CN1229691C - Photopolymer holographic storage material consisting of high-refractive-index epoxy resin and low-refractive-index vinyl monomer and preparation method thereof - Google Patents

Abstract

The invention belongs to the field of volume holographic photopolymer storage materials, and relates to a photopolymer volume holographic storage material composed of high refractive index epoxy resin and low refractive index monomer and a preparation method thereof. Under the protection of red light or light protection, the system is calculated by weight percentage, 15% to 45% of vinyl monomer, 0.01% to 0.1% of photosensitizer, 0.1% to 0.9% of photoinitiator, 0.1% to 1.0% Chain transfer agent, 0.1%~1.0% defoamer, 0.1%~1.0% leveling agent, 3%~15% epoxy resin reactive diluent and 30%~70% epoxy resin are mixed evenly , form a transparent sol solution; then add 5%-15% epoxy resin curing agent to the sol solution, mix it evenly and pour it into the container, after curing, the photopolymer body holographic storage material of the present invention is obtained . The preparation method is simple to operate, and a storage material with any volume and thickness can be prepared under room temperature conditions; the material has no shrinkage during the information recording process, and the stored information is stable and has a large amount of stored information.

Description

Photopolymer body holographic storage material composed of high refractive index epoxy resin and low refractive index ethylenic monomer and preparation method thereof

                      

The invention belongs to the field of volume holographic photopolymer storage materials, in particular to a photopolymer volume holographic storage material composed of high refractive index epoxy resin and low refractive index vinyl monomer and a preparation method thereof.

Background technique

The rapid growth of the amount of information has made traditional storage materials less and less able to meet people's needs for massive information storage. Many new storage materials and storage technologies have emerged. Among them, optical holographic storage has become popular in recent years due to its high redundancy, high storage capacity, fast data transmission rate and storage time, and parallel content addressing. attention. There are also many studies on its related storage materials. Photopolymerized refractive index change materials have become the research focus because of their high signal-to-noise ratio, high diffraction efficiency, low cost, convenient processing, good stability, and full "dry" processing. hotspot. So far, there are many photopolymer materials used for volume holographic storage reported, such as: the photopolymerizable film material-HRF series (U.S.Pat.No.5,470,662) for volume holographic storage of U.S. DuPont company, Polaroid company's ULSH series materials (U.S.Pat.No.5,759,721), etc., but based on the design principle, these materials all use a low refractive index matrix to match the high refractive index monomer molecules, and the volume of the material will shrink after the polymerization of the monomer is triggered by light. , thereby affecting the quality of recorded information. Moreover, due to the limitations of the manufacturing process of the existing materials, it is difficult to increase the thickness of the materials, and the information storage capacity is limited. These problems greatly limit its wide application.

Contents of the invention

One of the objectives of the present invention is to solve the problems of volume shrinkage, difficult increase in thickness and limited storage capacity of traditional photopolymer materials used in volume holographic storage, and provide a kind of epoxy resin with high refractive index as the matrix material. 1. A photopolymer volume holographic storage material containing polymerizable low-refractive-index ethylenic monomers, which does not shrink in volume during the volume holographic recording process.

Another object of the present invention is to combine the principle of photopolymer volume holographic storage to provide a method for preparing non-shrinkage volume holographic storage materials of different thicknesses with simple operation and low cost at room temperature.

The photopolymer material composed of high-refractive-index epoxy resin and low-refractive-index ethylenic monomers provided by the present invention can undergo photopolymerization under the action of light, and the low-refractive-index monomers migrate and concentrate at the same time to form polymerized Due to the refractive index difference between objects, the refractive index modulation of the light and dark parts of the grating appears. Using this principle, information can be recorded on the material.

The photopolymer volume holographic storage material provided by the present invention is a solid phase material, which can be of any desired volume depending on the volume holographic storage requirements. The material contains an epoxy resin matrix with a high refractive index and a polymerizable The low-refractive-index ethylenic monomers, the system is by weight percentage, and its composition and content are:

Epoxy resin 30% to 70%;

Vinyl monomers 15% to 45%;

Photosensitizer 0.01%～0.1%;

Photoinitiator 0.1%～0.9%;

Chain transfer agent 0.1%～1.0%;

Defoamer 0.1%～1.0%;

Leveling agent 0.1%～1.0%;

Epoxy resin curing agent 5% to 15%;

Epoxy resin reactive diluent 3% to 15%;

The photopolymer body holographic storage material of the present invention takes epoxy resin as the matrix, and the epoxy resin is mainly an epoxy resin compound with a high refractive index and a rigid benzene ring structure, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated novolac type epoxy resin, brominated bisphenol A type epoxy resin or a combination of these compounds Any ratio mixture.

The ethylenic monomers used in the present invention are various monofunctional or polyfunctional groups containing C=C unsaturated double bonds and a class of small molecule compounds with a lower refractive index relative to the epoxy resin matrix, such as various acrylic acid Esters such as methyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, isobornyl acrylate, tridecyl acrylate, glycidyl methacrylate, Tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate or dipentaerythritol pentaacrylate; other ethylenic monomers, such as vinyl acetate or acrylonitrile, can undergo addition polymerization of low refractive index monomers body; or a mixture of any ratio between the monomers.

The photosensitizer is various types of dyes with higher electron transfer efficiency, such as cyanine dyes, fluorescein dyes, coumarin ketone dyes, nitrogen-containing aromatic heterocyclic compounds, aromatic amine compounds, benzylidene Cycloalkane ketone compounds or mixtures of these compounds in any ratio, etc.

The photoinitiator is an onium salt, such as an iodonium salt or a sulfonium salt, etc.; a bis-imidazole, such as a hexaaryl bis-imidazole, etc.; an organometallic compound, such as a titanocene compound, a ferrocene salt or an aluminate Salt complexes, etc.; organic borides, such as butyl triphenyl borate, etc.; benzophenone or Michler's ketone; various alkyl-substituted thioxanthones; acetophenone derivatives, such as α-hydroxy - cyclohexyl acetophenone, etc.; benzoin ethers, such as benzoin dimethyl ether, etc.; α-aminoketones, such as Irgacure-907 or Irgacure-369 produced by Ciba; and α-hydroxy ketones, such as produced by Ciba Darocur-1173 or Darocur-4265; or the mixture of any ratio between these photoinitiators, etc.

The chain transfer agent is a thiol compound, such as dodecyl mercaptan, 4-methyl-4H-1,2,4-triazole-3-thiol or a mixture thereof in any proportion.

The epoxy resin curing agent used in the present invention is a medium and low temperature curing agent with a curing temperature of ≤60°C, such as triethylenetetramine, diethylenetriamine, tetraethylenepentamine, divinylpropylamine, N-aminoethylpiperazine , 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxa spiroundecane adduct, m-xylylenediamine or a mixture of these compounds in any ratio, etc.

The defoamer is a silicone defoamer, such as BYK-065, BYK-066, BYK-088, BYK-141 produced by BYK Company, or a mixture of them in any proportion.

The leveling agent is a silicone surface additive, such as BYK-306, BYK-310, BYK-344 produced by BYK, Deqian 455 and 466 produced by Deqian, or a mixture of them in any proportion.

The epoxy resin reactive diluent can be epichlorohydrin, oxirane, 1,2-propylene oxide, n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether , styrene oxide, phenyl glycidyl ether, cresol glycidyl ether, p-tert-butylphenyl glycidyl ether, tertiary carboxylic acid glycidyl ester, diglycidyl ester, polyethylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, butanediol diglycidyl ether, glycerol triglycidyl ether or a mixture of these compounds in any proportion.

The steps of the preparation method of the photopolymer body holographic storage material provided by the present invention are as follows, and the system is calculated by weight percentage:

(1) Preparation of photopolymer sol solution

Under the protection of red light or light protection, in a container equipped with stirring equipment, add 15% to 45% of vinyl monomers, 0.01% to 0.1% of photosensitizers, and 0.1% to 0.9% of photoinitiating agent, 0.1%~1.0% chain transfer agent, 0.1%~1.0% defoamer, 0.1%~1.0% leveling agent, 3%~15% epoxy resin reactive diluent and 30%~70% The epoxy resin is stirred until a single transparent sol solution is formed;

(2) Curing and forming of photopolymer sol solution

Under the protection of red light or light protection, add 5%-15% epoxy resin curing agent of the system to the sol solution obtained in step (1). The photopolymer body holographic storage material of the present invention is obtained by curing under the following conditions.

In the preparation method provided by the present invention, in the step (1), first add 15% to 45% of ethylenic monomer, 0.01% to 0.1% of photosensitizer, 0.1% to 0.9% of Photoinitiator, 0.1%~1.0% chain transfer agent, 0.1%~1.0% defoamer and 0.1%~1.0% leveling agent, stir at room temperature until uniform, and then add 3%~15% Continue to stir and dissolve the epoxy resin active diluent and 30% to 70% epoxy resin until a single transparent sol solution is formed.

In the preparation method provided by the present invention, in the step (2), after adding 5%-15% epoxy resin curing agent to the sol solution obtained in the step (1), stir at room temperature for 10-15 minutes, It can be mixed evenly; the curing time and temperature depend on the type of curing agent used, such as triethylenetetramine, curing at room temperature, the time is 3 days; curing with m-xylylenediamine, curing at 60°C, the time is 1 hour.

The preparation method of the photopolymer body holographic storage material composed of high-refractive-index epoxy resin and low-refractive-index ethylenic monomer provided by the invention has simple operation, can be solidified and molded at room temperature, and the thickness of the material can be controlled. According to the maximum absorption wavelength of the photosensitizer used, a laser with an appropriate wavelength can be selected for information storage to realize the mass storage function of information.

The photopolymer material for volume holographic storage and its preparation method provided by the present invention have the following significant advantages:

1. The preparation method of the material is simple to operate, and a storage material of any volume can be prepared at room temperature, and the cost is low, so the material of the present invention has broad application prospects.

2. Compared with traditional photopolymer materials for holographic storage, no volatile solvents are added in the production process of this material, the production cycle is short and the information storage process is not disturbed by residual solvents, and the stored information has no deformation.

3. Different from the design ideas of traditional photopolymer materials for holographic storage, the material of the present invention uses a rigid high-refractive-index matrix to match with a flexible low-refractive-index small molecule monomer, which realizes no shrinkage of the material during the information recording process, and storage The information is stable, achieving high-quality storage and reproduction of information.

4. Since the production process of this material is not limited by thickness, it can be used as a volume holographic storage material to realize mass storage of information.

5. After the information recording of this material is completed, the storage period is long, the recorded information is stable, the weather resistance is strong, and it is less affected by environmental factors.

Detailed ways

The present invention is specifically described below in conjunction with the examples.

Example 1

Under the protection of a red light, add 30 grams of methyl methacrylate, 0.01 grams of 2,5-bis[4-(dimethylamino)-benzylidene]cyclopentanone, 0.35 grams of Hexaarylbisimidazole, 0.41 g 4-methyl-4H-1,2,4-triazole-3-thiol, 5 g epichlorohydrin, 50 g bisphenol A epoxy 618, 0.1 g BYK-066 and 0.1 gram of BYK-306, mixed thoroughly to form a transparent sol solution; then added 12 grams of triethylenetetramine to the transparent sol solution, stirred at room temperature for 15 minutes, and then injected the mixed solution with a volume of 76mm×26mm×0.8 mm glass container, after curing at room temperature for 24 hours, and then curing at 45 ° C for 24 hours, the photopolymer material capable of volume holographic storage can be obtained. Using an argon ion laser with a wavelength of 514.5nm as the light source, the reference light intensity is 5mW/cm ² , and the maximum light intensity in the object light is 2.4mW/cm ² , and the image information can be processed at the same position through angle multiplexing technology. Holographic storage.

Example 2

Using the following formula, the photopolymer material was prepared according to the method of Example 1.

Bisphenol A epoxy 618 60g

Vinyl acetate 20 g

Epichlorohydrin 10 grams

2,5-bis[4-(dimethylamino)-benzylidene]cyclopentanone 0.01g

Diphenyliodonium salt 0.4 g

4-methyl-4H-1,2,4-triazole-3-thiol 0.41 g

BYK-066 0.1g

BYK-306 0.1g

Tetraethylenepentamine 12 grams

The difference from Embodiment 1 is that curing is performed at room temperature to obtain a photopolymer material capable of volume holographic storage. Using an argon ion laser with a wavelength of 514.5nm as the light source, the reference light intensity is 5mW/cm ² , the maximum light intensity in the object light is 2.4mW/cm ² , and the angle between the reference light and the object light is 30 degrees. Angle multiplexing technology can carry out holographic storage of image information.

Example 3

Using the following formula, the photopolymer material was prepared according to the method of Example 1.

Bisphenol F epoxy 50g

Methyl acrylate 30 grams

Styrene oxide 5 g

Tetraiodofluorescein 0.03 g

Hexaarylbiimidazole 0.35g

4-methyl-4H-1,2,4-triazole-3-thiol 0.41 g

BYK-354 0.1g

BYK-344 0.11g

m-xylylenediamine 10 grams

The difference from Embodiment 1 is that curing is performed at room temperature to obtain a photopolymer material capable of volume holographic storage. Using an argon ion laser with a wavelength of 488nm as the light source, the ratio of light intensity to object is 1:1, the angle between reference light and object light is 90 degrees, and the holographic storage of image information can be carried out at the same position through angle multiplexing technology.

Example 4

Using the following formula, the photopolymer material was prepared according to the method of Example 1.

Novolac epoxy resin 40g

Ethyl Acrylate 40g

1,2-propylene oxide 5 grams

Tetraiodofluorescein 0.03 g

Hexaarylbiimidazole 0.35g

Dodecylmercaptan 0.5g

BYK-066 0.1g

BYK-306 0.1g

Divinylpropylamine 10 grams

The difference from Embodiment 1 is that curing is performed at room temperature to obtain a photopolymer material capable of volume holographic storage. Using an argon ion laser with a wavelength of 488nm as the light source, the ratio of light intensity to object is 1:1, the angle between reference light and object light is 90 degrees, and the holographic storage of image information can be carried out at the same position through angle multiplexing technology.

Example 5

According to the method of Example 1, the photopolymer material was prepared according to the following formula.

Brominated Novolac Epoxy Resin 60g

Tridecyl acrylate 20g

Epichlorohydrin 10 grams

2,5-bis[4-(dimethylamino)-benzylidene]cyclopentanone 0.01 g

Diphenyliodonium salt 0.4 g

4-methyl-4H-1,2,4-triazole-3-thiol 0.41 g

BYK-066 0.1g

BYK-358 0.12g

N-Aminoethylpiperazine 12g

The difference from Embodiment 1 is that curing is performed at room temperature to obtain a photopolymer material capable of volume holographic storage. Using an argon ion laser with a wavelength of 514.5nm as the light source, the reference light intensity is 5mW/cm ² , the maximum light intensity in the object light is 2.4mW/cm ² , and the angle between the reference light and the object light is 30 degrees. Angle multiplexing technology can carry out holographic storage of image information.

Claims (5)

1. the photopolymerization object holographic storage material formed of high index of refraction epoxy resin and low-refraction vinyl monomer, it is a kind of solid phase material, it is characterized in that, this material contains the epoxy resin-base thing of high index of refraction and the vinyl monomer of polymerisable low-refraction, system by weight percentage, it is formed and content is:

Epoxy resin 30%～70%;

Vinyl monomer 15%～45%;

Photosensitizer 0.01%～0.1%;

Light trigger 0.1%～0.9%;

Chain-transferring agent 0.1%～1.0%;

Defoamer 0.1%～1.0%;

Levelling agent 0.1%～1.0%;

Epoxy curing agent 5%～15%;

Epoxide resin reactive diluent 3%～15%;

Wherein: described chain-transferring agent is a sulfur alcohol compound; Described defoamer is a silicone defoaming agent; Described levelling agent is an organosilicon surface auxiliary agent;

Described epoxy resin be bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, linear phenol aldehyde type epoxy resin, bisphenol-A epoxy resin, bromination phenol aldehyde type epoxy resin, brominated bisphenol a type epoxy resin or these compounds arbitrarily than potpourri;

Described vinyl monomer is acrylate, vinyl acetate, vinyl cyanide or the potpourri of arbitrary proportion between them;

Described photosensitizer is cyanine type dye, fluoresceins dyestuff, cumarin ketone dyestuff, nitrogenous heteroaromatic compounds, aromatic amine compounds, benzal cyclanone compound or the potpourri of arbitrary proportion between them;

Described light trigger is that salt, two imidazoles, organometallics, organic boride, benzophenone, michaelis ketone, alkyl replace thioxanthone, acetophenone derivs, styrax ethers, alpha-amido ketone, Alpha-hydroxy ketone or the potpourri of arbitrary proportion between them;

Described epoxy curing agent is triethylene tetramine, diethylenetriamine, TEPA, divinyl propylamine, N-aminoethyl piperazine, 3, two (the 3-aminopropyls)-2 of 9-, 4,8, the potpourri of arbitrary proportion between 10-four oxaspiro undecane adducts, m-xylene diamine or these hardening agent;

Described epoxide resin reactive diluent is epichlorokydrin, oxirane, 1,2-epoxypropane, n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidol ether, styrene oxide, phenyl glycidyl ether, cresylglycidylether, to tert-butyl-phenyl glycidol ether, three grades of carboxylic acid ethylene oxidic esters, 2-glycidyl ester, poly-ethanol diglycidyl ether, polypropylene glycol diglycidyl ether, butanediol diglycidyl ether, glycerine triglycidyl ether or the potpourri of arbitrary proportion between them.

2. photopolymerization object holographic storage material as claimed in claim 1, it is characterized in that described interior olefin(e) acid ester is methyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate, isobornyl acrylate, tridecyl acrylate, glycidyl methacrylate, tri (propylene glycol) diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate or dipentaerythritol five acrylate.

3. photopolymerization object holographic storage material as claimed in claim 1 is characterized in that described salt is salt compounded of iodine or sulfosalt; Described pair of imidazoles is hexa-aryl bi-imidazole; Described organometallics is two luxuriant titanium compounds, ferrocene salt or aluminate complex compound; Described organic boride is the butyl triphenyl borate; Described acetophenone derivs is Alpha-hydroxy-cyclohexyl benzene ethyl ketone; Described styrax ethers is a benzoin dimethylether; Irgacure-907 or Irgacure-369 that described alpha-amido ketone is produced for vapour Bagong department; Darocur-1173 or Darocur-4265 that described Alpha-hydroxy ketone is produced for vapour Bagong department.

4. photopolymerization object holographic storage material as claimed in claim 1 is characterized in that, described sulfur alcohol compound is lauryl mercaptan, 4-methyl-4H-1,2, and the potpourri of 4-triazole-3-mercaptan or its arbitrary proportion; BYK-065, BYK-066, BYK-088, the BYK-141 that described silicone defoaming agent is produced for BYK company or it is arbitrarily than potpourri; The moral that the modest company of BYK-306, BYK-310, BYK-344, moral that described organosilicon surface auxiliary agent is produced for BYK company produces is modest 455, moral modest 466 or it is arbitrarily than potpourri.

5. preparation method as any described photopolymerization object holographic storage material of claim 1～4 is characterized in that this method step is as follows:

(1) preparation of photopolymer sol solution

Under red light or lucifuge protection, in the container of mixing plant is housed, add 15%～45% vinyl monomer, 0.01%～0.1% photosensitizer, 0.1%～0.9% light trigger, 0.1%～1.0% chain-transferring agent, 0.1%～1.0% defoamer, 0.1%～1.0% levelling agent, 3%～15% epoxide resin reactive diluent and 30%～70% the epoxy resin of system respectively, stir until the sol solution that forms single transparent;

(2) curing molding of photopolymer sol solution

Under red light or lucifuge protection; in the sol solution that step (1) obtains, add the epoxy curing agent of the 5%-15% of system, after mixing, be poured in the container; under room temperature～60 ℃, be cured, promptly make photopolymerization object holographic storage material.