CN103091984A - Preparation method of laser holographic display photopolymer film - Google Patents
Preparation method of laser holographic display photopolymer film Download PDFInfo
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- CN103091984A CN103091984A CN2011103384461A CN201110338446A CN103091984A CN 103091984 A CN103091984 A CN 103091984A CN 2011103384461 A CN2011103384461 A CN 2011103384461A CN 201110338446 A CN201110338446 A CN 201110338446A CN 103091984 A CN103091984 A CN 103091984A
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Abstract
The invention relates to a laser holographic display photopolymer film composition and a preparation method thereof. According to the invention, under a red light condition, indanone, bisimidazole (O-CL-HABI), epoxy resin, and acetic anhydride are dissolved into a mixed solution of dichloropropane and methanol; the composition solution is coated on transparent PETG (poly(ethylene terephthalate)1,4-cyclohexane dimethylene terephthalate); and heating and curing are carried out in a convection constant-temperature box, such that the composition is prepared. The film has high diffraction efficiency and good light transmission performance. With the film, defects of poor storability and easy loss of image of the materials obtained with prior arts are overcome, and problems of over sensitivity to environmental humidity and easy volatilization of raw materials are effectively solved.
Description
Technical field
The present invention relates to the preparation method that a kind of laser hologram shows photic thin polymer film.
Background technology
Holographic high-tech crystallization as a kind of multidisciplinary intersection has obtained using extremely widely in fields such as 3-D display, three-dimensional storage, optical elements.As the laser holographic recording material, using at present is silver halide material more widely, dichromated gelatin material and photosensitive polymer material.
Being applied in of holography depends on to a great extent whether suitable hologram recording material is arranged, and in holographic material commonly used, silver salt has high sensitivity, but diffraction efficiency is lower, even adopt the method for bleaching or dilute development, diffraction efficiency also only reaches 40% left and right.The hologram of making of dichromated gelatin has very high diffraction efficiency, can reach more than 90%, the laser jewel that is commercially available, and much holographic elements are all made with this material, but it also has disadvantageous factor, and are as low in light sensitivity, light sensitive plate will be with using with making, can not long preservation etc., its deadly defect is to be subjected to the impact of environment very large with the hologram that this material is made, and is easy to the picture that disappears in the larger environment of humidity ratio.The photopolymer material can overcome the shortcoming of above-mentioned material.
At present, photopolymer is mainly used in false proof and looks squarely field of display, uses dichromated gelatin to make green sensitization holographic material in order to improve, and this manufacture craft is very strict to the requirement of environment, is not easy to large-scale production, and cost of manufacture is more expensive.
Therefore, the present invention has developed emphatically novel photosensitive material.The photopolymer Materials For Holography of newly developing has high-diffraction efficiency, long shelf-life, higher sensitivity, does not need the remarkable advantages such as chemical reagent processing and protection against the tide, and its spectral response is wide, processes easy.
Summary of the invention
The object of the present invention is to provide a kind of brand-new holographic photic polymeric material, by designing effective photosensitized initiation system, provide the technique of making hologram reflection-type photo-induced polyalcohol dry film.
In order to use in producing and processing more extensive and more easily, the present invention has changed initiating agent in the past and mainly could activate by the irradiation in ultraviolet spectrum district, the more effective various advantages of utilizing semiconductor laser are designed to light initiation system in visible range irradiation activation.Therefore, in the present invention, the configuration of light initiation system just seems even more important.
In all kinds of patents in the past, when relating to the light-initiated effect of visible spectrum, what great majority adopted is to affix one's name to the various dyestuffs such as red and methylene blue as the emulsion in light initiation system, but self instability of this dyestuff or dyestuff intermediate can cause photosensitive high molecular generation xanthochromia, embrittlement, and be difficult for very much preserving.
The invention provides and a kind ofly be essentially on photo-conductive film element solid, transparent by following preparation method the method that forms reflection hologram.
Reflection-type photo-induced polyalcohol film composite of the present invention, said composition is composed of the following components by weight percentage:
Because a lot of compounds that produce free radical all can be used in practical application of the present invention, the present invention has used a kind of reasonable dual initiator pattern.
through verification experimental verification, by indone and two imidazoles (O-CL-HABI) the photosensitive initiated polymerization system that can realize circulating, energy by the indone absorbing laser is more adjourned excited state, then generate exciplex with two imidazoles, then resolve into imidazole radical, wherein a part of son has basic trigger monomer polymerization, another part has basic bis oxide indanol, generate two indolones, this product and two imidazoles are under the effect of 410nm light, generate new bimolecular imidazole radical and indanol, thereby form the photosensitive initiated polymerization system of light circulation, greatly improved light sensitivity, up to 0.1mj/cm2.
The method for preparing the reflection-type photo-induced polyalcohol composition is characterized in that the method is comprised of following steps successively:
A) the propylene dichloride solution with 10% methanol solution and 90% mixes;
B) under the ruddiness condition, indone and two imidazoles (O-CL-HABI) are dissolved in the mixed solution of propylene dichloride and methyl alcohol;
C) epoxy resin, acrylic acid halo phenyl ester and acetic anhydride are dissolved in the mixed solution of propylene dichloride and methyl alcohol;
D) stir, until without any sediment;
E) mixed solution with final gained is coated on transparent PETG (polyethylene terephthalate-Isosorbide-5-Nitrae-cyclohexanedimethanol ester) uniformly;
F) be heating and curing at the temperature of 50 degrees centigrade;
G) coherent source exposes in film both sides, the recording body hologram;
H) heated 90 minutes at the temperature of 150 degrees centigrade;
I) stripping film.
The body of substrate support preferably that the present invention selects is PETG (polyethylene terephthalate-1 of modification, 4-cyclohexanedimethanol ester), the photosensitive high molecular solution that coating has prepared on the thin slice of PETG, heat in the convection current constant temperature oven of 150 degrees centigrade, make its surface cure, also can add again one deck polychloroethylene film as protection as needs; The substrate of PETG can keep, and also can depending on the circumstances or the needs of the situation light-sensitive surface be peeled off from the PETG substrate.
Embodiment
Further illustrate the present invention below by embodiment.In following examples, the reflection efficiency numerical value of film is higher, illustrates that the optical effect of film is better, and has spectrum selectivity uniqueness, and the photo-conductive film that has made has good thermal stability and water tolerance.
Embodiment 1
Configuration sensitization liquid will carry out under red light, and sensitizer is 5-chlorine indone, and initiating agent is two imidazoles O-CL-HABI, and monomer is selected acrylic acid 2,4,6 bromo phenyl esters, and film forming matter is epoxy resin, synthetic accelerator acetic anhydride.With above-mentioned medicine by a certain percentage order put into conical flask, with the solvent of methyl alcohol and propylene dichloride, it is dissolved one by one, after sensitization liquid prepares, it is coated on glass chip, then be placed on levelling bench natural drying.
Recording beam path figure as shown in Figure 1, record the reflective holographic grating, the laser beam that laser instrument 1 sends is first regulated through beam expanding lens 3, again through collimating mirror 4, then by beam splitter 5, laser is divided into the two-beam line, via catoptron 6, make this two bundle each other the light beam of ginseng, object light incide on recording sheet from the both sides of recording dry plate 7, in the equivalent optical path of reference light and object light will note the accommodation reflex mirror time.In addition, shutter 2 is used for controlling the time shutter.
Dry plate after exposure is taken out from recording beam path, be placed under the high pressure pumping lamp, to ultraviolet light and visible light exposure, carry out " photodevelopment "; Be placed on again in baking oven under 150 ℃ of conditions, heated 30～120 minutes, carry out " hot photographic fixing ".
Arrive the response of bandwidth due to the thickness effect of film, this method pays attention to realizing wide bandwidth response, and once the film thickness of preparation is chosen in about 20 μ m, can make like this film comprise more reflection strip.
If want to make prepared film to use very flexible and more easily; the preparation method of film can be adjusted into above-mentioned photosensitive material is spread upon on the film of clear PET G of 0.05 millimeter; and then cover with the equal material of 0.02 millimeter, realize the defencive function to photosensitive material.When using, peel off the protection protective seam, directly photosensitive material is affixed to desired area and get final product.
List the test figure result in following table 1.
Embodiment 2
Repeat the method for embodiment 1 according to the each component content of appointment in following table 1, but replace acrylic acid 2,4,6 bromo phenyl esters with acrylic acid 5 chloro phenyl esters, list the test figure result in table 1.
Repeat the method for embodiment 1 according to the each component content of appointment in following table 1, but replace 5-chlorine indone with acrylic acid 4-bromindion, list the test figure result in table 1.
Embodiment 4
Repeat the method for embodiment 1 according to the each component content of appointment in following table 1, but replace 5-chlorine indone with acrylic acid 4-bromindion, replace acrylic acid 2,4,6 bromo phenyl esters with acrylic acid 5 chloro phenyl esters, list the test figure result in table 1.
Table 1
Claims (7)
1. a laser hologram shows photic thin polymer film composition, and said composition is composed of the following components by weight percentage:
2. according to film composition claimed in claim 1, wherein the content of epoxy resin is 45～75%.
3. according to film composition claimed in claim 1, wherein the content of acetic anhydride is 0～15%.
4. according to film composition claimed in claim 1, wherein the content of acrylic acid halo phenyl ester is 15～50%.
5. according to film composition claimed in claim 1, it is acrylic acid chloro phenyl ester and bromo phenyl ester that acrylic acid halo phenyl ester wherein is selected from.
6. according to film composition claimed in claim 1, indone wherein is selected from 5-chlorine indone and 4-bromindion.
7. prepare the method for the described film composition of claim 1, the method is comprised of following steps:
A) under the ruddiness condition, indone and two imidazoles (O-CL-HABI) are dissolved in propylene dichloride and methyl alcohol and form solution;
B) epoxy resin, acrylic acid halo phenyl ester and acetic anhydride are dissolved in propylene dichloride and methyl alcohol form solution;
C) all components are mixed, mechanical raking is to even;
D) with the solution coat that mixes on transparent PETG (polyethylene terephthalate-Isosorbide-5-Nitrae-cyclohexanedimethanol ester);
E) be heating and curing at the temperature of 50 degrees centigrade;
F) coherent source exposes in film both sides, the recording body hologram;
G) heated 90 minutes at the temperature of 150 degrees centigrade;
H) stripping film.
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| CN2011103384461A CN103091984A (en) | 2011-11-01 | 2011-11-01 | Preparation method of laser holographic display photopolymer film |
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| CN2011103384461A CN103091984A (en) | 2011-11-01 | 2011-11-01 | Preparation method of laser holographic display photopolymer film |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109697941A (en) * | 2018-12-29 | 2019-04-30 | 广州欧科信息技术股份有限公司 | Historical and cultural heritage display systems based on hologram technology |
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| CN1972995A (en) * | 2004-06-21 | 2007-05-30 | 积水化学工业株式会社 | Binder resin composition, paste, and green sheet |
| CN101034257A (en) * | 2007-04-06 | 2007-09-12 | 上海复旦天臣新技术有限公司 | Photosensitive film used for holographic recording and manufacturing method |
| CN101231362A (en) * | 2007-01-25 | 2008-07-30 | 李妤 | Preparation of hologram reflection-type photo-induced polyalcohol dry film |
| JP2008181143A (en) * | 2003-09-09 | 2008-08-07 | Mitsubishi Chemicals Corp | Blue-violet laser-sensitive composition, and image forming material, photosensitive image forming material and image forming method using the same |
| CN102054498A (en) * | 2009-11-09 | 2011-05-11 | 中国科学院理化技术研究所 | Method for preparing photopolymer holographic storage optical disk |
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- 2011-11-01 CN CN2011103384461A patent/CN103091984A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008181143A (en) * | 2003-09-09 | 2008-08-07 | Mitsubishi Chemicals Corp | Blue-violet laser-sensitive composition, and image forming material, photosensitive image forming material and image forming method using the same |
| CN1972995A (en) * | 2004-06-21 | 2007-05-30 | 积水化学工业株式会社 | Binder resin composition, paste, and green sheet |
| CN101231362A (en) * | 2007-01-25 | 2008-07-30 | 李妤 | Preparation of hologram reflection-type photo-induced polyalcohol dry film |
| CN101034257A (en) * | 2007-04-06 | 2007-09-12 | 上海复旦天臣新技术有限公司 | Photosensitive film used for holographic recording and manufacturing method |
| CN102054498A (en) * | 2009-11-09 | 2011-05-11 | 中国科学院理化技术研究所 | Method for preparing photopolymer holographic storage optical disk |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109697941A (en) * | 2018-12-29 | 2019-04-30 | 广州欧科信息技术股份有限公司 | Historical and cultural heritage display systems based on hologram technology |
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Application publication date: 20130508 |