本发明的再一个目的是提供一种全息感光涂料,用于制备所述的感光聚合物薄膜材料。 [0008] A further object of the present invention to provide a holographic photosensitive paint, photosensitive polymeric film material for the preparation.

[0009] 本发明所说的全息感光涂料,包括感光聚合物涂料及与之匹配的溶剂,所述的感光聚合物涂料包括如下重量百分比的组分: [0009] The present invention is a hologram of said photosensitive coating, and a solvent comprising a photosensitive polymer coating matching, said polymer coating comprising photosensitive components by weight percentage:

[0010] 成膜剂 20%〜80%[0011] 纳米复合预聚体 4%〜20%[0012] 单体 10%〜50%[0013] 光引发剂 0. 5%〜Ί%[0014] 链转移剂 0. 3%〜5%[0015] 光敏剂 0. 05%〜2%[0016] 所说的全息感光涂料的重量含固量为5% [0010] 20% ~ 80% film forming agent [0011] nanocomposite prepolymer ~20% 4% [0012] 10% ~ 50% monomer [0013] The photoinitiator 0. 5% ~Ί% [0014] 0.3% ~ 5% [0015] photosensitizer 0.05% ~ 2% [0016] by weight of said hologram photosensitive coating solids chain transfer agent is 5%

Figure CN101320208BD00051

[0024] 所说的成膜剂是给体系提供基线折射率,连结纳米复合预聚体和单体、引发体系 [0024] said film forming agent is a refractive index to provide a baseline system, the coupling nanocomposite prepolymer and monomer, initiating system

及相关助剂的重要成分,且在曝光后对形成反射全息图所需的物理性能和折射率调制有着重要的贡献。 Important components and related auxiliaries, and after the exposure to form the desired physical properties of the reflection hologram and refractive index modulation has an important contribution. 其折射率、内聚力、粘结力、柔韧性、混溶性等,作为选择材料的重要指标,所说的成膜剂选自聚甲基丙烯酸甲酯、聚醋酸纤维素丁酯、醋酸纤维素丁酯与乙基乙烯基醚的共聚物、聚乙烯醇缩丁醛与醋酸纤维素的共混物、聚醋酸乙烯酯-丙烯酸丁酯-丙烯酸三元共聚物或聚苯乙烯丙烯腈等,或上述聚合物与含氟聚合物的混合材料,所说的含氟聚合物选自三氟氯乙烯醋酸乙烯基醚的共聚物或四氟乙烯与乙基乙烯基醚的共聚物; Refractive index, cohesion, adhesion, flexibility, miscibility, etc., as an important indicator of the selected material, said film forming agent is selected from polymethyl methacrylate, polybutyl cellulose acetate, cellulose acetate butyrate ester copolymer and ethyl vinyl ether, polyvinyl butyral aldehyde with a blend of cellulose acetate, polyvinyl acetate - butyl acrylate - acrylic acid terpolymer, or polystyrene acrylonitrile or above mixing a polymer material with a fluoropolymer, said fluoropolymer is selected from vinyl acetate copolymer of chlorotrifluoroethylene or tetrafluoroethylene ether copolymer of ethylene and ethyl vinyl ether;

[0025] 所说的单体选自单官能团或双官能团的丙烯酸酯类、N-乙烯基咔唑类、乙氧基化的双酚A的二丙烯酸酯或三环癸烷二甲醇二丙烯酸酯中的两种以上,两种单体之间的重量比例为1 : 0. 4〜0. 9 ; [0025] said monomer is selected from monofunctional or difunctional acrylates, N- vinylcarbazole, ethoxylated diacrylate of bisphenol A or a tricyclodecane dimethanol diacrylate the two or more, the weight ratio between the two monomers was 1: 4~0 0. 9;.

[0026] 优选的,所说的单体为N-乙烯基咔唑和三环癸烷二甲醇二丙烯酸酯的混合物,重量比为1 : 0. 5〜0. 8 ; [0026] Preferably, said monomer is a mixture of diacrylate and N- vinylcarbazole tricyclodecane dimethanol, a weight ratio of 1: 5~0 0. 8;

[0027] 所说的纳米复合预聚体是一种末端位置上含有烯基基团的单体与纳米颗粒采用原位聚合方法制备的产物; [0027] The nanocomposite of said prepolymer with a monomer containing alkenyl groups nanoparticles using the product prepared in situ polymerization method for terminal position;

[0028] 所说末端位置上含有烯基基团的单体的结构通式如下: [0028] The general structure of the alkenyl group-containing monomer of said terminal position follows:

[0029] [0029]

Figure CN101320208BD00052

[0030]其中: [0030] wherein:

[0031 ] R1 代表H 或CH3 ;R2 代表C00CH3、COOC4H9 或| [0031] R1 represents H or CH3; R2 Representative C00CH3, COOC4H9 or |

[0032] 所说的末端位置上含有烯基基团的单体优选甲基丙烯酸甲酯、甲基丙烯酸丁酯或4-巯甲基苯乙烯; [0032] The monomer is preferably methyl methacrylate, an alkenyl group of said terminal positions, butyl methacrylate, or 4-mercapto-methylstyrene;

[0033] 所说的纳米颗粒选自TiO2、ZnO或ZnS颗粒,粒径为20〜50纳米; [0033] said nanoparticles are selected from TiO2, ZnO or ZnS particles, a particle size of 20~50 nm;

[0034] 考虑材料的相容性,优选的纳米复合预聚体为含有ZnS颗粒的甲基丙烯酸甲酯的原位聚合产物或含有ZnS颗粒的4-巯甲基苯乙烯的原位聚合产物。 [0034] consideration the compatibility of the material, preferably the pre-polymer nanocomposite situ polymerization product or in situ polymerization product of 4-mercaptomethyl-containing ZnS particles containing a styrene methyl methacrylate ZnS particles.

[0035] 纳米颗粒在纳米复合预聚体中的重量含量为0. 2%〜2%,优选0. 6〜1. 0% ; [0035] The weight content of the nanoparticles in the nanocomposite prepolymer is 0.2% ~ 2%, preferably 0% 0. 6~1.;

[0036] 优选的纳米复合预聚体的重均分子量为5000〜50000 ; [0036] The nanocomposite preferably has a weight average molecular weight of the prepolymer is 5000~50000;

[0037] 所述的纳米复合预聚体,由预聚体包裹的纳米颗粒,是一种具有较高折射率的纳 Sodium [0037] The nanocomposite prepolymer, the prepolymer encapsulated nanoparticles having a high refractive index

5米复合材料,可以根据纳米颗粒的含量来控制材料的折射率,目的在于提高感光后参与聚合的材料射率调制值; Composite 5 m, refractive index material can be controlled depending on the content of nanoparticles, materials designed to improve the reflectance modulation value photosensitive participating in aggregation;

[0038] 所说的纳米复合预聚体的制备方法可以采用原位聚合的方法,简述如下: [0038] The method for preparing said nanocomposite prepolymer may be employed in situ polymerization, summarized as follows:

[0039] 将引发剂、末端位置上含有不饱和基团的烯基不饱和类单体和纳米颗粒在惰性气氛中,70〜75°C反应20〜30分钟,冷却,冷藏保存待用。 [0039] The initiator, an unsaturated alkenyl group and an unsaturated monomer nanoparticles in an inert atmosphere, 70~75 ° C 20 to 30 minutes the reaction was cooled, refrigerated stand-terminal position.

[0040] 光引发剂、链转移剂和光敏剂构成光引发体系,引发体系是决定感光灵敏度的重要因素,引发体系包含一种或多种当用光辐射激发时,能直接产生自由基的化合物,其自由基可以引发单体进行聚合; [0040] Compound a photoinitiator, a chain transfer agent and a photosensitizer photoinitiator system constituting initiator system is an important factor in determining the sensitivity of the photosensitive initiator system comprises one or more excited when irradiated with light, can generate free radicals directly which can initiate free radical polymerization of monomers;

[0041] 优选的光引发剂选自2,4,6-三苯基咪唑基双联体或联苯甲酰; [0041] Preferred photoinitiators are selected from 2,4,6-triphenyl-imidazolyl double or dibenzoyl;

[0042] 优选的光敏剂选自藻红B、二乙氨基-亚苄基环戊酮、米氏酮或1,3,3_三甲基-2- [5- (1,3,3-三甲基-2-吲哚叉)-1,3-戊二烯]吲哚碘盐等; [0042] Preferred photosensitizers are selected from erythrosine B, diethylamino - benzylidene cyclopentanone, Michler's ketone or 1,3,3_ trimethyl-2- [5- (1,3,3- trimethyl-2-indol-fork) 1,3-pentadiene] indol-iodized salt;

[0043] 优选的链转移剂选自2-巯基苯并噁唑、十二硫醇或巯基苯并噻唑; [0043] The preferred chain transfer agent is selected from 2-mercaptobenzoxazole, dodecyl mercaptan or mercapto benzothiazole;

[0044] 所说的溶剂为丁酮/ 二氯甲烷/甲醇的混合溶剂,其重量比例为4〜6 : 0. 5〜 1. 5 : 0. 5 〜1. 5,优选的为:5 : 1 : 1 ; [0044] said solvent is a mixed solvent of methyl ethyl ketone / dichloromethane / methanol in a weight ratio of 4 ~ 6: 0. -5 to 1.5: 0.5 ~ 1 5, preferably: 5: 1: 1;

[0045] 优选的,所述的感光聚合物涂料还包括感光聚合物涂料总重量0. 5〜3%的增塑剂和/或0. 1〜1 %的紫外吸收剂和/或0. 1〜1 %的非离子表面活性剂; [0045] Preferably, the coating further comprises a photopolymer photosensitive polymer coating on the total weight of 0. 5~3% plasticizer and / or 0. 1~1% UV absorber and / or 0.1 ~ 1% of a nonionic surfactant;

[0046] 增塑剂选自邻苯二甲酸酯,烷基二酸酯、聚乙二醇羧酸酯或癸二酸二乙酯,紫外吸收剂选自2-羟基-4-甲氧基二苯甲酮或2-(2H-苯并三唑-2)-4,6-二(1-甲基-1-苯乙基)苯酚,非离子表面活性剂选自聚乙二醇、甲氧基聚乙二醇或3M公司生产的氟素表面活性剂Fluorad ® FC-4430 (CAS No. 108-88-3),用以调节涂覆性能。 [0046] The plasticizer is selected from phthalates, dialkyl esters, polyethylene glycol carboxylic acid ester or diethyl sebacate, a UV absorber selected from 2-hydroxy-4-methoxy benzophenone, or 2- (2H- benzotriazol -2) -4,6-bis (1-methyl-1-phenylethyl) phenol, a nonionic surfactant selected from polyethylene glycol, methyl group or a polyethylene glycol manufactured by 3M fluorocarbon surfactant Fluorad ® FC-4430 (CAS No. 108-88-3), to adjust the coating properties.

[0047] 本发明所说的可以记录反射全息的感光聚合物薄膜,包括基膜和涂复在基膜一侧上的缓冲层、涂复在缓冲层另一侧上的全息感光涂料形成的感光聚合物涂层和覆盖在感光聚合物涂料层表面的表面保护膜,干燥后的感光聚合物涂料层的厚度为3〜50μπι ; [0047] The photoreceptor of the present invention may be mentioned reflection holographic photopolymer recording film comprising a base film and a base film coated on one side of the buffer layer, coated on the other side of the buffer layer is formed of a hologram photosensitive coating and a polymeric coating covering the surface of the surface protective layer coating the photosensitive polymer film, polymer coating thickness of the photosensitive layer after drying was 3~50μπι;

[0048] 所说的基膜选自20〜100 μ m的PVC、PET或BOPP膜,厚度为20〜100 μ m ; [0048] said base film is selected from the PVC 20~100 μ m, PET or BOPP film, having a thickness of 20~100 μ m;

[0049] 所说的缓冲层是感光聚合物涂料层与基膜的连接层,所用材料可采用与基膜折射率相近的醋酸乙烯酯和丙烯酸酯类共聚物、偏氯乙烯苯乙烯醋酸乙烯酯共聚物或采用丙烯酸酯类等光固化涂层,涂层厚度为1〜2μπι。 [0049] The buffer layer is connected to said polymer coating layer of the photosensitive layer and the base film, the base film may be employed close to the refractive index of vinyl acetate and acrylic copolymer material, styrene-vinylidene chloride-vinyl acetate copolymer or the like using light-cured acrylate coating, a coating thickness of 1~2μπι.

[0050] 所说的表面保护膜,可采用已有离型涂层的基材,优选厚度为16〜23μπι的PET 膜、BOPP膜、PE或PVC膜,这种有离型涂层的PET膜、BOPP膜、PE或PVC膜在市场上均可以采购到,如日本东丽公司的PET膜产品; [0050] surface of said protective film, has been employed from the substrate type coating, preferably a thickness of a PET film 16~23μπι, BOPP film, PE or PVC film, PET film of such a release coating , BOPP film, PE or PVC film can be in the market to purchase, such as Japan's Toray PET film products;

[0051] 本发明所说的反射全息薄膜,在所说的可以记录反射全息的感光聚合物薄膜的感光聚合物涂层上记录有全息图像或双变色图文的干涉条纹; [0051] The present invention reflection of said hologram film, is recorded on the photopolymer coating said photopolymer reflection hologram may be recorded with a hologram film or dual color graphic interference fringes;

[0052] 所说的反射全息薄膜C的制备方法,包括如下步骤: [0052] A method of preparing said film C of the reflection hologram, comprising the steps of:

[0053] (1)涂布材料的制备:在避光条件或在红色光线下,按比例将成膜剂、纳米复合预聚单体、单体、引发剂和光敏剂加到溶剂中,搅拌溶解,获得所说的感光涂料Α,优选的,可同时加入增塑剂、紫外吸收剂和/或表面活性剂等组分; [0053] Preparation of coating material (1): In dark conditions or under red light, in proportion to the film former, the nanocomposite prepolymerization monomer, monomer, initiator and a photosensitizer added to the solvent, stirring dissolve, to obtain a photosensitive coating of said [alpha], preferably, may be added a plasticizer, an ultraviolet absorber and / or a surfactant component simultaneously;

[0054] (2)感光聚合物薄膜材料B的制备:在涂布基膜上涂布缓冲层,在避光条件或在红色光线下,将步骤的感光涂料Α,涂布在已有缓冲层的基膜上,在65-75°C下干燥1〜5分钟,干燥后覆盖保护膜,即获得所说的感光聚合物薄膜材料B ;[0055] (3)反射全息薄膜C的制备:将步骤⑵的产物揭开保护膜,采用反射全息记录方法,将全息图记录在感光聚合物薄膜材料B上,然后在紫外固化机上对膜进行紫外和可见光全部曝光,120°C加热2〜50分钟,即获得反射全息薄膜C,为一种固态透明薄膜感光材料,具有一定的柔韧性; Preparation of [0054] (2) a photosensitive polymer film material B: in coating buffer layer coating the base film, in dark conditions or under red light, the photosensitive coating Α step, the buffer layer has been coated the base film, and dried at 65-75 ° C 1~5 minutes, covered with a protective film after drying, to obtain said photosensitive polymeric film material B; preparation of [0055] (3) a reflective holographic film C: the the product of step ⑵, remove the protective film, reflective hologram recording method, a hologram recorded on a photopolymer film material B, and then the film is subjected to UV curing machine overall exposure to ultraviolet and visible, 120 ° C heating 2~50 minutes , i.e., reflection hologram film C is obtained, as a solid, transparent, photosensitive film material, having a certain flexibility;

[0056] 所说的红色光线的波长应大于600nm,采用避光条件或红色光线,其目的是避免感光涂料A的曝光; [0056] wavelength of said red light of 600 nm should be greater than, or protected from light using red light, whose purpose is to avoid exposure of the photosensitive coating A;

[0057] 激光光源的波长为514. 5nm或532nm,光强为60〜1 lOmw/cm2,曝光时间在0. 1-1. Os,激光光源可采用氩离子激光器(波长为514nm)或半导体固体激光器(波长532nm); Wavelength [0057] The light source is a laser or 514. 5nm 532nm, light intensity 60~1 lOmw / cm2, exposure time 0. 1-1. Os, the laser light source can be an argon ion laser (wavelength 514nm) or a semiconductor solid laser (wavelength 532nm);

[0058] 所说的激光记录方法为一种现有技术,如李普曼记录法和Danisyuk法等,有关技术人员可参照实施。 [0058] A method of said recording laser beam as a prior art, such as Lippmann Danisyuk recording method and method, reference may be related art embodiment.

[0059] 本发明的感光聚合物薄膜B,是一种利用两种不同折射率聚合物的感光材料,通过相干光束的参考光和物光从相反两侧(或同侧)干涉进入记录介质,激发单体进行自由基聚合,单体也参与纳米复合预聚体进行共聚,形成高折射率的聚合物条纹,形成全息图,得到高衍射效率全息图像。 [0059] The photosensitive polymer film B according to the present invention, a photosensitive material using two polymers of different refractive indices, by a coherent reference light and object light beams from opposite sides of the interference (or ipsilateral) into the recording medium, excitation of radical polymerizing monomers, monomers are also involved in the nanocomposite prepolymer copolymerize to form a polymer of a high refractive index stripe, holograms are formed to obtain a high diffraction efficiency holographic image.

[0060] 本发明利用上述高聚物全息感光材料,运用光学干涉原理,在该高聚物全息感光材料中形成特定波长的亮暗相间的反射条纹。 [0060] The present invention utilizes the above-described polymer hologram photosensitive material, using principles of optical interference, forming a specific wavelength of light and dark stripes and white reflective holographic polymer in the photosensitive material. 光聚合是通过光化学的方法产生自由基引发单体、纳米复合预聚体进行聚合,光引发体系在受到一定能量特定波长的光辐射,吸收光子跃迁到激发态,生成自由基,引发单体和纳米复合预聚体进行聚合,在亮条纹处发生聚合, 致使暗条纹处的单体向单体稀少的亮条纹发生迁移,同时纳米复合预聚体也随单体一同向亮条纹迁移加入自由基的聚合,形成了不同于成膜剂折射率的纳米聚合物,得到显示明亮全息图。 A radical photopolymerization is produced by a method of photochemical initiator monomer nanocomposite prepolymer polymerization, a photoinitiator system is subject to certain optical radiation energy in a particular wavelength, they absorb photons to an excited state to generate radicals, the monomer and initiator nanocomposite prepolymer polymerization, the polymerization occurs in the bright stripes, the resulting dark stripe monomers migrate to the monomer at a rare bright stripes, while the nanocomposite prepolymer also join with the monomer to radical migration bright stripes is polymerized to form a polymer film former is different from the refractive index of the nano to obtain bright display holograms.

[0061] 由上述公开的技术方案可见,本发明的全息感光薄膜B,有较好的灵敏度、很高的反射效率和较高的折射率调制值,储存寿命长,全息图受环境的影响小,不同于感光材料常规的湿法处理方法,所得到的记录图像只需经过光固化和热增强处理,便可达到反射效率大于95%的反射图像或双变色图像,适宜于批量化生产。 [0061] seen from the above disclosed technical solution, the hologram photosensitive film B according to the present invention, a better sensitivity, a high reflection efficiency and a high refractive index modulation, long storage life, the hologram little affected by the environment , conventional wet processing method is different from the light-sensitive material, the resultant recorded images only after photocurable and heat reinforcing treatment, can achieve a double reflection image or color image reflection efficiency greater than 95%, it is suitable for mass production.

附图说明 BRIEF DESCRIPTION

[0062] 图1为用于全息记录的感光聚合物薄膜结构示意图。 [0062] Figure 1 is a schematic view of the structure of the photopolymer holographic recording film is used.

[0063] 图2为反射全息薄膜激光记录和光路测试示意图。 [0063] FIG. 2 is a laser reflection hologram recording film and the optical test path schematic.

具体实施方式 Detailed ways

[0064] 参见图1,本发明所说的感光聚合物薄膜,包括基膜1和涂复在基膜1 一侧上的缓冲层2、涂复在缓冲层2另一侧上的全息感光涂料形成的感光聚合物涂层3和覆盖在感光聚合物涂料层表面的表面保护膜4,感光聚合物涂料层3上可刻录全息图像或双变色图文的干涉条纹。 [0064] Referring to Figure 1, the present invention said photosensitive polymeric film comprising a base film, and coated on one side of the base film 1 a buffer layer 2, coated on the other side of the buffer layer 2 hologram photosensitive coating photopolymer coating layer 3 formed covering the surface of the surface protective layer coating the photosensitive polymer film 4, a recordable dual-color holographic image or graphic on an interference fringe photosensitive polymer coating layer 3.

[0065] 以下通过实施例说明本发明,但这些实施例只是示例性的,本发明并不局限此。 [0065] The present invention is described below by way of examples, but these are merely exemplary embodiments of the exemplary embodiment, the present invention is not limited thereto.

[0066] 实施例1 [0066] Example 1

[0067] 将0.012g偶氮二异丁腈、30g甲基丙烯酸甲酯和0. 2g SiS (粒径在20nm),投入到IOOmL装有电动搅拌器、冷凝管和通氮气管的磨口三口瓶中,开启冷却水,通氮气,开动搅拌器,搅拌速度为800转/min)。 [0067] The 0.012g of azobisisobutyronitrile, and 30g of methyl methacrylate 0. 2g SiS (particle size 20 nm), with a ground IOOmL into three electric stirrer, a condenser, and a nitrogen tube bottle, open cooling water, nitrogen, start stirrer, a stirring speed of 800 revolutions / min). 加热至75°C,20min后取样,制成含有ZnS纳米颗粒的甲基丙烯酸甲酯预聚体,则停止加热,冷却至室温。 It was heated to 75 ° C, 20min after sampling, made of methyl methacrylate containing ZnS nanoparticles prepolymer, the heating was stopped, cooled to room temperature. 冲氮气冷藏保存待用。 Chong nitrogen refrigerated for later use. 纳米颗粒的重量含量为0. 66%,测得重均分子量为5600。 Weight content of nanoparticles is 0.66%, measured by weight average molecular weight of 5,600.

[0068] 实施例2 [0068] Example 2

[0069] 将0. 02g联苯甲酰、36g4-巯甲基苯乙烯和0. !35g SiS (粒径在30nm),投入到IOOmL装有电动搅拌器、冷凝管和通氮气管的磨口三口瓶中,开启冷却水,通氮气,开动搅拌器混和均勻(搅拌速度为1200转/min)。 [0069] The dibenzoyl 0. 02g, 36g4- mercaptomethyl styrene and 0.! 35g SiS (particle size 30 nm), into a ground IOOmL equipped with electric stirrer, a condenser, and a nitrogen tube three-neck flask, open cooling water, nitrogen, stirrer was started uniformly mixing (stirring speed 1200 rpm / min). 加热至75°C,20min后取样。 It was heated to 75 ° C, 20min after sampling. 制成含有ZnS纳米颗粒的4-巯甲基苯乙烯预聚体,则停止加热,冷却至室温。 Made of 4-mercaptomethyl-ZnS nanoparticles containing styrene prepolymer, the heating was stopped, cooled to room temperature. 冲氮气冷藏保存待用。 Chong nitrogen refrigerated for later use. 纳米颗粒的重量含量为0. 96%,测试得重均分子量为12000。 Weight content of nanoparticles is 0.96%, the test weight average molecular weight was 12,000.

[0070] 实施例3 [0070] Example 3

[0071] 在波长大于600nm的红色安全灯下,将9.2克(77wt%)成膜剂聚醋酸乙烯酯-丙烯酸丁酯-丙烯酸三元共聚物,单体N-乙烯基咔唑1. O克(8. 3wt % ),单体三环癸烷二甲醇二丙烯酸酯0.6克(5wt%),含有ZnS纳米颗粒的甲基丙烯酸甲酯预聚体0. 53克实施例1),光引发剂2,4,6-三苯基咪唑基双联体0. 078克(0. 65wt % ),光敏剂二乙氨基-亚苄基环戊酮0.067克(0.056wt% ),链转移剂2-巯基苯并噻唑0.04克(0. 33wt%),紫外吸收剂2-羟基-4-甲氧基二苯甲酮0.02克(0. 17wt% ),非离子表面活性剂Fluorad ® FC-44300. 11克(0. 92wt% ),增塑剂癸二酸二乙酯0. 34克(2. 8wt% )加到混合溶液(丁酮:二氯甲烷:甲醇=5 : 1 : 1,重量比)中,重量固含量为8%,室温搅拌至溶解,测得粘度为llcp(25°C ),过滤,获得感光涂料,待用; [0071] In a wavelength greater than 600nm red safelight, 9.2 g (77wt%) polyvinyl acetate film forming agent - butyl acrylate - acrylic acid terpolymer, N- vinyl carbazole monomers 1. O g (8. 3wt%), the monomer tricyclodecane dimethanol diacrylate 0.6 g (5wt%), methyl methacrylate-containing ZnS nanoparticles prepolymers Example 1 0.53 g), a photoinitiator 2,4,6-triphenyl-imidazolyl doublets 0.078 g (0. 65wt%), photosensitizer diethylamino - benzylidene cyclopentanone 0.067 g (0.056wt%), a chain transfer agent is 2- mercapto benzothiazole 0.04 g (0. 33wt%), UV absorber 2-hydroxy-4-methoxy benzophenone 0.02 g (0. 17wt%), nonionic surfactant Fluorad ® FC-44300. 11 g (0. 92wt%), diethyl sebacate plasticizer, 0.34 g (2. 8wt%) was added to a mixed solution (ketone: dichloromethane: methanol = 5: 1: 1 weight ratio) , the solids content of 8% by weight, stirred at room temperature until dissolved, the measured viscosity was llcp (25 ° C), filtered to obtain a photosensitive coating, stand;

[0072] 选取50 μ m高透明度的PET膜为基膜1,配制重量浓度为40%偏氯乙烯苯乙烯醋酸乙烯酯共聚物溶液,用120线的网纹辊涂布于基膜1,与60°C烘干,得到缓冲层2,缓冲层的厚度为iym; [0072] Select 50 μ m transparent PET film to the base film 1 to prepare a concentration of 40% by weight of styrene-vinylidene chloride-vinyl acetate copolymer solution, with 120 line anilox roller is applied to the base film 1, and 60 ° C and drying, to obtain a buffer layer 2, the thickness of the buffer layer IYM;

[0073] 调整刮刀与涂布头的间隙为200 μ m,将上述感光聚合物涂料涂布于已涂有缓冲层2,厚度为50 μ m的PET膜上,在75。 [0073] The regulating blade and the coating head gap 200 μ m, the above-described coating composition to the photopolymer coated with a buffer layer 2 has a thickness of 50 μ m PET film at 75. C的对流干燥箱内烘干覆膜,涂层厚度为10 μ m,覆盖已有离型涂层厚度为23微米的PET膜4,获得用于全息记录的感光聚合物薄膜; C in a convection drying oven drying the coating film, a coating thickness of 10 μ m, the release cover has a coating thickness of 23 micron PET film 4 to obtain a photosensitive polymer film for holographic recording;

[0074] 反射全息薄膜的制备: [0074] reflection hologram film prepared:

[0075] 采用“在轴”反射全息记录方法,具体参见图2所示,将所说的用于全息记录的感光聚合物薄膜裁切成30*30mm的片材,揭去表面保护膜(4)后粘贴于反射镜43,氩离子激光器激光(514nm)的光束300通过带有针孔滤波器的扩束镜41和非球面准直凸透镜42形成平行光束301,光强为60mW/Cm2,辐射于感光聚合物薄膜,平型光301从基膜1入射,经过缓冲层2和感光聚合物涂层3到达反射镜43,曝光时间在0. Is,,从而将全息图记录在用于全息记录的感光聚合物薄膜上,然后在紫外固化机上对膜进行紫外和可见光全部曝光,120°C 加热2分钟,即获得反射全息薄膜,视觉可见为全息反射镜。 [0075] The "on-axis" reflection hologram recording method, see in particular figure, the said holographic recording photopolymer film was cut into a 30 * 30mm sheet 2, the surface protective film peeled (4 ) attached to the reflecting mirror 43, a parallel laser beam 301 argon ion laser (514nm) light beam by the beam expander 300 is formed with a pinhole filter 41 and collimating lens 42 aspheric, the light intensity of 60mW / Cm2, radiation the photosensitive polymer film, flat incident light 301 from the base film 1, through the buffer layer 2 and the photosensitive polymer coating layer 3 reaches the reflective mirror 43, the exposure time is 0. Is ,, so that the hologram recording in a hologram recording the photosensitive polymer film, then the film is subjected to UV curing machine overall exposure to ultraviolet and visible, 120 ° C for 2 minutes to obtain a reflection hologram film i.e., a visually observable holographic mirror. 该薄膜为一种固态透明薄膜材料,具有一定的柔韧性。 The film is a transparent film of a solid material having a certain flexibility.

[0076] 实施例4 [0076] Example 4

[0077] 在波长大于600nm的红色安全灯下,将成膜剂聚乙烯醇缩丁醛与醋酸纤维素的共混物,2. 86克Owt% ),单体N-乙烯基咔唑2. 66克2wt% ),单体乙氧基化的双酚A的二丙烯酸酯1.77克(16. lwt%),含有ZnS纳米颗粒的4-巯甲基苯乙烯预聚体2. 11克(19. 2wt%实施例2)光引发剂异丁基苯偶姻醚0. 73克(6. 6wt % ),光敏剂米氏酮0. 19克(1. 7wt%),链转移剂2-巯基苯并噻唑0. 51克(4. 6wt%),紫外吸收剂2-羟基-4-甲氧基二苯甲酮0. 96克(0. 88wt% ),非离子表面活性剂甲氧基聚乙二醇0. 018克(0. 16wt% ), 增塑剂癸二酸二乙酯0.0594克(0.5#t%)加到混合溶液(丁酮:二氯甲烷:甲醇= 5:1: 1,重量比)中,重量固含量为46.3%,室温搅拌至溶解,测得粘度^.3cp(25°C ), 过滤,获得感光涂料,待用; [0077] In a red safelight wavelength of more than 600nm, the film former, polyvinyl butyral and cellulose acetate blend, 2.86 g Owt%), N- vinyl carbazole monomers 2. 66 g 2wt%), ethoxylated diacrylate monomer bisphenol a 1.77 g (16. lwt%), ZnS nanoparticles containing 4-mercaptomethyl-styrene prepolymer 2.11 g (19 . 2wt% Example 2) photoinitiator benzoin isobutyl ether, 0.73 g (6. 6wt%), 0.19 g of photosensitizer Michler's ketone (1. 7wt%), 2-mercaptoethanol chain transfer agent benzothiazole 0.51 g (4. 6wt%), UV absorber 2-hydroxy-4-methoxy benzophenone 0.96 g (0. 88wt%), nonionic surfactant methoxypoly 0.018 g of ethylene glycol (0. 16wt%), diethyl sebacate plasticizer 0.0594 g (0.5 # t%) was added to a mixed solution (ketone: dichloromethane: methanol = 5: 1: 1 , weight ratio), a weight solids content of 46.3%, was stirred at room temperature until dissolved, the measured viscosity ^ .3cp (25 ° C), filtered to obtain a photosensitive coating, stand;

[0078] 选取36 μ m高透明度的PET膜为基膜1,配制重量浓度为30%醋酸乙烯酯和丙烯酸丁酯的共聚物溶液,用100线的网纹辊涂布于基膜1,在50〜70°C的烘箱烘干,得到带有缓冲层2的基膜,缓冲层的厚度为2 μ m。 [0078] Select 36 μ m transparent PET film to the base film 1 to prepare a concentration of 30% by weight of vinyl acetate and butyl acrylate was treated with 100 line anilox roller is applied to the base film 1, in 50~70 ° C drying oven to obtain the base film 2 with a buffer layer, the buffer layer has a thickness of 2 μ m.

[0079] 调整刮刀与涂布头的间隙为180μπι,将上述的感光涂料涂布于已涂有缓冲层2, 厚度为30 μ m的PET膜上,在75 °C的对流干燥箱内烘干覆膜,涂层厚度为8 μ m,覆盖厚度为16微米的镀铝PET膜,获得用于全息记录的感光聚合物薄膜; [0079] The regulating blade and the coating head clearance for 180μπι, the above-described photosensitive coating applied to the buffer layer 2 has been coated with a thickness of 30 μ m on a PET film, dried in a convection drying oven of 75 ° C coating a coating thickness of 8 μ m, a thickness of aluminum covered with a PET film 16 m, to obtain a photosensitive polymer film for holographic recording;

[0080] 采用反射全息记录的方法,见图2,将上述的用于全息记录的感光聚合物薄膜裁切成30*30mm的片材,揭去表面保护膜4后,粘贴于反射镜43,用半导体固体激光器532nm记录光源300,通过带有针孔滤波器的扩束镜41和非球面准直凸透镜42形成平行光束301 其光强为lOOmw/cm2,辐射于用于全息记录的感光聚合物薄膜,平型光301从基膜1入射,经过缓冲层2和感光层3到达反射镜43或镀铝PET膜,原路反射回感光层,两束光干涉,将全息图记录在用于全息记录的感光聚合物薄膜上,然后在紫外固化机上对膜进行紫外和可见光全部曝光,120°C加热2分钟,即获得反射全息薄膜,反光膜的面积为50 X 50mm,其光强为lOOmw/cm2,该反光薄膜在一个角度观察为绿色,当改变观察角度后,便可见蓝色。 [0080] employing a reflective hologram recording method, shown in Figure 2, the above-mentioned photopolymer holographic recording film was cut into a 30 * 30mm sheet, peeled back surface protective film 4, attached to the mirror 43, recording semiconductor solid-state laser light source 300 532nm, 41 and aspheric collimating lens 42 is formed by a parallel beam with a beam expander, a pinhole 301 which filters light intensity lOOmw / cm2, irradiation at a holographic recording photopolymer thin, flat light is incident from the base film 301, through the buffer layer 2 and the photosensitive layer 3 to reflector 43 or aluminized PET film, the photosensitive layer is reflected back the same way, two beams of interference light, a hologram in a holographic recording photopolymer film record, and then the ultraviolet curing film for ultraviolet and visible overall exposure, 120 ° C for 2 minutes, that is to obtain the area of ​​the reflective holographic film, reflective film is 50 X 50mm, the light intensity of lOOmw / cm2, which was observed as green reflective film, when the observation angle is changed, it is visible blue at an angle.

[0081] 实施例5 [0081] Example 5

[0082] 反射全息薄膜的评定,可参照图2的方法,可以通过相干光“在轴”记录技术,在感光聚合物薄膜上进行全息成像记录。 [0082] Evaluation reflection hologram film, the method can be referred to FIG. 2, may be recorded by a coherent optical techniques "on-axis", recorded holographic image on the photosensitive polymer film.

[0083] 将上述的用于全息记录的感光聚合物薄膜,裁切成30*30mm的片材,揭去表面保护膜4后,平整的粘贴于反射镜43。 [0083] The above photopolymer holographic recording film is used, cut into sheets of 30 * 30mm, thrown off the surface protective film 4, attached to the flat mirror 43. 以波长532nm激光器为光源,光束300通过带有针孔滤波器的扩束镜41和非球面准直凸透镜42形成平行光束301辐射于感光聚合物薄膜,平型光301从基膜1入射,经过缓冲层2和感光聚合物涂层3到达反射镜43,原路反射回感光聚合物涂层3,形成记录光栅。 532nm wavelength laser as a light source, a beam 300 of radiation to form a parallel light beam 301 by the beam expander 41 and the filter with a pinhole collimator lens 42 aspheric photosensitive polymeric film from a flat light incident on the base film 301, after The buffer layer 2 and the photosensitive polymer coating 3 to reflector 43, back to the photopolymer coating are reflected back 3, the grating is formed recording. 辐射直径为15mm。 Radiation having a diameter of 15mm. 分别记录在同等光强下的不同记录时间的反射光栅。 Reflective grating different recording times are recorded in the same light intensity. 记录后的材料经高压水银汞灯固化,用S-53紫外-可见光分光光度计测试,设没有反射光栅处的透过率为Itl,测试每个不同曝光时间下反射光栅的最小透过率I,以及该点位置的波长λ,得到全息记录后的波长λ = 525nm、通过算式η = 1-1/%,计算得最大反射效率n = 85%、折射率调制=0. 031。 Recording material was cured by a high-pressure mercury lamp, with the S-53 UV - visible spectrophotometer testing, provided there is no reflection grating transmittance is at Itl, minimum permeability test of each reflection grating at different exposure times I , and the wavelength λ of the spot position, obtained after the holographic recording wavelength λ = 525nm, by the equation η = 1-1 /%, calculated maximum reflection efficiency n = 85%, the refractive index modulation = 0.031. 测试后的材料放入115°C的对流干燥烘箱,加热5分钟,再次用上述同样的方法进行测试,通过数据对比,得到材料的灵敏度为21. 2mj/cm2、 波长λ = 525nm、最大反射效率η = 99. 9 %、通过算式M =〔 λ tanh-1 V η〕/ ji d,计算得折射率调制=0.0763。 The test material was placed in 115 ° C convection drying oven, heated for 5 minutes, and tested again by the same method described above, by data comparison, the sensitivity of the material obtained was 21. 2mj / cm2, wavelength λ = 525nm, the maximum reflection efficiency η = 99. 9%, by the equation M = [λ tanh-1 V η] / ji d, calculated refractive index modulation = 0.0763. 检测结果表明材料在记录光栅未经热处理时,反射效率已经达到78%,而经热处理后,反射效率升高致99.9%,这种干法处理完全可以符合材料的要求。 When the detection result indicates that the recording material is not heat treated in the grating, the reflection efficiency of 78% has been reached, and after heat treatment, induced by increased reflection efficiency of 99.9%, this dry process can meet the material requirements. 经处理后的材料,分别进行酸碱及加湿处理,图像没有消退。 Was treated material, respectively and pH humidity treatment, not faded image.

Claims (11)

1. 一种全息感光涂料,其特征在于,包括感光聚合物涂料及与之匹配的溶剂,所述的感光聚合物涂料包括如下重量百分比的组分:成膜剂 20%〜80%纳米复合预聚体 4%〜20%单体 10%〜50%光引发剂 0.5%〜7%链转移剂 0.3%〜5%光敏剂 0.05%〜2%所述的纳米复合预聚体是一种末端位置上含有烯基基团的单体与纳米颗粒采用原位聚合方法制备的产物,所述的末端位置上含有烯基基团的单体为甲基丙烯酸甲酯、甲基丙烯酸丁酯或4-巯甲基苯乙烯;所述的纳米颗粒选自Ti02、Zn0或ZnS颗粒;纳米颗粒在纳米复合预聚体中的重量含量为0. 2%〜2% ;纳米复合预聚体的重均分子量为5000〜50000 ; 所述的成膜剂选自聚甲基丙烯酸甲酯、聚醋酸纤维素丁酯、醋酸纤维素丁酯与乙基乙烯基醚的共聚物、聚乙烯醇缩丁醛与醋酸纤维素的共混物、聚醋酸乙烯酯-丙烯酸丁酯-丙烯酸三元共聚物或聚 1. A holographic photosensitive coating material, wherein the photosensitive polymer coating comprising a solvent and a matching, said polymer coating comprising photosensitive components by weight percentage: 20% ~ 80% film former pre nanocomposite the poly ~20% 4% 10% ~ 50% monomer photoinitiator 0.5% to ~ 7% chain transfer agent, 0.3% ~ 5% 0.05% ~ 2% photosensitizer nanocomposite prepolymer is a terminal position the nanoparticle-containing monomer with an alkenyl group using the product prepared in situ polymerization method, a monomer containing alkenyl groups according to end position on methyl methacrylate, butyl methacrylate or 4- mercapto-methyl styrene; said nanoparticles are selected from Ti02, Zn0 or ZnS particles; nanoparticles nanocomposite body weight content of the prepolymer is 0.2% ~ 2%; nanocomposite weight average molecular weight of the prepolymer It is 5000~50000; forming agent is selected from polymethyl methacrylate, polybutyl cellulose acetate, cellulose butyl acetate copolymer and ethyl vinyl ether, polyvinyl butyral and acetic acid a blend of cellulose, polyvinyl acetate - butyl acrylate - acrylic acid terpolymer, or poly 乙烯丙烯腈,或上述聚合物与含氟聚合物的混合材料,所述的含氟聚合物选自三氟氯乙烯醋酸乙烯基醚的共聚物或四氟乙烯与乙基乙烯基醚的共聚物; 所述的单体选自单官能团或双官能团的丙烯酸酯类或N-乙烯基咔唑类中的一种以上。 Acrylonitrile, ethylene, or a mixed material of the polymer and a fluoropolymer, said fluoropolymer is selected from vinyl acetate copolymer of chlorotrifluoroethylene or tetrafluoroethylene ether and ethyl vinyl ether ; said monomer is selected from monofunctional acrylates or N- vinylcarbazole or difunctional in one or more.
2.根据权利要求1所述的全息感光涂料,其特征在于,纳米复合预聚体为含有ZnS颗粒的甲基丙烯酸甲酯的原位聚合产物或含有ZnS颗粒的4-巯甲基苯乙烯。 The hologram photosensitive material to the claim 1, wherein the nanocomposite in situ polymerization product of a prepolymer containing methyl methacrylate or ZnS particles containing 4-mercapto-methylstyrene ZnS particles.
3.根据权利要求1所述的全息感光涂料,其特征在于,光引发剂选自2,4,6_三苯基咪唑基双联体或联苯甲酰,光敏剂选自藻红B、二乙氨基-亚苄基环戊酮、米氏酮或1,3,3-三甲基-2-[5-(l,3,3-三甲基-2-吲哚叉)-1,3_戊二烯]吲哚碘盐,链转移剂选自2-巯基苯并噁唑、十二硫醇或巯基苯并噻唑,溶剂为丁酮/ 二氯甲烷/甲醇的混合溶剂,其重量比例为4 〜6 : 0.5 〜1.5 : 0.5 〜1.5。 The hologram photosensitive coating according to claim 1, wherein the photoinitiator is selected 2,4,6_ triphenyl imidazolyl double or dibenzoyl, the photosensitizer is selected from phycoerythrin B, diethylamino - benzylidene cyclopentanone, Michler's ketone, or 1,3,3-trimethyl--2- [5- (l, 3,3- trimethyl-2-indol-fork) -1, 3_ pentadienyl] indole salt, the chain transfer agent is selected from 2-mercaptobenzoxazole, dodecyl mercaptan, or a mercapto benzothiazole, and the solvent is acetone / methylene chloride / methanol mixed solvent, weight a ratio of 4 ~ 6: 0.5 ~ 1.5: 0.5 ~ 1.5.
4.根据权利要求1所述的全息感光涂料,其特征在于,所述的全息感光涂料的重量含固量为5% -50%。 According to claim 1 of the hologram photosensitive coating material, wherein the weight of the holographic photosensitive coating solids in an amount of 5% to 50%.
5.根据权利要求1〜4任一项所述的全息感光涂料,其特征在于,包括如下重量百分比的组分:成膜剂 30%〜70%纳米复合预聚体 8 %〜20 %单体 15. 0%〜40.0%光引发剂 2. 0^-7.0%链转移剂 1.0%〜3.0%光敏剂 0.5%〜2.0%。 5. The holographic photosensitive coating according to claim any one of claims 1 ~ 4, characterized in that it comprises the following components by weight percentage: 30% ~ 70% film former nanocomposite prepolymer of 8% ~20% monomer 15.0% ~40.0% photoinitiator 2.0 ^ -7.0% chain transfer agent, 1.0% ~3.0% 0.5% ~2.0% photosensitizer.
6.根据权利要求5所述的全息感光涂料,其特征在于,所述的感光聚合物涂料还包括感光聚合物涂料总重量0.5〜3%的增塑剂、0. 1〜的紫外吸收剂或0. 1〜的非离子表面活性剂中的一种以上;增塑剂选自邻苯二甲酸酯,烷基二酸酯、聚乙二醇羧酸酯或癸二酸二乙酯,紫外吸收剂选自2-羟基-4-甲氧基二苯甲酮或242H-苯并三唑-2)-4,6-二(1-甲基-1-苯乙基) 苯酚,非离子表面活性剂选自聚乙二醇、甲氧基聚乙二醇或氟素表面活性剂。 The hologram photosensitive coating according to claim 5, wherein said coating further comprises a photopolymer 0.5~3% of the total weight of the photosensitive polymer coating of a plasticizer, 0. 1 ~ UV absorber or 1 ~ 0. nonionic surfactant is one or more; plasticizer selected from phthalates, dialkyl esters, polyethylene glycol carboxylic acid ester or diethyl sebacate, ultraviolet absorbent selected from 2-hydroxy-4-methoxy-benzophenone or benzotriazole 242H- -2) -4,6-bis (1-methyl-1-phenylethyl) phenol, a nonionic surfactant active agent is selected from polyethylene glycol, methoxy polyethylene glycol and fluorine surfactants.
7. 一种用于全息记录的感光聚合物薄膜材料,其特征在于,包括基膜和涂复在基膜一侧上的缓冲层、涂复在缓冲层另一侧上的权利要求1〜6任一项所述的全息感光涂料形成的感光聚合物涂层和覆盖在感光聚合物涂料层表面的表面保护膜。 A photopolymer holographic recording film material, characterized in that, comprising a base film and a base film coated on one side of the buffer layer, coated on the other side of the complex as claimed in the buffer layer is required 1~6 and a photosensitive polymer coating covering the surface of the surface layer of the photosensitive polymer coating film according to any one of the protective hologram photosensitive coating formed.
8.根据权利要求7所述的用于全息记录的感光聚合物薄膜材料,其特征在于,干燥后的感光聚合物涂料层的厚度为3〜50 μ m。 8. The photosensitive polymer film material for hologram recording according to claim 7, characterized in that the polymer coating thickness of the photosensitive layer after drying was 3~50 μ m.
9.根据权利要求7所述的用于全息记录的感光聚合物薄膜材料,其特征在于,所述的基膜选自20〜100 μ m的PVC、PET或BOPP膜,厚度为20〜100 μ m ;所述的缓冲层材料为醋酸乙烯酯和丙烯酸酯类共聚物、偏氯乙烯苯乙烯醋酸乙烯酯共聚物或采用丙烯酸酯类光固化涂层,涂层厚度为1〜2 μ m ;所述的表面保护膜为有离型涂层的基材,厚度为16〜23 μ m的PET膜、BOPP膜、PE或PVC 膜。 9. The photosensitive polymer film material for hologram recording according to claim 7, wherein said base film is selected from the PVC 20~100 μ m, PET or BOPP film, having a thickness of 20~100 μ m; the buffer layer material is a vinyl acetate and acrylic copolymer, styrene-vinylidene chloride-vinyl acetate copolymer or an acrylic-based photo-curing a coating having a thickness of 1~2 μ m; the said surface protective film from the substrate there is a type of coating, the thickness is 16~23 μ m PET film, BOPP film, PE or PVC film.
10. 一种反射全息薄膜,其特征在于,在权利要求7、8或9任一项所述的感光聚合物薄膜材料的感光聚合物涂层上记录有全息图像或双变色图文的干涉条纹。 10. A reflective holographic film, characterized in that the recording on the photosensitive coating film polymeric material as claimed in claim 7, 8 photopolymer according to any one of claims 9 or hologram interference fringes or dual color graphic .
11.根据权利要求10所述的反射全息薄膜的制备方法,包括如下步骤:(1)涂布材料的制备:在避光条件或在红色光线下,按比例将成膜剂、纳米复合预聚单体、单体、引发剂和光敏剂加到溶剂中,搅拌溶解,获得权利1〜6任一项所述的全息感光涂料;(2)用于全息记录的感光聚合物薄膜材料的制备:在涂布基膜上涂布缓冲层,在避光条件或在红色光线下,将步骤(1)的感光涂料,涂布在已有缓冲层的基膜上,在65-75°C下干燥1〜5分钟,干燥后覆盖保护膜,即获得用于全息记录的感光聚合物薄膜材料;(3)反射全息薄膜的制备:将步骤O)的产物揭开保护膜,采用反射全息记录方法,将全息图记录在感光聚合物薄膜材料上,然后在紫外固化机上对膜进行紫外和可见光全部曝光,120°C加热2〜50分钟,即获得反射全息薄膜。 11. A method for preparing a thin film of the reflection hologram according to claim 10, comprising the steps of: preparing a coating material (1): dark conditions or under red light, in proportion to the film former, the prepolymerization nanocomposite monomers, monomer, initiator and a photosensitizer added to a solvent, dissolved by stirring to obtain a photosensitive coating of claim 1~6 according to any one of the hologram; (2) preparation of film material for holographic recording photopolymer: coating the base coating film in the buffer layer, dark conditions or under red light, in step (1) of the photosensitive coating applied onto a base film prior buffer layer, dried at 65-75 ° C ~ 5 minutes, covered with a protective film after drying, i.e., to obtain a photopolymer holographic recording film material; (3) preparation of a reflective hologram film: step O) the product, remove the protective film, reflective hologram recording method, the hologram recorded on the photosensitive material is a polymer film, then the film is exposed to ultraviolet and visible on all of the UV curing machine, 120 ° C heating 2~50 minutes, i.e., reflection hologram film is obtained.
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