CN106008977A - Holographic recording material and preparation method thereof - Google Patents
Holographic recording material and preparation method thereof Download PDFInfo
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- CN106008977A CN106008977A CN201610343055.1A CN201610343055A CN106008977A CN 106008977 A CN106008977 A CN 106008977A CN 201610343055 A CN201610343055 A CN 201610343055A CN 106008977 A CN106008977 A CN 106008977A
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- recording material
- polyfunctionality
- hologram recording
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- 0 CCCC(C1)=CCC1C1*2(CCC2)C1*C Chemical compound CCCC(C1)=CCC1C1*2(CCC2)C1*C 0.000 description 3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
- C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
Abstract
The invention discloses a holographic recording material and a preparation method thereof. The holographic recording material is prepared from the following ingredients in percentage by mass: 8 percent to 60 percent of polyfunctionality thioalcohol monomers, 8 percent to 60 percent of polyfunctionality acrylic ester monomers and 8 percent to 60 percent of polyfunctionality allyl monomers, wherein the polyfunctionality thioalcohol monomers contain 12 to 20-CH2- bonds and at least two mercapto groups; the polyfunctionality acrylic ester monomers contain 10 to 20 -CH2- bonds and at least two electron-defect carbon-carbon double bonds; the polyfunctionality allyl monomers contain 8 to 18 -CH2- bonds and at least two electron-rich carbon-carbon double bonds. By the preparation method, through the selection on monomers participating in the reaction and the control on the reaction conditions, so that the prepared holographic recording material simultaneously meets the requirements of high modulus and high diffraction efficiency; good application prospects are realized.
Description
Technical field
The invention belongs to photopolymerization material technical field, more particularly, to a kind of hologram recording material and preparation side thereof
Method.
Background technology
Fake and forged harm national security and the orthobiosis of people, development anti-counterfeiting technology is to hitting manufacturing and marketing the fake, promotion
The normal construction of orderly market is particularly important.Anti-counterfeiting technology is broadly divided into two big classes: a class need not by any instrument i.e.
The distinguishable true and false, observer changes angle or by touching safety letters such as just can identifying material, hardness, lines, picture and text, color
Breath.The visual color change utilizing the chiral structures such as cholesteric liquid crystal polymer, photoetching grating and multistep polarization polymerization to obtain is false proof
Technology just belongs to this kind of.Another kind of needs could identify by extraneous instrument, and such as invisible-bar-number and function solenoid are false proof.The former
Easily differentiate, but technology of preparing threshold is relatively low, be not easily forged person's imitation；The latter's antifalse effect is good, but is difficult to the whole people and popularizes, Er Qiesui
The development of science and technology, such anti-counterfeiting technology also faces new challenges, and the bank card duplicator such as occurred recently just destroys
The authority of such anti-counterfeiting technology.In order to improve false proof safety and monopoly, and it is easy to general public discriminating, need to develop new
Techniques of Optical Security.3D hologram anti-counterfeiting technology is an important developing direction.
Hologram recording material is the basis of 3D hologram anti-counterfeiting technology, the modulus of holographic material and the optical grating diffraction effect prepared
Rate determines that it loads picture and text brightness, and then affects its antifalse effect.But, the existing holographic recording material obtained by two-step method
Material, its modulus is less than 104Handkerchief, diffraction efficiency is less than 85%, and relatively low modulus and diffraction efficiency make existing holographic recording
Material is difficult to meet requirement in high-end field of anti-counterfeit technology.
Summary of the invention
For disadvantages described above or the Improvement requirement of prior art, the invention provides a kind of holographic material and preparation side thereof
Method, its object is to select monomer so that holographic material meets the requirement of high-modulus and high-diffraction efficiency simultaneously.
For achieving the above object, according to one aspect of the present invention, it is provided that a kind of hologram recording material, described holographic note
Record material is in terms of mass fraction, including the polyfunctionality polythiol monomer of 8%～60%, the polyfunctionality acrylic acid of 8%～60%
Ester monomer and 8%～60% polyfunctionality allyl monomer；Wherein, described polyfunctionality polythiol monomer includes 12～20
Individual CH2And at least 2 thin bases, described polyfunctional acrylic ester monomer includes 10～20 CH2And at least
2 electron deficiency carbon-carbon double bonds, described polyfunctionality allyl monomer includes 8～18 CH2And at least 2 electron riches
Carbon-carbon double bond.
Preferably, the chemical structural formula of described polyfunctionality polythiol monomer isWherein, R11For carbon
Atom or phenyl, R12ForR13It is each independently C1～C8Alkyl orR121It is each independently C1～C8Alkyl, R122It is each independently SH, CH3
Or OH.
As it is further preferred that described polyfunctionality polythiol monomer is tetramethylolmethane four mercaptoacetate, tetramethylolmethane
Four mercaptopentanoic acid esters, tetramethylolmethane four mercaptobutylate, tetramethylolmethane four mercaptohexanoic acid ester or trimethylolpropane tris (3-sulfydryl
Propionic ester).
Preferably, the chemical structural formula of described polyfunctional acrylic ester monomer is Wherein, R21For carbon atom or phenyl,
R22ForR23For C1～C8Hydroxy alkyl orR24For CH2, phenyl
OrR25For C1～C8Hydroxy alkyl, R221It is each independently C1～C8Alkyl, R222Independently of one another
For C=CH2、—CH3Or OH, n are 5～10.
As it is further preferred that described polyfunctional acrylic ester monomer is tetramethylol methane tetraacrylate, two (three hydroxyls
Methybutane) tetraacrylate, tetramethylolmethane four butenoate, tetramethylolmethane four pentenoate or molecular weight 200～600 poly-
Glycol diacrylate.
Preferably, the chemical structural formula of described polyfunctionality allyl monomer is Wherein, R31It is each independently C1～C8Alkyl, R32The most independent
Ground is C1～C8Alkyl, R33For carbon atom or phenyl, R34For C4～C8Alkyl.
As it is further preferred that described polyfunctionality allyl monomer be 1,3,5-triolefin heptane bases-1,3,5-triazines-
2,4,6 (1H, 3H, 5H) triketone, Trimethylolhexane diene butyl ether, trihydroxy methyl pentane diene amyl ether, three butanediols two
Cyclobutenyl ether or three hexanediol diallyl ethers.
Preferably, described hologram recording material also includes the light trigger of 0.1%～1.9%；Described light trigger is 3,
3 '-carbonyl double (7-diethylamine coumarin) and the mixture that mass ratio is 1:5～5:1 of N-phenylglycine, two (2,6-diformazans
Epoxide benzoyl) mass ratio of-2,4,4-tri-methyl-amyl phosphorous oxide and 2 hydroxy-2-methyl-1-phenylacetones is 1:3～3:1
Mixture, the mass ratio of Rose Bengal Sodium salt and N-phenylglycine is the mixture of 1:5～5:1, or double (1-
(2,4 difluorobenzene base)-3-pyrrole radicals) titanocenes.
Preferably, described hologram recording material also includes the catalyst of 0.1%～1.9%；Described catalyst be triethylamine,
Pyridine or Grignard reagent.
It is another aspect of this invention to provide that additionally provide the preparation method of above-mentioned hologram recording material, comprise the following steps:
(1) the gross mass number by reaction mixture is in terms of 100 parts, by the polyfunctionality polythiol monomer of 8 parts～60 parts, 8
Part～the polyfunctionality allyl monomer of the polyfunctional acrylic ester monomer of 60 parts, 8 parts～60 parts and 0.1 part～1.9 parts
Light trigger uniformly mix acquisition reaction mixture；
(2) in described reaction mixture, 0.1 part～the catalyst of 1.9 parts are added so that described polyfunctionality mercaptan list
In body, the thin base of 20%～80% and the electron deficiency carbon-carbon double bond in described polyfunctional acrylic ester monomer occur Michael to add
Become reaction, it is thus achieved that hologram recording material presoma；
(3) hologram recording material presoma is irradiated under coherent laser so that remaining in polyfunctionality polythiol monomer
Dredge base and the electron rich carbon-carbon double bond generation Radical Addition in described polyfunctionality allyl monomer, it is thus achieved that described holography
Recording materials.
Preferably, the mixed uniformly method in described step (1) is: at a temperature of 20 DEG C～90 DEG C, magnetic agitation or
Ultrasonic 0.1h～2.0h.
Preferably, in described step (2), in described polyfunctionality polythiol monomer, the thin base of 33%～72% is with described many
Electron deficiency carbon-carbon double bond generation Michael addition reaction in degree of functionality acrylate monomer.
Preferably, in described step (2), use up-differential scanning calorimetry controls to dredge in polyfunctionality polythiol monomer base
Response rate.
Preferably, in described step (3), the wavelength of coherent laser is 432nm～532nm.
As it is further preferred that the irradiation time in described step (3) is 10s～45s.
In general, by the contemplated above technical scheme of the present invention compared with prior art, owing to reaction is participated in
The wavelength of thing and coherent laser is optimized, it is possible to obtain following beneficial effect:
1, present invention utilizes Michael addition reaction different from the mechanism of action of Radical Addition and reaction condition,
Make the thin base in polyfunctionality polythiol monomer and the substep addition of different compounds, make use of polyfunctional acrylic ester simultaneously
Modulus is improved the raising characteristic to diffraction efficiency of characteristic and polyfunctionality allyl monomer by monomer, makes preparation produce
Hologram recording material has high-modulus and high-diffraction efficiency simultaneously；
2, the flexible methylene (CH of three kinds of monomers2) quantity is 8～20, is not only involved in the group of reaction
Between there is less steric effect, the reaction between group is more thorough, so that the degree of cross linking of product increases, modular ratio is existing
Having technology modulus to improve 2 orders of magnitude, diffraction efficiency also improves about 12%；Meanwhile, it is unlikely to owing to strand is long,
Molecular weight is excessive affects the quantity of effective group in product；
3, the reaction condition of the preparation method of the present invention is insensitive to oxygen and water, it is not necessary to harsh preparation condition, more
There is preparation and application prospect；
4, coherent laser wavelength is preferably 432nm～532nm, and the coherent laser penetration capacity of this wave-length coverage is relatively strong, and
Energy is relatively low, polyfunctionality polythiol monomer can be made more complete with the reaction of polyfunctionality allyl monomer, improve holography
The combined coefficient of recording materials.
Accompanying drawing explanation
Fig. 1 is embodiment 1, embodiment 2, embodiment 3 gained hologram recording material diffraction efficiency figure；
Fig. 2 is embodiment 4 gained hologram recording material modulus change figure；
Fig. 3 is embodiment 5 gained hologram recording material modulus change figure；
Fig. 4 is embodiment 7 gained hologram recording material modulus change figure.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, right
The present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, and
It is not used in the restriction present invention.If additionally, technical characteristic involved in each embodiment of invention described below
The conflict of not constituting each other just can be mutually combined.
The invention provides a kind of hologram recording material, described hologram recording material in terms of mass fraction, including 8%～
The polyfunctionality polythiol monomer of 60%, the polyfunctional acrylic ester monomer of 8%～60%, 8%～60% polyfunctionality allyl
Base monomer, the light trigger of 0.1%～1.9% and 0.1%～the catalyst of 1.9%；
Wherein, described polyfunctionality polythiol monomer includes 12～20 CH2And at least 2 thin bases, its chemistry
Structural formula isWherein, R11For carbon atom or phenyl, R12ForR13
It is each independently C1～C8Alkyl orR121It is each independently C1～C8Alkyl,
R122It is each independently SH, CH3Or OH；Such as, tetramethylolmethane four mercaptoacetate, tetramethylolmethane four mercaptopentanoic acid
Ester, tetramethylolmethane four mercaptobutylate, tetramethylolmethane four mercaptohexanoic acid ester or trimethylolpropane tris (3-thiopropionate) etc.；
Described polyfunctional acrylic ester monomer includes 10～20 CH2And at least 2 electron deficiency carbon-carbon double bonds, its
Chemical structural formula is
Wherein, R21For carbon atom or phenyl, R22ForR23For C1～C8Hydroxy alkyl or
R24For CH2, phenyl orR25For C1～C8Hydroxy alkyl, R221It is each independently C1～C8Alkane
Base, R222It is each independently C=CH2、—CH3Or OH, n are 5～10；Such as tetramethylol methane tetraacrylate, two (three hydroxyls
Methybutane) tetraacrylate, tetramethylolmethane four butenoate, tetramethylolmethane four pentenoate or molecular weight 200～600 poly-
Glycol diacrylate (PEGDA)；
Described polyfunctionality allyl monomer includes 8～18 CH2And at least 2 electron rich carbon-carbon double bonds,
Its chemical structural formula is Wherein, R31
It is each independently C1～C8Alkyl, R32It is each independently C1～C8Alkyl, R33For carbon atom or phenyl, R34For C4~
C8Alkyl；Such as 1,3,5-triolefin heptane base-1,3,5-triazine-2,4,6 (1H, 3H, 5H) triketone, Trimethylolhexane diene
Butyl ether, trihydroxy methyl pentane diene amyl ether, three butanediol dibutene base ethers or three hexanediol diallyl ethers etc..
The preparation method of above-mentioned hologram recording material, comprises the following steps:
(1) the gross mass number by reaction mixture is in terms of 100 parts, by the polyfunctionality polythiol monomer of 8 parts～60 parts, 8
Part～the polyfunctionality allyl monomer of the polyfunctional acrylic ester monomer of 60 parts, 8 parts～60 parts and 0.1 part～1.9 parts
Light trigger mixing, and in 20 DEG C～90 DEG C of water-baths, magnetic agitation or ultrasonic 0.1h～2.0h make it uniformly mix acquisition
Reaction mixture；
Wherein, polyfunctionality polythiol monomer, polyfunctional acrylic ester monomer and the tool of polyfunctionality allyl monomer
Depending on weight mark then quantity according to the thin base contained by the molecular weight of above-mentioned monomer and compound or carbon-carbon double bond；It is
High quality mark is roughly the same with the quantity of carbon-carbon double bond so that dredging base, and in carbon-carbon double bond, electron rich carbon-carbon double bond is with scarce
The ratio of electronics carbon-carbon double bond is 1:4～4:1；
And light trigger is the light trigger of the Radical Addition that coherent laser excites be applicable to step (3), example
As, 3,3 '-carbonyl double (7-diethylamine coumarin) and the mixture that mass ratio is 1:5～5:1 of N-phenylglycine, two (2,
6-dimethoxybenzoyl) mass ratio of-2,4,4-tri-methyl-amyl phosphorous oxide and 2 hydroxy-2-methyl-1-phenylacetones is 1:
The mixture of 3～3:1, the mass ratio of Rose Bengal Sodium salt and N-phenylglycine is the mixture of 1:5～5:1, or
Double (1-(2,4 difluorobenzene the base)-3-pyrrole radicals) titanocenes of person；
(2) in described reaction mixture, add 0.1 part～the catalyst of 1.9 parts, and be poured on rapidly on substrate so that institute
State the thin base of 20%～80% and the electron deficiency carbon carbon in described polyfunctional acrylic ester monomer in polyfunctionality polythiol monomer
Double bond generation Michael addition reaction, and utilize differential photo-scanning calorimetry method (Photo-DSC) control dredge base response rate be
20%～80%, it is thus achieved that hologram recording material presoma；Described catalyst is the catalyst for Michael addition reaction, such as three
Ethamine, pyridine or Grignard reagent etc.；Substrate preferably transparent material is so that accepting the irradiation of coherent laser in next step；Dredge base
The too low modulus that can affect final hologram recording material of response rate, response rate is too high, can make the holographic note that this step obtains
The viscosity of record material precursor is excessive and hinders the carrying out of step (3), and then is difficult to be formed grating under coherent laser, thus shadow
Ringing the diffraction efficiency of hologram recording material, the response rate therefore dredging base is preferably 33%～72%；
(3) hologram recording material presoma is irradiated under wavelength is 432nm～532nm coherent laser 10s～45s, make
Obtain remaining thin base in polyfunctionality polythiol monomer to occur with the electron rich carbon-carbon double bond in described polyfunctionality allyl monomer
Radical Addition, it is thus achieved that described hologram recording material.
Embodiment 1
(1) by tetramethylolmethane four mercaptobutylate of 1.024g, the Polyethylene Glycol diacrylate of the molecular weight 200 of 3.84g
Ester (PEGDA), 1,3,5-triolefin heptane base-1,3,5-triazine-2,4,6 (1H, 3H, the 5H) triketone and the 3 of 0.243g of 7.68g,
3 '-carbonyl double (7-diethylamine coumarin) and the mixture of N-phenylglycine (mass ratio 1:5), mixing is placed in water-bath
1.0 hours, bath temperature 40 DEG C, ultrasonic mix homogeneously, obtain solution A.
(2) adding the triethylamine of 0.013g in solution A, stirring 10 seconds, obtain B solution rapidly.B solution is poured on rapidly
On transparent glass substrate, verify through light-differential scanning calorimeter (Photo-DSC), tetramethylolmethane four mercaptobutylate is dredged base
The extent of reaction be 33%, it is thus achieved that hologram recording material presoma.
(3) hologram recording material presoma is reacted 30 seconds under the coherent laser illumination that wavelength is 442nm, obtain thickness
It it is the hologram recording material of 50 μm.
Use the diffraction efficiency of liquid crystal device parametric synthesis tester detection gained hologram recording material, acquired results such as figure
Shown in 1, when PEGDA molecular weight is 200, the diffraction efficiency of holographic material is 0.1%.
Embodiment 2
(1) by tetramethylolmethane four mercaptobutylate of 1.024g, the Polyethylene Glycol diacrylate of the molecular weight 400 of 3.84g
Ester, 1,3,5-triolefin heptane base-1,3,5-triazine-2,4,6 (1H, 3H, the 5H) triketone of 7.68g and the 3,3 '-carbonyl of 0.243g
Base double (7-diethylamine coumarin) and the mixture of N-phenylglycine (mass ratio 1:5), mix that to be placed in water-bath 1.0 little
Time, bath temperature 40 DEG C, ultrasonic mix homogeneously, obtain solution A.
(2) adding the triethylamine of 0.013g in solution A, stirring 10 seconds, obtain B solution rapidly.B solution is poured on rapidly
On transparent glass substrate, verify through light-differential scanning calorimeter (Photo-DSC), tetramethylolmethane four mercaptobutylate is dredged base
The extent of reaction be 33%, it is thus achieved that hologram recording material presoma.
(3) hologram recording material presoma is reacted 30 seconds under the coherent laser illumination that wavelength is 442nm, obtain thickness
It it is the hologram recording material of 50 μm.
Use the diffraction efficiency of liquid crystal device parametric synthesis tester detection gained hologram recording material, acquired results such as figure
Shown in 1, when PEGDA molecular weight is 400, the diffraction efficiency of holographic material is 3.3%.
Embodiment 3
(1) by tetramethylolmethane four mercaptobutylate of 1.024g, the Polyethylene Glycol diacrylate of the molecular weight 600 of 3.84g
Ester, 1,3,5-triolefin heptane base-1,3,5-triazine-2,4,6 (1H, 3H, the 5H) triketone of 7.68g and the 3,3 '-carbonyl of 0.243g
Double (7-diethylamine coumarins) and the mixture of N-phenylglycine (mass ratio 1:5), mixing is placed in water-bath 1.0 hours,
Bath temperature 40 DEG C, ultrasonic mix homogeneously, obtain solution A.
(2) adding the triethylamine of 0.013g in solution A, stirring 10 seconds, obtain B solution rapidly.B solution is poured on rapidly
On transparent glass substrate, verify through light-differential scanning calorimeter (Photo-DSC), tetramethylolmethane four mercaptobutylate is dredged base
The extent of reaction be 33%, it is thus achieved that hologram recording material presoma.
(3) hologram recording material presoma is reacted 30 seconds under the coherent laser illumination that wavelength is 442nm, obtain thickness
It it is the hologram recording material of 50 μm.
Use the diffraction efficiency of liquid crystal device parametric synthesis tester detection gained hologram recording material, acquired results such as figure
Shown in 1, when PEGDA molecular weight is 600, the diffraction efficiency of holographic material is 10.8%.
Embodiment 4
(1) by the Trimethylolhexane three (3-mercaptopentanoic acid ester) of 2.56g, the Polyethylene Glycol two of the molecular weight 400 of 2.56g
Two (the 2,6-dimethoxybenzoyl)-2 of acrylate, the Trimethylolhexane diene butyl ether of 7.424g and 0.077g,
4,4-tri-methyl-amyl phosphorous oxide and the mixture of 2 hydroxy-2-methyl-1-phenylacetones (mass ratio 1:3), mixing is placed on water
In bath 2.0 hours, bath temperature 60 DEG C, magnetic agitation mix homogeneously, obtain solution A.
(2) adding the catalyst of 0.179g in solution A, stirring 20 seconds, obtain B solution rapidly.B solution is poured on rapidly
On transparent glass substrate, verify through light-differential scanning calorimeter (Photo-DSC), Trimethylolhexane three (3-mercaptopentanoic acid
Ester) in dredge base the extent of reaction be 42%, it is thus achieved that hologram recording material presoma.
(3) hologram recording material presoma is reacted 20 seconds under the coherent laser illumination that wavelength is 532nm, obtain holographic note
Record material.
B solution is poured into rapidly on the transparency glass plate stove of rotational rheometer, uses rotational rheometer continuous detecting B
Solution is under catalyst action and light intensity is 6.0mw/cm2532nm coherent laser illumination under its storage modulus G', loss modulus
G ＂ modulus changes over and changes.
Acquired results as in figure 2 it is shown, in figure curve 1 represent that storage modulus G', curve 2 represent loss modulus G ＂.From figure
It can be seen that the modulus of the holographic material presoma obtained is less by (1.9 × 102Pa), moving of monomer in subsequent reactions can be met
Move unobstructed, make reaction more complete, and the modulus of the holographic material obtained increases along with the increase of light application time, reaches
High-modulus requirement.
Embodiment 5
(1) by the tetramethylolmethane four mercaptopentanoic acid ester of 7.68g, the tetramethylol methane tetraacrylate of 2.56g, the three of 2.304g
Two (2,6-dimethoxybenzoyl)-2,4,4-tri-methyl-amyl phosphorous oxide of methylol pentane diene amyl ether and 0.180g
With the mixture of 2 hydroxy-2-methyl-1-phenylacetones (mass ratio 3:1), mixing is placed in water-bath 2.0 hours, bath temperature
90 DEG C, magnetic agitation mix homogeneously, obtain solution A.
(2) adding the triethylamine of 0.076g in solution A, stirring 15 seconds, obtain B solution rapidly.B solution is poured on rapidly
On transparent plastic substrate, verify through light-differential scanning calorimeter (Photo-DSC), tetramethylolmethane four mercaptopentanoic acid ester is dredged base
The extent of reaction be 58%, it is thus achieved that hologram recording material presoma.
(3) hologram recording material presoma is reacted 45 seconds under the coherent laser illumination that wavelength is 532nm, obtain holographic note
Record material.
B solution is poured into rapidly on the clear glass board clamp of rotational rheometer, uses rotational rheometer continuous detecting B
Solution is under catalyst action and light intensity is 6.0mw/cm2532nm coherent laser illumination under its storage modulus G', loss modulus
G ＂ modulus changes over and changes.
Acquired results as it is shown on figure 3, in figure curve 1 represent that storage modulus G', curve 2 represent loss modulus G ＂.From figure
It can be seen that the modulus of the holographic material presoma obtained is less by (1.5 × 103Pa), moving of monomer in subsequent reactions can be met
Move unobstructed, be conducive to reaction completely, and the modulus of the holographic material obtained increases along with the increase of light application time, reaches
High-modulus requirement.
Embodiment 6
(1) by the tri hydroxy methyl butane three (3-mercaptobutylate) of 7.68g, the Polyethylene Glycol of the molecular weight 400 of 1.024g
Diacrylate, the three butanediol dibutene base ethers of 3.712g and two (the 2,6-dimethoxybenzoyl)-2,4 of 0.243g,
4-tri-methyl-amyl phosphorous oxide and the mixture of 2 hydroxy-2-methyl-1-phenylacetones (mass ratio 12:5), mixing is placed on water
In bath 0.5 hour, bath temperature 20 DEG C, ultrasonic mix homogeneously, obtain solution A.
(2) adding the Grignard reagent of 0.013g in solution A, stirring 60 seconds, obtain B solution rapidly.B solution is fallen rapidly
On a transparent plastic substrate, verify through light-differential scanning calorimeter (Photo-DSC), tri hydroxy methyl butane three (3-mercaptobutyric acid
Ester) in dredge base the extent of reaction be 45%, it is thus achieved that hologram recording material presoma.
(3) hologram recording material presoma is reacted 20 seconds under the coherent laser illumination that wavelength is 432nm, obtain holographic note
Record material.
Embodiment 7
(1) by tetramethylolmethane four mercaptobutylate of 7.68g, two (tri hydroxy methyl butane) tetraacrylate of 3.84g,
The three hexanediol diallyl ethers of 1.024g and the 3,3 '-carbonyl of 0.064g double (7-diethylamine coumarin) and N-phenylglycine
The mixture of (mass ratio 2:1), mixing is placed in water-bath 1.5 hours, bath temperature 75 DEG C, magnetic agitation mix homogeneously,
To solution A.
(2) adding the pyridine of 0.192g in solution A, stirring 5 seconds, obtain B solution rapidly.B solution is poured on rapidly
On bright glass substrate, verify through light-differential scanning calorimeter (Photo-DSC), tetramethylolmethane four mercaptobutylate is dredged base
The extent of reaction is 68%, it is thus achieved that hologram recording material presoma.
(3) hologram recording material presoma is reacted 35 seconds under the coherent laser illumination that wavelength is 532nm, obtain holographic note
Record material.
B solution is poured into rapidly on the clear glass board clamp of rotational rheometer, uses rotational rheometer continuous detecting B
Solution is under catalyst action and light intensity is 6.0mw/cm2532nm coherent laser illumination under its storage modulus G', loss modulus
G ＂ modulus changes over and changes.
As shown in Figure 4, in figure, curve 1 represents that storage modulus G', curve 2 represent loss modulus G ＂ to acquired results.From figure
It can be seen that the modulus bigger than normal (0.9 × 10 of the holographic material presoma obtained4Pa), the migration of monomer in subsequent reactions is had
Hinder, be unfavorable for the carrying out of reaction, but the hologram recording material modulus obtained is up to 105Handkerchief, meets high-modulus requirement.
Embodiment 8
(1) by the trimethylolpropane tris (3-mercaptobutylate) of 3.84g, tetramethylolmethane four butenoate of 5.12g,
1,3,5-triolefin hexyl-1,3,5-triazine-2,4,6 (1H, 3H, the 5H) triketone of 6.016g and the 3,3 '-carbonyl of 0.192g are double
(7-diethylamine coumarin) and the mixture of N-phenylglycine (mass ratio 3:1), mixing is placed in water-bath 0.1 hour, water
Bath temperature 80 DEG C, ultrasonic mix homogeneously, obtain solution A.
(2) adding the grignard reagent of 0.192g in solution A, stirring 20 seconds, obtain B solution rapidly.B solution is fallen rapidly
On a transparent plastic substrate, verify through light-differential scanning calorimeter (Photo-DSC), trimethylolpropane tris (3-mercaptobutyric acid
Ester) in dredge base the extent of reaction be 62%, it is thus achieved that hologram recording material presoma.
(3) hologram recording material presoma is reacted 15 seconds under the coherent laser illumination that wavelength is 532nm, obtain holographic note
Record material.
Embodiment 9
(1) by the tetramethylolmethane four mercaptohexanoic acid ester of 6.4g, tetramethylolmethane four pentenoate of 4.48g, the three of 1.792g
Double (1-(2,4 difluorobenzene base)-3-pyrrole radicals) titanocenes mixing of hexanediol diallyl ether and 0.064g are placed on water-bath
In 0.6 hour, bath temperature 65 DEG C, ultrasonic mix homogeneously, obtain solution A.
(2) adding the pyridine of 0.064g in solution A, stirring 45 seconds, obtain B solution rapidly.B solution is poured on rapidly
On bright glass substrate, verify through light-differential scanning calorimeter (Photo-DSC), tetramethylolmethane four mercaptohexanoic acid ester is dredged base
The extent of reaction is 70%, it is thus achieved that hologram recording material presoma.
(3) hologram recording material presoma is reacted 30 seconds under the coherent laser illumination that wavelength is 442nm, obtain holographic note
Record material.
Table 1 embodiment 1-9 monomer, light trigger and catalyst quality and mass fraction
Continued 1
As it will be easily appreciated by one skilled in the art that and the foregoing is only presently preferred embodiments of the present invention, not in order to
Limit the present invention, all any amendment, equivalent and improvement etc. made within the spirit and principles in the present invention, all should comprise
Within protection scope of the present invention.
Claims (10)
1. a hologram recording material, it is characterised in that described hologram recording material is in terms of mass fraction, including 8%～60%
Polyfunctionality polythiol monomer, the polyfunctional acrylic ester monomer of 8%～60% and 8%～60% polyfunctionality pi-allyl
Monomer；Wherein, described polyfunctionality polythiol monomer includes 12～20 CH2And at least 2 thin bases, described multifunctional
Degree acrylate monomer includes 10～20 CH2And at least 2 electron deficiency carbon-carbon double bonds, described polyfunctionality allyl
Base monomer includes 8～18 CH2And at least 2 electron rich carbon-carbon double bonds.
2. hologram recording material as claimed in claim 1, it is characterised in that the chemical constitution of described polyfunctionality polythiol monomer
Formula isWherein, R11For carbon atom or phenyl, R12ForR13Each
Independently be C1～C8Alkyl orR121It is each independently C1～C8Alkyl, R122Respectively
From independently be SH, CH3Or OH.
3. hologram recording material as claimed in claim 1, it is characterised in that the chemical constitution of described polyfunctional acrylic ester monomer
Formula is Its
In, R21For carbon atom or phenyl, R22ForR23For C1～C8Hydroxy alkyl or
R24For CH2, phenyl orR25For C1～C8Hydroxy alkyl, R221It is each independently C1～C8Alkane
Base, R222It is each independently C=CH2、—CH3Or OH, n are 5～10.
4. hologram recording material as claimed in claim 1, it is characterised in that the chemistry knot of described polyfunctionality allyl monomer
Structure formula is Wherein, R31
It is each independently C1～C8Alkyl, R32It is each independently C1～C8Alkyl, R33For carbon atom or phenyl, R34For C4~
C8Alkyl.
5. hologram recording material as claimed in claim 1, it is characterised in that described hologram recording material also include 0.1%～
The light trigger of 1.9%；Described light trigger is 3,3 '-carbonyl double (7-diethylamine coumarin) and quality of N-phenylglycine
Than the mixture for 1:5～5:1, two (2,6-dimethoxybenzoyl)-2,4,4-tri-methyl-amyl phosphorous oxide and 2 hydroxyl-2-
The mass ratio of methyl isophthalic acid-phenylacetone is the mixture of 1:3～3:1, Rose Bengal Sodium salt and N-phenylglycine
Mass ratio is the mixture of 1:5～5:1, or double (1-(2,4 difluorobenzene base)-3-pyrrole radicals) titanocenes.
6. hologram recording material as claimed in claim 1, it is characterised in that described hologram recording material also include 0.1%～
The catalyst of 1.9%；Described catalyst is triethylamine, pyridine or Grignard reagent.
7. the preparation method of hologram recording material as described in any one in claim 1-6, it is characterised in that include following step
Rapid:
(1) the gross mass number by reaction mixture is in terms of 100 parts, by the polyfunctionality polythiol monomer of 8 parts～60 parts, 8 parts～
The polyfunctionality allyl monomer of polyfunctional acrylic ester monomer, 8 parts～60 parts of 60 parts and 0.1 part～the light of 1.9 parts
Initiator uniformly mixes acquisition reaction mixture；
(2) in described reaction mixture, 0.1 part～the catalyst of 1.9 parts are added so that in described polyfunctionality polythiol monomer
The thin base of 20%～80% and the electron deficiency carbon-carbon double bond in described polyfunctional acrylic ester monomer occur Michael's addition anti-
Should, it is thus achieved that hologram recording material presoma；
(3) hologram recording material presoma is irradiated under coherent laser so that remaining thin base in polyfunctionality polythiol monomer
With the electron rich carbon-carbon double bond generation Radical Addition in described polyfunctionality allyl monomer, it is thus achieved that described holographic recording
Material.
8. preparation method as claimed in claim 7, it is characterised in that the mixed uniformly method in described step (1) is: 20
DEG C～90 DEG C at a temperature of, magnetic agitation or ultrasonic 0.1h～2.0h.
9. preparation method as claimed in claim 7, it is characterised in that in described step (2), described polyfunctionality mercaptan list
In body, the thin base of 33%～72% and the electron deficiency carbon-carbon double bond in described polyfunctional acrylic ester monomer occur Michael to add
Become reaction.
10. preparation method as claimed in claim 7, it is characterised in that in described step (3), the wavelength of coherent laser is
432nm～532nm, irradiation time is 10s～45s.
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| CN201610343055.1A CN106008977A (en) | 2016-05-23 | 2016-05-23 | Holographic recording material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110527523A (en) * | 2018-05-23 | 2019-12-03 | 华中科技大学 | A kind of dual imaging storage material, preparation method and application |
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| CN1317513A (en) * | 2000-04-13 | 2001-10-17 | 大曹株式会社 | Cross-linkable solidifying resin compsn. |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1317513A (en) * | 2000-04-13 | 2001-10-17 | 大曹株式会社 | Cross-linkable solidifying resin compsn. |
| US20090253805A1 (en) * | 2008-04-07 | 2009-10-08 | Hoyle Charles E | Photocurable Thiol-Ene Low Gas Permeability Membranes |
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| CN110527523A (en) * | 2018-05-23 | 2019-12-03 | 华中科技大学 | A kind of dual imaging storage material, preparation method and application |
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