CN101622582A - Volume hologram laminate manufacturing method - Google Patents

Volume hologram laminate manufacturing method Download PDF

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Publication number
CN101622582A
CN101622582A CN200880006462.7A CN200880006462A CN101622582A CN 101622582 A CN101622582 A CN 101622582A CN 200880006462 A CN200880006462 A CN 200880006462A CN 101622582 A CN101622582 A CN 101622582A
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Prior art keywords
volume hologram
resin bed
layer
mentioned
laminate
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CN101622582B (en
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阿座上实
卫藤浩司
大泷浩幸
前野义人
羽鸟樱子
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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Priority claimed from JP2007248694A external-priority patent/JP5228427B2/en
Application filed by Dai Nippon Printing Co Ltd filed Critical Dai Nippon Printing Co Ltd
Priority to CN201310288722.7A priority Critical patent/CN103472703B/en
Priority claimed from PCT/JP2008/053560 external-priority patent/WO2008105510A1/en
Publication of CN101622582A publication Critical patent/CN101622582A/en
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Abstract

A method for manufacturing a volume hologram laminate for enabling reproduction of a hologram image with a given wavelength at an easy process. In the method, a volume hologram forming substrate having a base, a volume hologram layer formed on the base and containing a photopolymerizable substance, and a resin layer so formed over the base as to be in contact with the volume hologram layer and containing resin and a polymerizable compound is used. The method is characterized by comprising a hologram imaging step of recording a volume hologram in the volume hologram layer of the volume hologram forming substrate, a substance transfer step of transferring the polymerizable compound into the volume hologram layer, and a post-processing step of polymerizing the polymerizable compound.

Description

The manufacture method of volume hologram laminate
Technical field
The present invention relates to possess the manufacture method of the volume hologram laminate of the volume hologram layer that has write down volume hologram.The invention still further relates to volume hologram laminate that possesses the volume hologram layer that has write down volume hologram and the volume hologram transfer foil that has used this volume hologram laminate, volume hologram label.And then, the invention still further relates to the volume hologram laminate and the manufacture method thereof of antifalsification (anti-again utilize), designability excellence.
Background technology
Hologram is interfered for two light by wavelength is equated (object light and with reference to light), thereby the corrugated of object light is recorded in photosensitive material as interference fringe and must schemes, when the light with reference to light and the same terms when interference fringe writes down meets, the diffraction phenomena that then interferes striped and caused can reproduce and the identical corrugated of object light originally.This hologram is categorized as several (surface undulation type hologram, volume holograms etc.) according to the recording mode of interference fringe.
Here, above-mentioned surface undulation hologram is for to form hologram by giving fine relief pattern on the surface of hologram layer.On the other hand, above-mentioned volume hologram be by with interference fringe that interference of light produced as the different striped three-dimensional ground record on thickness direction of diffraction efficiency, thereby form hologram.
Above-mentioned volume hologram can use the hologram master in industrial batch process, be compared to the advantage that above-mentioned fluctuating type hologram has the commercial production excellence, but industrial employed Wavelength of Laser is limited, and this is a present situation.Therefore, for the light that the hologram image with the volume hologram of industrial batch process reproduces, wavelength is also limited, therefore utilizes in the mode at daily hologram, is difficult to reproduce bright hologram image.
For this problem, in recent years when making volume hologram, use following method, promptly, by the volume hologram layer that has write down interference fringe being implemented processing afterwards, change originally the cycle of the interference fringe of record, used light wavelength diverse ways when making the playback wavelength of hologram image and recording interference fringe.
That is to say, because the playback wavelength of volume hologram is consistent with the cycle of the interference fringe that is recorded in hologram layer, therefore by change the cycle of the interference fringe that is recorded in hologram layer afterwards, make cycle of interference fringe become consistent with the very high light wavelength of daily frequency of utilization.Can to reproduce the aspect of volume hologram layer of bright hologram image in the mode useful for being produced on daily utilizing for the method that so afterwards changes the fringe period that is recorded in hologram layer.
As the method for this playback wavelength that changes hologram image is known afterwards several methods arranged, can enumerate the method that patent documentation 1 is put down in writing as general method.Patent documentation 1 discloses by the layer that contains monomer and/or plastifier is contacted with the volume hologram layer that has write down interference fringe and has carried out heat treated etc., makes above-mentioned monomer and/or plastifier shift to the volume hologram layer, increases the method in the cycle of interference fringe.This method the cycle that can positively increase interference fringe, with playback wavelength to long wavelength's direction move aspect useful.But, have the little problem of the variable period amount of interference fringe or the problem of complex procedures on the other hand.
And then volume hologram is can record the information on the thickness direction, can carry out the method for the record-playback of stereo-picture in addition, owing to utilize the interference of light look to show, therefore has the outward appearance that other image forming methods are difficult to obtain.The manufacture method of volume hologram itself is known, but when making owing to need use the accurate operation of optical apparatus, therefore the simulation of volume hologram is difficult, and the above-mentioned characteristic of utilizing this volume hologram to have is used in the anti-simulation of I.D., bank card etc.The inventor etc. are for this anti-analogue technique, for example shown in patent documentation 2, patent documentation 3, carried out and to have peeled off the volume hologram layer from the I.D. that is pasted with the volume hologram layer, even if peel off the various researchs that volume hologram also can ruined anti-counterfeiting, but the volume hologram laminate that will write down volume hologram is as master, when utilizing the laser trial contact copying of single wavelength, possibility with simulation volume hologram, the expectation exploitation is difficult to simulate the volume hologram laminate of volume hologram.
Patent documentation 1: Japanese kokai publication hei 3-46687 communique
Patent documentation 2: Japanese kokai publication sho 63-284586 communique
Patent documentation 3: TOHKEMY 2002-358018 communique
Summary of the invention
The present invention finishes in view of the above problems, and providing can be with the manufacture method of the volume hologram laminate of the volume hologram laminate of any wavelength reconstructing hologram picture with the simple procedures manufacturing; The volume hologram laminate that the control playback wavelength can reproduce bright hologram image, can make with simple procedures; Even and if utilize the laser of single wavelength to attempt contact copying, its manufacture method that also is difficult to simulate the volume hologram laminate of volume hologram and can utilizes simple procedures to make.
In order to solve above-mentioned problem, the invention provides a kind of manufacture method of volume hologram laminate, it is characterized in that comprising following operation: use volume hologram to form and use substrate, the hologram of recording volume type hologram is taken operation on above-mentioned volume hologram layer, wherein, volume hologram forms the resin bed that contains resin and polymerizable compound that has base material, is formed on the above-mentioned base material and contains the volume hologram layer of optical polymerism material and be positioned on the above-mentioned base material and form in the mode that is contacted with on the above-mentioned volume hologram layer with substrate; Make above-mentioned polymerizable compound shift to the material mobile process of above-mentioned volume hologram layer; Make the postprocessing working procedures of above-mentioned polymerizable compound polymerization.
According to the present invention, use substrate by using to form as above-mentioned volume hologram with above-mentioned resin bed and the stacked substrate of the contacted mode of above-mentioned volume hologram layer, take in the operation at above-mentioned hologram, behind recording volume type hologram on the above-mentioned volume hologram layer, in the above-mentioned substance mobile process, make polymerizable compound shift to above-mentioned volume hologram layer from above-mentioned resin bed, thus can be in the cycle that at random changes the interference fringe that constitutes above-mentioned volume hologram afterwards.
Therefore, by the present invention, the enough simple operation manufacturings of energy can be with the volume hologram laminate of any wavelength reconstructing hologram picture.
Among the present invention, above-mentioned polymerizable compound is preferably the material that moves from above-mentioned volume hologram layer.By making the compound of above-mentioned polymerizable compound for moving from above-mentioned volume hologram layer, for example by behind the stacked resin bed that only constitutes on the above-mentioned volume hologram layer by above-mentioned resin, make the contained polymerizable compound of above-mentioned volume hologram layer move to resin bed, can make the volume hologram formation substrate that the present invention uses.Its reason is, can implement the manufacture method of volume hologram laminate of the present invention thus with simpler method.Its reason is in addition, by making the compound of above-mentioned polymerizable compound for moving from above-mentioned volume hologram layer, is easy to make above-mentioned polymerizable compound to shift to above-mentioned volume hologram layer in the above-mentioned substance mobile process.
Among the present invention, above-mentioned optical polymerism material contains free-radical polymerised compound and cationically polymerizable compound, and above-mentioned polymerizable compound is preferably above-mentioned cationically polymerizable compound.Its reason is that the volume hologram laminate that the present invention is made becomes the duplexer that can reproduce the high hologram image of contrast.
In addition, consistent by the constitute that makes the contained optical polymerism material of contained polymerizable compound of above-mentioned resin bed and above-mentioned volume hologram layer, utilize the present invention to make volume hologram laminate with simpler operation.
In order to solve above-mentioned problem, the invention provides a kind of volume hologram laminate, it has base material and volume hologram laminated section, this volume hologram laminated section comprises and is formed on the above-mentioned base material and contains the optical polymerism compound and by forming the volume hologram layer that interference fringe has write down volume hologram, and the resin bed that contains transparent resin that forms in the mode that is contacted with on the above-mentioned volume hologram layer, it is characterized in that, on above-mentioned resin bed, be formed with interference fringe.
According to the present invention, on above-mentioned resin bed, also be formed with interference fringe, by at random controlling the fringe period that is formed at above-mentioned volume hologram layer and above-mentioned resin bed respectively, can obtain to reproduce with any wavelength the volume hologram laminate of bright hologram image.In addition, according to the present invention by forming above-mentioned resin bed in the mode that is contacted with above-mentioned volume hologram layer, for example after directly forming the volume hologram layer on the above-mentioned resin bed,, can make volume hologram laminate of the present invention by the method for while recording interference fringe on these layers.Therefore, can obtain according to the present invention can be with the volume hologram laminate of simple operation manufacturing.Thus, the present invention can provide the may command playback wavelength, reproduce bright hologram image, can be with the volume hologram laminate of simple procedures manufacturing.
Among the present invention, be preferably formed in the fringe period of above-mentioned volume hologram layer different with the fringe period that is formed at above-mentioned resin bed.Its reason is, like this can by with the light of any consistent wavelength of cycle of the interference fringe that is formed at above-mentioned resin bed and volume hologram layer, hologram image is reproduced, therefore can hologram image be reproduced with a plurality of playback wavelengths, make volume hologram laminate of the present invention can reproduce more bright hologram image.
In addition, among the present invention, the transmissivity of preferred visible region shows the minimum transmission peak wavelength more than 2.Its reason is, makes volume hologram laminate of the present invention can reproduce more bright hologram image thus.
The present invention also provides a kind of volume hologram transfer foil, it is characterized in that, has the volume hologram laminate of the invention described above, and is formed on the above-mentioned volume hologram laminated section of above-mentioned volume hologram laminate and contains the hot sealing layer of thermoplastic resin.
Can obtain following volume hologram transfer foil according to the present invention, this volume hologram transfer foil is by using the volume hologram laminate of the invention described above, but the cycle that transfer printing is formed at the interference fringe of the above-mentioned volume hologram layer of above-mentioned volume hologram laminate and above-mentioned resin bed by control at random respectively can be reproduced the volume hologram of bright hologram image with any wavelength.
In the volume hologram transfer foil of the present invention, preferably between the above-mentioned volume hologram laminated section of above-mentioned volume hologram laminate and above-mentioned base material, form release layer.Its reason is, by forming above-mentioned release layer, can adjust the adaptation of above-mentioned base material and above-mentioned volume hologram laminated section, the result, from the above-mentioned volume hologram laminated section of volume hologram transfer foil transfer printing of the present invention the time, can improve the fissility of volume hologram laminated section.
The present invention also provides a kind of volume hologram label, it is characterized in that, has the volume hologram laminate of the invention described above, and the cement layer that is formed at the above-mentioned volume hologram laminated section of above-mentioned volume hologram laminate.
Can obtain the volume hologram label according to the present invention, this volume hologram label is by using the volume hologram laminate of the invention described above, can paste the volume hologram that the fringe period that is formed at the above-mentioned volume hologram layer of above-mentioned volume hologram laminate and above-mentioned resin bed by control at random respectively can reproduce bright hologram image with any wavelength.
Volume hologram laminate of the present invention be base material top be provided with resin bed in, adjacent on this resin bed and at the folded volume hologram laminate that the volume hologram layer is arranged of above-mentioned layers on substrates, it is characterized in that, when on above-mentioned resin bed, being formed with volume hologram, different with the reproduction centre wavelength of the part that resin bed is not set in the part that is provided with resin bed of volume hologram laminate.
It is characterized in that above-mentioned resin bed and above-mentioned base material adjacent.In addition, it is characterized in that, between above-mentioned resin bed and above-mentioned base material, be formed with undercoat.
It is characterized in that, the volume hologram layer is the volume hologram layer from the volume hologram recording materials that contain free radical polymerization monomer and cationically polymerizable monomer, is formed with based on the volume hologram that moves from the polymerizable monomer of adjacent volume hologram recording materials at resin bed simultaneously.
It is characterized in that, resin bed contains the resin that is selected from plexiglass, polyvinyl acetate (PVA), vibrin, the reproduction centre wavelength of the part that is provided with resin bed of volume hologram laminate is compared with the reproduction centre wavelength of the part that resin bed is not set simultaneously, is in long wavelength side.
It is characterized in that, resin bed contains the resin that is selected from polyvinyl butyral resin, polyvinyl acetal resin, the reproduction centre wavelength of the part that is provided with resin bed of volume hologram laminate is compared with the reproduction centre wavelength of the part that resin bed is not set simultaneously, is in short wavelength side.
It is characterized in that the reproduction centre wavelength of the part that is provided with resin bed of volume hologram laminate is at least more than the 10nm with the difference of the reproduction centre wavelength of the part that resin bed is not set.
The manufacture method of volume hologram laminate of the present invention is characterised in that, after the coating of ground, base material top forms resin bed, form the volume hologram recording materials layer that contains free radical polymerization monomer and cationically polymerizable monomer adjacent to being coated with on this resin bed and on above-mentioned base material, afterwards the gained duplexer implemented following operation successively:
(1) implements etching processing, make polymerizable monomer in the above-mentioned volume hologram recording materials layer shift to the operation of resin bed;
(2) be used to hologram exposure operation from the laser explosure of base material side;
(3) implement heat treated and ultraviolet treatment with irradiation, above-mentioned polymerizable monomer is moved between resin bed and volume hologram recording materials layer, simultaneously that hologram is fixing operation,
At the volume hologram of above-mentioned resin bed formation, make the part that is provided with resin bed in the above-mentioned duplexer different simultaneously with the reproduction centre wavelength at the part place that resin bed is not set based on the polymerizable monomer that moves from adjacent volume hologram recording material layer.
The present invention's the 1st volume hologram transfer is characterised in that with sheet material, is provided with the cement layer on the volume hologram layer of volume hologram laminate of the present invention.
The 2nd volume hologram transfer of the present invention is characterised in that with sheet material, strippable the 2nd base material is set on the volume hologram layer of volume hologram laminate of the present invention, on resin bed that exposes the peeling off base material of above-mentioned volume hologram laminate simultaneously and the volume hologram layer cement layer is set.Perhaps, it is characterized in that, strippable the 2nd base material is set on the volume hologram layer of volume hologram laminate of the present invention, on the face of peeling off base material of above-mentioned volume hologram laminate, the cement layer is set simultaneously.
It is characterized in that the 1st or the 2nd volume hologram transfer sheet material is that to make its cement layer be the volume hologram transfer foil of hot sealing layer, or the volume hologram transfer label that to make this cement layer be adhesive phase.
It is characterized in that volume hologram fitting body of the present invention is from above-mentioned the 1st volume hologram transfer is glued to the lining body with the cement layer side of sheet material when, base material is stripped from and is removed or the residual protective seam that becomes the volume hologram layer.
It is characterized in that volume hologram fitting body of the present invention is from above-mentioned the 2nd volume hologram transfer is glued to the lining body with the adhesive layer side of sheet material when, the 2nd base material is stripped from and is removed or the residual protective seam that becomes the volume hologram layer.
The effect of invention
The manufacture method of volume hologram laminate of the present invention has can be with the effect of the volume hologram laminate of any wavelength reconstructing hologram picture with simple operation manufacturing.In addition, volume hologram laminate of the present invention plays the effect that the may command playback wavelength reproduces bright hologram image, can make with simple operation.In volume hologram laminate of the present invention, the volume hologram fitting body, compare with the fringe period of the volume hologram layer of part not adjacent on layer direction at the fringe period of the adjacent volume hologram layer of the resin bed that is provided with part on the layer direction with resin bed, owing to formed the volume hologram of the fringe period that amplifies or dwindle, therefore can make the position that is provided with resin bed of volume hologram different with the reproduction centre wavelength at the position that resin bed is not set, designability is also unprecedented.In addition, with volume hologram laminate of the present invention is master, driving fit volume hologram recording materials layer thereon, be purpose, utilize the laser of single wavelength to attempt carrying out contact copying with the volume hologram that duplicates the part that resin bed is not set, owing to be provided with resin bed, reproducing the different part place deepening of centre wavelength, can't duplicate gallantly, therefore become the volume hologram laminate of false proof excellence.In addition, the manufacture method of volume hologram laminate of the present invention can be with the volume hologram laminate of simple operation designing for manufacturing, false proof excellence, in addition, when using volume hologram transfer of the present invention to use sheet material, can easily make the volume hologram fitting body by transfer printing.
Description of drawings
Fig. 1 is the skeleton diagram of an example of expression volume hologram laminate manufacture method of the present invention.
Fig. 2 is the skeleton diagram of explanation by the method for spectral transmission curve calculation diffraction efficiency, half-peak breadth and reproduction centre wavelength.
Fig. 3 is the electron micrograph of an example of the bulbous region that shows the volume hologram layer be formed at the volume hologram laminate of making by the manufacture method of volume hologram laminate of the present invention and resin bed.
Fig. 4 is the electron micrograph of other examples of the bulbous region that shows the volume hologram layer be formed at the volume hologram laminate of making by the manufacture method of volume hologram laminate of the present invention and resin bed.
Fig. 5 is the electron micrograph of other examples of the bulbous region that shows the volume hologram layer be formed at the volume hologram laminate of making by the manufacture method of volume hologram laminate of the present invention and resin bed.
Fig. 6 is the skeleton diagram of an example of expression volume hologram laminate of the present invention (the 1st mode).
Fig. 7 is the summary sectional view of an example of expression volume hologram transfer foil of the present invention.
Fig. 8 is the summary sectional view of an example of expression volume hologram label of the present invention.
Fig. 9 is the sectional view of expression volume hologram laminate of the present invention (the 2nd mode).
Figure 10 is the sectional view of expression the present invention the 1st volume hologram transfer with sheet material.
Figure 11 uses the sectional view of the 1st volume hologram transfer of the present invention with the volume hologram fitting body of sheet material making for expression.
Figure 12 is the sectional view of expression the present invention the 2nd volume hologram transfer with sheet material.
Figure 13 is for using the sectional view of the present invention's the 2nd volume hologram transfer with the volume hologram fitting body of sheet material making.
Figure 14 is the chart of the spectral transmission curve of the volume hologram laminate of expression embodiment and comparative example.
Figure 15 is in the volume hologram laminate of the present invention (the 2nd mode), 70% reduction print product of the scanning electron microscope photo of the longitudinal section of resin bed laminated section (15000 times).
The spectral transmission curve of part that the resin bed that Figure 16 represents volume hologram laminate of the present invention (the 2nd mode) forms through pattern and the part that forms without pattern.
The spectral transmission curve of part that the resin bed that Figure 17 represents volume hologram laminate of the present invention (the 2nd mode) forms through pattern and the part that forms without pattern.
Symbol description
11 ... base material
12 ... resin bed
13 ... the volume hologram layer
110 ... volume hologram laminate
110 ' ... volume hologram forms uses substrate
21 ... base material
22 ... the volume hologram laminated section
22a ... the volume hologram layer
22b ... resin bed
210 ... volume hologram laminate
220 ... volume hologram transfer foil
221 ... hot sealing layer
230 ... the volume hologram label
231 ... knitting layer
1 ... base material
2 ... resin bed
3 ... the volume hologram layer
4 ... the cement layer
5 ... the fissility sheet material
6 ... the lining body
7 ... the 2nd base material
8 ... undercoat
Embodiment
Below explain each invention of the present invention.
A. the manufacture method of volume hologram laminate
The manufacture method of volume hologram laminate of the present invention at first is described.As mentioned above, the manufacture method of volume hologram laminate of the present invention is characterised in that to have following operation: use volume hologram to form and use substrate, take operation at the hologram of volume hologram layer recording volume type hologram, above-mentioned volume hologram forms the resin bed that contains resin and polymerizable compound that has base material, is formed on the above-mentioned base material and contains the volume hologram layer of optical polymerism material and be positioned on the above-mentioned base material and form in the mode that is contacted with on the above-mentioned volume hologram layer with substrate; And, make above-mentioned polymerizable compound move to the material mobile process of above-mentioned volume hologram layer; The postprocessing working procedures of the above-mentioned polymerizable compound of polymerization.
The manufacture method of this volume hologram laminate of the present invention is described on one side with reference to accompanying drawing on one side.Fig. 1 is the skeleton diagram of expression volume hologram laminate manufacture method one example of the present invention.As shown in Figure 1, the manufacture method of volume hologram laminate of the present invention is characterised in that, has following operation: use volume hologram to form with substrate 110 ' (Fig. 1 (a)), the hologram of recording volume type hologram is taken operation (Fig. 1 * (b)) on volume hologram layer 13, and above-mentioned volume hologram forms with substrate to have base material 11, be formed on the above-mentioned base material 11 and contain the resin bed 12 of resin and polymerizable compound, the volume hologram layer 13 that contains the optical polymerism material to form adjacent to the mode on the above-mentioned resin bed 12; Above-mentioned resin bed 12 contained polymerizable compounds are moved to the material mobile process (Fig. 1 (c)) of above-mentioned volume hologram layer 13; Make the postprocessing working procedures (Fig. 1 (d)) of the polymerizable compound polymerization that moves to above-mentioned volume hologram layer 13, make the volume hologram layer 110 (Fig. 1 (e)) that on base material 11, has resin bed 12 at least, write down the volume hologram layer 13 of volume hologram.
According to the present invention, contact and stacked substrate according to above-mentioned resin bed and above-mentioned volume hologram layer with the substrate use as above-mentioned volume hologram formation, take in the operation volume hologram recording behind above-mentioned volume hologram layer at above-mentioned hologram, in the above-mentioned substance mobile process, polymerizable compound is moved to above-mentioned volume hologram layer from above-mentioned resin bed, thus can be in the cycle that changes the interference fringe that constitutes above-mentioned volume hologram afterwards.Its reason is, because the playback wavelength of volume hologram is consistent with the cycle of the interference fringe that constitutes it, therefore write down in the volume hologram layer of volume hologram by above-mentioned polymerizable compound is moved to, thereby can on the direction that increases the fringe period that has been formed at the volume hologram layer, make its change.Among the present invention, by adjusting the amount of movement of above-mentioned polymerizable compound, can increase to any degree the cycle of above-mentioned interference striped, therefore the amount of movement of used light wavelength and above-mentioned polymerizable compound when suitably being adjusted at above-mentioned hologram and taking recording volume type hologram in the operation, can adjust, the volume hologram that is recorded in the volume hologram layer is become can be with any wavelength reconstructing hologram picture afterwards.In addition, by selecting the kind of above-mentioned resin bed, can also shorten to any degree the cycle of above-mentioned interference striped among the present invention.
Therefore, the present invention can be with the volume hologram laminate of any wavelength reconstructing hologram picture with simple operation manufacturing.
The manufacture method of volume hologram laminate of the present invention has hologram at least and takes operation, material mobile process, postprocessing working procedures, also can have other any operations as required.
Each used operation of next coming in order explanation the present invention.
1. hologram is taken operation
Hologram shooting operation of the present invention at first is described.This operation is used substrate for using volume hologram to form, the operation of recording volume type hologram on above-mentioned volume hologram layer, wherein, volume hologram form with substrate have base material, be formed on the above-mentioned base material and contain the optical polymerism material the volume hologram layer, be positioned on the above-mentioned base material and the resin bed that contains resin and polymerizable compound to form adjacent to the mode on the above-mentioned volume hologram layer.
Below, explain this hologram and take operation.
(1) volume hologram forms and uses substrate
At first, the volume hologram formation substrate that this operation is used is described.The volume hologram that this operation is used forms has volume hologram layer, resin bed and base material at least with substrate.
A. resin bed
The resin that uses among the present invention is described.Resin bed used in the present invention contains polymerizable compound and resin at least.Use this resin among the present invention, in aftermentioned material mobile process, make above-mentioned polymerizable compound move to the volume hologram layer, can be thereby can make with the volume hologram laminate of any wavelength reconstructing hologram picture.
(polymerizable compound)
Above-mentioned polymerizable compound is so long as be movable to the material of volume hologram layer and then be not particularly limited in aftermentioned material mobile process.Therefore, the polymerizable compound that uses among the present invention can suitably be selected to use according to the composition of aftermentioned resin, volume hologram layer and the embodiment of material mobile process etc.Wherein, the material that above-mentioned polymerizable compound preferably moves from above-mentioned volume hologram layer among the present invention.Its reason is, thus behind the stacked resin bed that only constitutes on the above-mentioned volume hologram layer by above-mentioned resin, make the contained polymerizable compound of above-mentioned volume hologram layer move to resin bed, can make the volume hologram formation substrate that uses among the present invention, therefore can implement the present invention with simpler method.Its reason is in addition, because above-mentioned polymerizable compound is the material that moves from above-mentioned hologram layer, therefore the situation about moving to the volume hologram layer of being easy to is arranged in aftermentioned material mobile process.
In addition, the polymerizable compound that uses among the present invention preferably can be not illuminated in the photopolymerisable material of above-mentioned volume hologram layer during recording volume type hologram in this operation.Its reason is, during photopolymerization that above-mentioned polymerizable compound uses when being recorded volume hologram in this operation, in aftermentioned material mobile process, is difficult to make above-mentioned polymerizable compound to move to the volume hologram layer.
As the polymerizable compound that uses among the present invention, can enumerate thermal polymerization compound, optical polymerism compound, can preferably use any compound in these among the present invention.In addition, the polymerizable compound that uses among the present invention can only be a kind, perhaps can be for more than 2 kinds.Wherein, above-mentioned polymerizable compound preferably uses the material that contains in the contained optical polymerism material of aftermentioned volume hologram layer among the present invention.As above-mentioned polymerizable compound,, can easily form resin bed by using and the general material of the contained optical polymerism material of above-mentioned volume hologram layer.Promptly, volume hologram used in the present invention forms with substrate owing to being that resin bed and volume hologram layer are in contact with one another and stacked, therefore after for example forming the volume hologram layer, when forming resin bed thereon, by making the contained optical polymerism compound of above-mentioned volume hologram layer shift to resin bed, can easily form the resin bed that contains polymerizable compound.
In addition, when the contained optical polymerism material of aftermentioned volume hologram layer contains free-radical polymerised compound and cationically polymerizable compound, the contained polymerizable compound of resin bed preferably with the identical compound of above-mentioned cationically polymerizable compound.It the reasons are as follows described.
That is, among the present invention by using free-radical polymerised compound and cationically polymerizable compound as above-mentioned optical polymerism material, can the high volume hologram of recorded cost, at this moment, in this operation optionally with the free-radical polymerised compound polymerization.Therefore, by using the cationically polymerizable compound as above-mentioned polymerizable compound, above-mentioned polymerizable compound is aggregated in this operation, in material mobile process described later, seldom can hinder polymerizable compound moving to the volume hologram layer.
Illustrated, for above-mentioned cationically polymerizable compound, in " b. volume hologram layer " described later item, described in detail, therefore omitted its explanation here.
The amount of the polymerizable compound that resin bed is contained just is not particularly limited so long as the polymerizable compound of aequum can be moved in the scope of volume hologram layer in material mobile process described later.Concrete content depends on the kind of the used resin of resin bed, the composition of volume hologram layer, a variety of causes such as thickness of resin bed, wherein is preferably in the scope that is preferably 0.1 quality %～20 quality % in the scope of 0.1 quality %～30 quality %, especially among the present invention, more preferably in the scope of 1 quality %～10 quality %.
(resin)
Then, the resin that resin bed is used is described.As long as having the required transparency, the used resin of the present invention then is not particularly limited.Wherein, resin preferred molecular weight used in the present invention is bigger.Its reason is, because the big person of molecular weight of resin is easy to polymerizable compound is moved to the volume hologram layer in aftermentioned material mobile process, the playback wavelength that therefore can make hologram image from this operation during recording volume type hologram used light wavelength to more long wavelength side skew.The molecular weight of resin used in the present invention more specifically is preferably in 5000～1000000 the scope, wherein more preferably in 5000～500000 the scope, in preferred especially 10000～300000 the scope.
The object lesson of the resin that uses among the present invention for example can be enumerated acrylic resin, phenylethylene resin series, polyester based resin, polyurethane series resin, polyethylene-based resin, cellulose-based resin, alkyd is resin, petroleum line resin, ketone resin, epoxy is a resin, melamine is a resin, fluorine resin, the silicon-type resin, cellulose derivative, rubber is various synthetic resins or their potpourris more than 2 kinds such as resin, plasticity resins such as multipolymer, melamine are resin, phenolic aldehyde is a resin, urea is resin, epoxy is a resin, unsaturated polyester (UP) is a resin, the diallyl phthalic acid ester is a resin, polyurethane series resin, alkyd amino is heat-curing resin or acrylic ester resins such as resin, urethane acrylate is a resin, ester group acrylic ester resin, epoxy acrylate is the irradiation of process ultraviolet rays such as resin or electron ray etc. and curable resins such as ionizing radiation curable resin of solidifying etc.
In addition, when using polyvinyl butyral resin, polyvinyl acetal resin, reproduction centre wavelength is offset to short wavelength side as above-mentioned resin.
Illustrated that the resin that uses among the present invention can only be a kind, perhaps can be for more than 2 kinds.
(compound arbitrarily)
Except above-mentioned resin and above-mentioned polymerizable compound, also can contain other any compound in the used resin bed of the present invention.Above-mentioned any compound is not particularly limited, and the purposes of volume hologram laminate that can be constructed in accordance at random selects to give the compound of resin bed required function.This any compound for example can be enumerated antioxidant, ultraviolet light absorber, light stabilizer, thermal stabilizer, plastifier, lubricant, antistatic agent, fire retardant, filling agent etc.Can use these compounds separately among the present invention, use also capable of being combined is more than 2 kinds.
(resin bed)
The thickness of the resin bed that uses among the present invention so long as can contain according to the kind of above-mentioned resin in the scope of aequum polymerizable compound then is not particularly limited.Here, the thickness of above-mentioned resin bed is big more, then may contain the polymerizable compound of volume more at resin bed, it is moved to the volume hologram layer, so the thickness of resin bed is big more, and then the adjusting range of the side-play amount of playback wavelength is big more.Therefore, the thickness of above-mentioned resin bed can be according to playback wavelength is suitably adjusted within the required range.Wherein, among the present invention the thickness of above-mentioned resin bed be preferably in the scope that is preferably 0.5 μ m～5 μ m in the scope of 0.1 μ m～10 μ m, especially, more preferably in the scope of 0.5 μ m～3 μ m.
B. volume hologram layer
Then, the volume hologram layer that the present invention is used is described.The used volume hologram layer of the present invention contains the optical polymerism material, forms interference fringe by taking in the operation at hologram described later, but recording volume type hologram.
Below explain this volume hologram layer.
(optical polymerism material)
The optical polymerism material that the present invention is used at first is described.Optical polymerism material used in the present invention so long as by irradiation institute light requirement can carry out polyreaction, the material that can form interference fringe on the volume hologram layer promptly is not particularly limited.Wherein, preferably use at least 1 person of free-radical polymerised or cationically polymerizable compound among the present invention at least, from writing down the viewpoint of the high hologram image of contrast, preferred especially also with free-radical polymerised compound and cationically polymerizable compound.
And then, when using free-radical polymerised compound,, preferably use the optical free radical polymerization initiator in order to cause the polyreaction of this free-radical polymerised compound as above-mentioned optical polymerism material.On the other hand, when using the cationically polymerizable compound,, preferably make with light cationic polymerization initiators system from same reason as the optical polymerism material.
In addition, when using free-radical polymerised compound and cationically polymerizable compound, preferably use optical free radical polymerization initiator system and light cationic polymerization initiators to be as above-mentioned optical polymerism material.
Illustrated, volume hologram form with in the substrate because volume hologram is the state before the recording volume type hologram, so above-mentioned optical polymerism material is present in the volume hologram layer with unpolymerized state.
Free-radical polymerised compound, cationically polymerizable compound, optical free radical polymerization initiator system and light cationic polymerization initiators system that next coming in order explanation the present invention is used.
The cationically polymerizable compound that the present invention uses at first is described.The cationically polymerizable compound that the present invention uses is to accept energy exposure, the compound that cationic polymerization takes place this cautious acid of the Boulogne that decomposition produced or the lewis acid by aftermentioned light cationic polymerization initiators system.
Here, when using free-radical polymerised compound and cationically polymerizable compound as above-mentioned optical polymerism material, the record of the volume hologram of this operation is following carrying out usually: after interfering exposure, after the big part place of the light intensity of interference fringe makes the free-radical polymerised compound polymerization, by irradiation energy all sidedly with the uncured material polymerization of cationically polymerizable compound etc.At this moment, laser when forming hologram image etc. and the energy that comprehensively carries out energy exposure use different wavelength usually, so used cationically polymerizable compound is preferably under the wavelength of used light source when the formation hologram image polymeric compounds does not take place among the present invention.
In addition, from the viewpoint that the polymerization of above-mentioned free-radical polymerised compound is preferably carried out more low viscous composition, the used preferred normal temperature of cationically polymerizable compound of the present invention is liquid state down.
This cationically polymerizable compound for example can be enumerated the compound that Chemtec.Oct.J.V.Crivello, the 624th page (1980), Japanese kokai publication sho 62-149784 communique, Japan's joint association's will (the 26th volume, No.5, the 179th～187 page (1990)) and Japanese kokai publication hei 5-107999 communique, TOHKEMY 2002-236439 communique, TOHKEMY 2002-236440 communique etc. are put down in writing.
Among the present invention, can preferably use these any cationically polymerizable compounds, wherein preferably use per molecule to have the cationically polymerizable compound of the above polymerism of 3 officials energy functional group.Thus, owing to the cross-linking density that can improve in the volume hologram layer, therefore can optimize the cutting property of paper tinsel (foil cuttability) of volume hologram layer.
Illustrated that the cationically polymerizable compound that uses among the present invention can only be a kind, perhaps is more than 2 kinds.
Then, the used free-radical polymerised compound of the present invention is described.As long as the free-radical polymerised compound that uses among the present invention is when forming the volume hologram layer, for example by laser radiation etc., polymeric compounds takes place and just is not particularly limited in the effect by the living radical that produced by aftermentioned optical free radical polymerization initiator, has at least 1 ethene unsaturated double-bond in the preferred molecule among the present invention.
Here, the volume hologram layer for example light by laser or coherence's excellence etc. forms interference fringe with the free-radical polymerised compound polymerization, forms hologram image.Therefore, free-radical polymerised compound is selected the different material of diffraction efficiency separately usually with the cationically polymerizable compound.The free-radical polymerised compound that the present invention uses and the diffraction efficiency magnitude relationship of cationically polymerizable compound are not particularly limited, wherein from the aspect of material selectivity, the average diffraction efficiency of preferred free-radical polymerised compound is greater than above-mentioned cationically polymerizable compound, specifically, the difference of preferred average diffraction efficiency is more than 0.20.Its reason is, when the difference of the average diffraction efficiency of free-radical polymerised compound and above-mentioned cationically polymerizable compound was lower than above-mentioned value, the diffraction efficiency modulation became not enough, is difficult to form high meticulous hologram image.
Illustrated that said average diffraction efficiency is meant the mean value to the diffraction efficiency that makes the polymer determination after cationically polymerizable compound or the free-radical polymerised compound polymerization here.In addition, average diffraction efficiency of the present invention is meant the value of utilizing the Abbe diffractometer to measure.
The free-radical polymerised compound that the present invention uses can be enumerated the compound of records such as Japanese kokai publication hei 5-107999 communique, TOHKEMY 2002-236439 communique, TOHKEMY 2002-236440 communique.Can use a kind or be mixed with two or more among the present invention.
Then, the optical free radical polymerization initiator system that uses among the present invention is described.The optical free radical polymerization initiator system that the present invention uses so long as in this operation on the volume hologram layer during recording volume type hologram, can produce living radical by the light of irradiation, the material of above-mentioned free-radical polymerised compound polymerization just is not particularly limited.This optical free radical polymerization initiator is for example can enumerate United States Patent (USP) No. 4766055, No. the 4868092nd, United States Patent (USP), No. the 4965171st, United States Patent (USP), Japanese kokai publication sho 54-151024 communique, Japanese kokai publication sho 58-15503 communique, the spy opens clear 58-29803 communique, Japanese kokai publication sho 59-189340 communique, Japanese kokai publication sho 60-76735 communique, Japanese kokai publication hei 1-28715 communique, the flat 3-5569 of Japanese Patent Application number and PROCEEDING OFCONFERENCE ON RADIATION CURING ASIA are (P.461-477,1988) etc. the initiating agent system etc. of record.
Then, the light cationic polymerization initiators that uses among the present invention is described.This picks acid or lewis acid so long as can produce Boulogne by energy exposure in the light cationic polymerization initiators that uses among the present invention system, and the material of above-mentioned cationically polymerizable compound polymerization then is not particularly limited.Wherein, preferably do not react among the present invention, pass through the low photosensitivity material of the energy generation sensitization of irradiation comprehensively afterwards with respect to the laser of the above-mentioned free-radical polymerised compound of polymerization or the light of coherence's excellence etc.Its reason is, when above-mentioned free-radical polymerised compound polymerization, owing to can not make the cationically polymerizable compound residual substantially corresponsively, therefore can obtain very big diffraction efficiency modulation in the volume hologram layer thus.
Here, with respect to the light of laser or coherence's excellence is the light cationic polymerization initiators of low photosensitivity when being meant that carrying out heat under the following conditions analyzes, because the maximal value of the DSC value that photopolymerization caused that is caused by the light cationic polymerization initiators is that every 1mg mensuration sample is the material that (comprises 0mW) below the 500mW.
(condition determination)
Determinator: use differential scanning calorimetry DSC220 and light supply apparatus UV-1 in Seiko electronics industry (strain) the system SSC5200H thermal analysis system.
Measure sample: be dissolved in system UVR-6110 (cationically polymerizable compound) the 3 quality % of ユ ニ オ Application calcium carbide society by light cationic polymerization initiators system and modulate (add organic solvent make it after the dissolving also can with organic solvent evaporation) with object.
Irradiates light: use interference filter (the about 10nm of half-peak breadth), irradiation 200mJ/cm 2Be adjusted to light with the light equal extent of laser or coherence's excellence.
This smooth cationic polymerization initiators for example can use " UV curing; Science and technology " the 23rd～76 page, S.Peter Pappss are compiled, A Technology Marketing Publication and Coments Inorg.Chem, B.Klingert, the material that M.Riediker and A.Roloff, the 7th volume, No. 3, the 109th～138 page (1988), Japanese kokai publication hei 5-107999 communique, TOHKEMY 2002-236439 communique and TOHKEMY 2002-236440 communique are put down in writing.Can use more than a kind or 2 kinds among the present invention.
(any compound)
Except above-mentioned optical polymerism material, also can contain compound arbitrarily in the volume hologram layer that uses among the present invention.As long as any compound of using among the present invention can then be not particularly limited according to the material that the purposes of the volume hologram laminate by manufacturing of the present invention etc. is given volume hologram layer required function.This any compound for example can be enumerated enhanced sensitivity pigment, particulate, thermal polymerization and prevent agent, silane coupling agent, plastifier, colorant and macromolecule bond etc.Wherein, among the present invention, preferred especially the use engages resin, particulate and enhanced sensitivity pigment.By use engaging resin, can make the volume hologram layer even, the hologram image that is easy to keep the polymerization by above-mentioned free-radical polymerised compound to form.
In addition, its reason is can easily give the volume hologram layer required cutting property of paper tinsel by using particulate.
And then its reason is that above-mentioned optical polymerism material is many ultraviolet ray had activity, but has activity by using the enhanced sensitivity pigment that visible light is also become, and can use visible laser recording volume type hologram.
Above-mentioned joint resin for example can be enumerated polymethacrylate or its partial hydrolystate; polyvinyl acetate (PVA) or its hydrolysate; polyvinyl alcohol (PVA) or its part acetal thing; tri acetyl cellulose; polyisoprene; polybutadiene; the polychlorostyrene pentadiene; organic silicon rubber; polystyrene; polyvinyl butyral; Polyvinylchloride; polyacrylate; haloflex; chlorinated polypropylene; poly-N-vinyl carbazole or derivatives thereof; poly-N-vinyl pyrrolidone or derivatives thereof; the multipolymer of styrene and maleic anhydride or its half ester etc.In addition, the multipolymer that also can use at least a kind of monomer polymerization of polymerisable monomers such as will being selected from acrylic acid, acrylate, methacrylic acid, methacrylate, acrylamide, vinyl cyanide, ethene, propylene, vinyl chloride, vinyl acetate to form.And then the present invention also can use these to engage more than a kind or 2 kinds of resin.
In addition, also can use the oligomeric curable resin as above-mentioned joint resin among the present invention.This resin for example can enumerate bisphenol-A, bisphenol S, novolac, orthoresol novolac resin, to epoxy compounds that condensation reaction produced of various phenolic compounds such as alkyl phenolic novolac resin and dichloro table alcohol etc.
(volume hologram layer)
The volume hologram layer preferred glass transition temperature that the present invention uses is more than 100 ℃.Its reason is, even if when thus volume hologram layer being applied heat, also can obtain stable product, can utilize thermal transfer transfer printing volume hologram layer.
In addition, the thickness of the volume hologram layer that uses among the present invention be so long as can write down the degree of required hologram image and then be not particularly limited, be generally in the scope of 1 μ m～50 μ m, more preferably in the scope of 3 μ m～40 μ m, further in the scope of preferred 5 μ m～30 μ m.
C. base material
The base material that the present invention is used then is described.The base material that the present invention uses has the function that supports above-mentioned resin bed and volume hologram layer.
As long as base material used in the present invention can support above-mentioned resin bed and the volume hologram layer then is not particularly limited, for example can use general base materials such as polyester film such as polyethylene terephthalate film.
In addition, the purposes of the volume hologram laminate that the thickness of the base material that the present invention uses is constructed in accordance or kind etc. are suitably selected, and are generally 2 μ m～200 μ m, more preferably in the scope of 10 μ m～50 μ m.
Illustrated, when the base material that the present invention uses and the adaptation of resin bed or volume hologram layer are not enough, by to surface treatments such as substrate surface embodiment such as corona treatment, ozone treatment, Cement Composite Treated by Plasma, ionizing radiation processing, dichromic acid processing, grappling or primary coat processing, can improve the adaptation between base material and resin bed or the volume hologram layer.As various silane coupling agents such as for example known polyurethane series of priming paint, acrylic acid series, ethylene-vinyl acetate copolymer system, vinyl chloride-vinyl acetate copolymer systems, can be from wherein selecting to be suitable for the use of base material.
D. volume hologram forms and uses substrate
The volume hologram that this operation is used forms has above-mentioned base material, resin bed and volume hologram layer with substrate, as their generation type so long as then be not particularly limited according to the above-mentioned resin bed stacked mode that contacts with the volume hologram layer.Therefore, it can be the form that stacks gradually resin bed, volume hologram layer on base material that the volume hologram that uses among the present invention forms with substrate, can also be the form that stacks gradually volume hologram layer, resin bed on base material.For the used volume hologram of the present invention is formed with substrate to for which kind of form, can take suitably selections such as being used for the employed method of recording volume type hologram in the operation according to the aftermentioned hologram.When for example hologram is taken the method for using hologram master recording volume type hologram in the operation, preferably dispose the hologram master in the mode that is contacted with the volume hologram layer, volume hologram therefore used in the present invention forms and is preferably the form that stacks gradually resin bed, volume hologram layer on base material with substrate.
The volume hologram that the present invention uses forms has above-mentioned resin bed, volume hologram layer and base material at least with substrate, also can have other as required and constitute arbitrarily.Any formation of using among the present invention is not particularly limited, and the purposes of volume hologram laminate that can be constructed in accordance is used has the formation of required function.This other configuration examples are as enumerating hard conating, antistatic backing, printed layers, ink-receiver layer, release layer etc.
E. volume hologram forms the method for making with substrate
Then, illustrate that making the used volume hologram of the present invention forms the method for using substrate.Volume hologram used in the present invention forms with substrate and can make by the method that forms resin bed, volume hologram layer successively, respectively on base material.But from the viewpoint that can make with simpler operation, the preferred use after formation on the base material does not contain the resin bed of polymerizable compound, on above-mentioned resin bed, form the volume hologram layer, and then make the part of the contained optical polymerism material of above-mentioned volume hologram layer move to method on the above-mentioned resin bed; Perhaps after forming the volume hologram layer on the base material, on above-mentioned volume hologram layer, form and do not contain the resin bed of polymerizable compound, and then make the part of the contained polymeric materials of above-mentioned volume hologram layer move to method on the above-mentioned resin bed.
Following as the example of the used volume hologram formation of the present invention with the method for making of substrate, this method is described.
The method that forms the resin bed that does not contain polymerizable compound on above-mentioned base material at first is described.As the method that forms the resin bed that does not contain polymerizable compound on above-mentioned base material, the method that contains the layer of resin material as formation generally can be used known method.This method can be enumerated with the fused mass of resin or with the coating fluid of resin dissolves in solvent and coat method on the above-mentioned base material; Perhaps will be pasted on method on the above-mentioned base material etc. by the film that resin constitutes.Among the present invention, can preferably use any method according to the kind of the employed resin of above-mentioned resin bed.
Then, the method that forms the volume hologram layer on above-mentioned resin bed is described.As the method that on above-mentioned resin bed, forms the volume hologram layer, for example can enumerate that the coating fluid that will be dissolved with the optical polymerism material in solvent is coated on method on the above-mentioned resin bed, the film that will contain the optical polymerism material is pasted on the method on the above-mentioned resin bed.
Then, the method that makes the contained optical polymerism material of above-mentioned volume hologram layer move to above-mentioned resin bed is described.After making both be in contact with one another by stacked above-mentioned resin bed and above-mentioned volume hologram layer, heat above-mentioned resin bed and volume hologram layer usually together, thereby can make above-mentioned optical polymerism material move to resin bed by the principle that balance moves.At this moment, by control heat time heating time or heating-up temperature, can adjust the amount of movement of optical polymerism material arbitrarily.
Illustrated, as the method that on above-mentioned resin bed, forms the volume hologram layer, when use will be dissolved with the optical polymerism material in solvent coating fluid is coated method on the above-mentioned resin bed, because when being applied to this coating fluid on the resin bed, because coating fluid infiltrates into above-mentioned resin bed, can make the optical polymerism material move to resin bed, therefore not need to implement in addition above-mentioned processing such as heating sometimes.
On the other hand, when using after forming the volume hologram layer on the base material, on above-mentioned volume hologram layer, form the resin bed that does not contain polymerizable compound, and then the method making volume hologram that a part that makes the contained polymeric materials of above-mentioned volume hologram layer moves on the above-mentioned resin bed forms when using substrate, except the formation reversed order that makes resin bed and volume hologram, can make volume hologram formation substrate by said method.
(2) volumetric The Method for Making A Holograms method
Then, the method that forms recording volume type hologram on the volume hologram layer that possesses with substrate in this operation at above-mentioned volume hologram is described.
Volume hologram as the different striped of refractive index, fixedly comes recording holographic image with the optical polymerism material by the interference fringe that will utilize the interference of light and produce.Therefore, in this operation as the method for recording volume type hologram, so long as can on the volume hologram layer, the method for the interference fringe of recording prescribed then be not particularly limited.This method for example can be enumerated from volume hologram and form base material side irradiation with substrate with reference to light, from volume hologram layer side incident object light, in above-mentioned volume hologram layer with the method for these interference of light; Perhaps configuration hologram master on the volume hologram layer, by from base material side incident light, make this incident light and by the reflected light of above-mentioned hologram master reflection in the method for above-mentioned volume hologram layer internal interference etc.Can preferably use any operation in this operation, the wherein preferred method of using above-mentioned hologram master.By this method, recording volume type hologram simply.
Illustrated that when adopting the method for using above-mentioned hologram master in this operation, the volume hologram formation substrate as using in this operation uses the substrate with the formation that is laminated with resin bed, volume hologram layer on base material in order.
The used optical polymerism material of volume hologram layer uses when containing independent optical polymerism compound, comes recording volume type hologram by this optical polymerism compound of polymerization in this operation.But, use when containing more than 2 kinds the optical polymerism compound as above-mentioned optical polymerism material, can write down above-mentioned volume hologram by the optical polymerism compound of at least a kind of polymerization in this operation.
Illustrated, when containing the material of above-mentioned free-radical polymerised compound and cationically polymerizable compound, passed through polymerization free radical polymerizable compound, recording volume type hologram usually in this operation as above-mentioned optical polymerism material use.
2. material mobile process
Material mobile process of the present invention then is described.This operation is the contained polymerizable compound of resin bed to be moved to by above-mentioned hologram take the operation that operation has write down the volume hologram layer of volume hologram.In addition, this operation can also be by making above-mentioned polymerizable compound move to the volume hologram layer from above-mentioned resin bed, can increase arbitrarily the interference fringe that is recorded in above-mentioned volume hologram layer cycle, can reproduce the operation of the volume hologram that be recorded in the volume hologram layer with any wavelength.
In this operation, as making polymerizable compound move to the method for volume hologram layer, so long as the polymerizable compound of mobile aequum, to make cycle of the interference fringe that is recorded in the volume hologram layer be that method in the fixed range then is not particularly limited from resin bed.As this method, can enumerate the state that is in contact with one another with above-mentioned resin bed and above-mentioned volume hologram layer and place the method for stipulated time, heat the method etc. of above-mentioned resin bed and above-mentioned volume hologram layer together.Can preferably use these any methods in this operation, wherein preferably heat the method for above-mentioned resin bed and above-mentioned volume hologram layer together.Utilize this method,, can easily adjust the amount of movement of above-mentioned polymerizable compound arbitrarily by control heat time heating time or heating-up temperature etc.
3. postprocessing working procedures
Postprocessing working procedures of the present invention then is described.This operation is the operation of the above-mentioned polymerizable compound of polymerization.
Method as the above-mentioned polymerizable compound of polymerization in this operation is suitably selected according to the kind of above-mentioned polymerizable compound.That is, when above-mentioned polymerizable compound is the optical polymerism compound, but the kind of the optical polymerism functional group that is had according to this optical polymerism compound is used the method for the light of irradiation induced polymerization reaction.On the other hand, when above-mentioned polymerizable compound was the thermal polymerization compound, use can be induced the heating treatment method of degree of the polyreaction of the thermal polymerization functional group that this thermal polymerization compound had.
Here, because in the above-mentioned substance mobile process, above-mentioned polymerizable compound moves to the volume hologram layer, therefore when implementing this operation, contains above-mentioned polymerizable compound both of resin bed and volume hologram layer.Therefore, common polymer resin layer and the contained polymerizable compound of volume hologram layer simultaneously in this operation.
Illustrated that therefore contained polymerizable compound in resin bed and the volume hologram layer can not move later owing to solidify by being aggregated in this operation.Therefore, in this operation the playback wavelength of volume hologram is fixed.
4. volume hologram laminate
Then, the volume hologram laminate of making by the present invention is described.The volume hologram laminate that the present invention makes use substrate owing to use above-mentioned volume hologram to form, and therefore the volume hologram laminate by manufacturing of the present invention has base material, is formed at resin bed on the above-mentioned base material, is on the above-mentioned base material and the formed volume hologram layer of adjacent above-mentioned resin bed.
In addition, volume hologram laminate by manufacturing of the present invention is owing to record the volume hologram layer on above-mentioned volume hologram layer, therefore on above-mentioned volume hologram layer, record interference fringe at least, but, the situation that also forms interference fringe on above-mentioned resin bed is arranged also according to the kind of the contained polymerizable compound of above-mentioned resin bed.At this moment, when cycle of cycle of the interference fringe that is formed at above-mentioned volume hologram layer and the interference fringe that is formed at above-mentioned resin bed not simultaneously, can hologram image be reproduced with a plurality of wavelength, therefore can obtain to reproduce the volume hologram laminate of bright hologram image.
Here, the volume hologram laminate by manufacturing of the present invention is characterised in that, makes by the manufacture method of volume hologram of the present invention.That is, the volume hologram laminate by manufacturing of the present invention is characterised in that the spherical zone of formation at least 1 person of above-mentioned volume hologram layer and above-mentioned resin bed.
In the volume hologram laminate of making by the present invention,, specifically describe by the one example for the bulbous region that is formed at above-mentioned volume hologram layer and above-mentioned resin bed.Be formed at the electron micrograph of bulbous region one example of above-mentioned volume hologram layer and above-mentioned resin bed in the volume hologram laminate of Fig. 3～Fig. 5 for expression manufacturing of the present invention.As Fig. 3～shown in Figure 5, the volume hologram laminate by manufacturing of the present invention is formed with spherical zone on volume hologram layer and resin bed.
So, volume hologram laminate by manufacturing of the present invention is characterised in that, on above-mentioned volume hologram layer and above-mentioned resin bed, be formed with spherical zone, therefore whether be for manufacture method manufacturing of the present invention for volume hologram laminate arbitrarily, by confirming whether exist above-mentioned bulbous region easily to judge.By utilizing transmission electron microscope to observe the cross section of above-mentioned hologram layer and resin bed, can clearly confirm having or not of above-mentioned spheric region.
B. volume hologram laminate (the 1st mode)
The volume hologram laminate of the present invention's the 1st mode then, is described.
Volume hologram laminate of the present invention has base material and volume hologram laminated section, this volume hologram laminated section have be formed on the above-mentioned base material, contain the optical polymerism compound, by forming the volume hologram layer that interference fringe records volume hologram, with the resin bed that contains transparent resin that forms adjacent to above-mentioned volume hologram layer, it is characterized in that, on above-mentioned resin bed, be formed with interference fringe.
With reference to accompanying drawing this volume hologram laminate of the present invention is described on one side on one side.Fig. 6 is the skeleton diagram of expression volume hologram laminate one example of the present invention.As shown in Figure 6, volume hologram laminate 210 of the present invention has base material 21 and volume hologram laminated section 22, and this volume hologram laminated section 22 has volume hologram layer 22a that is formed on the above-mentioned base material 21 and the resin bed 22b that contains transparent resin that forms adjacent to above-mentioned volume hologram layer 22a.Here, above-mentioned volume hologram layer 22a contains the optical polymerism compound, by forming interference fringe recording volume hologram.In this example, volume hologram laminate 210 of the present invention is characterised in that on above-mentioned resin bed 22b the formation interference fringe is arranged.In other words, volume hologram laminate 210 of the present invention is characterised in that, is formed with interference fringe on above-mentioned volume hologram layer 22a and above-mentioned resin bed 22b.
Here, above-mentioned Fig. 6 shows the example that has the formation that stacks gradually volume hologram layer and resin bed on base material as volume hologram laminate of the present invention, but volume hologram laminate of the present invention is not to be defined in this formation.Therefore, volume hologram laminate of the present invention can also have the formation that is laminated with resin bed and volume hologram layer on base material in order.
According to the present invention, by on above-mentioned resin bed, also forming interference fringe, can obtain by at random controlling the cycle of the interference fringe that is formed at above-mentioned volume hologram layer and above-mentioned resin bed respectively, can be with the volume hologram laminate of any wavelength reconstructing hologram picture.In addition, according to the present invention by forming above-mentioned resin bed in the mode that is contacted with above-mentioned volume hologram layer, for example utilize after directly forming the volume hologram layer on the above-mentioned resin bed, the method for while recording interference fringe can be made volume hologram laminate of the present invention on these layers.Therefore, by the present invention, can obtain the volume hologram laminate that can utilize simple procedures to make.Thus, can provide the control volume hologram laminate that playback wavelength can reproduce bright hologram image, can make with simple operation by the present invention.
Volume hologram laminate of the present invention has base material and volume hologram laminated section at least, also can have other formations as required.Next coming in order explanation each formation used in the present invention.
1. volume hologram laminated section
The volume hologram laminated section that uses among the present invention at first is described.The volume hologram laminated section that the present invention uses is for forming with the resin bed that contains transparent resin according to being in contact with one another the stacked volume hologram layer that records volume hologram.
1-1: resin bed
The resin bed that uses among the present invention at first is described.The resin bed that uses among the present invention is characterised in that, contains transparent resin, is formed with interference fringe.This resin bed below is described.
(1) interference fringe
As mentioned above, resin bed used in the present invention is characterised in that, be formed with interference fringe, the cycle that is formed at the interference fringe of above-mentioned resin bed is not particularly limited, can be according to the decisions at random such as cycle of the interference fringe that is formed at aftermentioned volume hologram layer.
Here, forming interference fringe at the used resin bed of the present invention can confirm by the section that utilizes transmission electron microscope (TEM) to observe to block on thickness direction resin bed to obtain.
In addition, " cycle of interference fringe " is meant between the adjacent bright striped or the distance between adjacent dark fringe among the present invention.The cycle of interference fringe also can try to achieve by the transmissivity wavelength dependency of measuring resin bed except the method for being obtained according to the TEM multiplying power by the interference fringe of taking transmission electron microscope (TEM) photo in the cross section.Promptly, be incident to by certain angle in the light of resin bed, owing to the light of the wavelength that satisfies the Bragg condition that is determined by fringe period is diffracted in resin bed, so the wavelength dependency of the transmissivity of resin bed shows minimum value under the wavelength that satisfies the Bragg condition that is determined by fringe period.Therefore, the minimum transmission peak wavelength of the wavelength dependency by trying to achieve transmissivity can be obtained cycle of above-mentioned interference striped.Illustrated, use above-mentioned transmission electron microscope to try to achieve in the method in cycle, in captured interference fringe, photographed the cycle of representing the interference fringe of above-mentioned resin bed average period of the part of regular periods clearly.
The cycle that is formed at the interference fringe of the used resin bed of the present invention can be stable in whole resin bed, also can be different.When interference fringe has a plurality of different cycles, as the mode of the interference fringe that forms different cycles, can be to change continuously in cycle of interference fringe and the mode that forms, perhaps can be the mode that forms different interference fringe of cycle discontinuously.
In addition, the cycle that is formed at the interference fringe of resin bed used herein can be identical with the cycle of the interference fringe that is formed at aftermentioned volume hologram layer, and is perhaps different.Wherein, be preferably formed among the present invention in the cycle of the interference fringe of resin bed different with the cycle of the interference fringe that is formed at aftermentioned volume hologram layer.Its reason is, but thus since by with the light reconstructing hologram picture of any one corresponding to wavelength of cycle of the interference fringe that is formed at above-mentioned resin bed and volume hologram layer, therefore can utilize a plurality of playback wavelength reconstructing hologram pictures, thereby make volume hologram laminate of the present invention can reproduce more bright hologram image.
Be formed at above-mentioned resin bed interference fringe cycle be formed at aftermentioned volume hologram layer interference fringe cycle not simultaneously, the cycle that is formed at the interference fringe of resin bed can be greater than or less than the cycle of the interference fringe that is formed at above-mentioned volume hologram layer.
Here, among the present invention, the cycle that is formed at the interference fringe of resin bed is meant that with the fringe period that is formed at aftermentioned volume hologram layer " different " there is the above difference of 3nm in the cycle of two-layer at least interference fringe.
(2) transparent resin
Transparent resin of the present invention then is described.As long as having the required transparency, transparent resin used in the present invention then is not particularly limited.Here, the transparent resin that uses among the present invention since with above-mentioned " manufacture method of A. volume hologram laminate " illustrated the same, therefore omission explanation here.
(3) any compound
Except above-mentioned transparent resin, also can contain other compounds arbitrarily in the resin bed used in the present invention.Above-mentioned compound arbitrarily is not particularly limited, can be according to the present invention the purposes of volume hologram laminate at random select to use the material that can give the resin bed required function.Here, above-mentioned any compound since with above-mentioned " manufacture method of A. volume hologram laminate " illustrated the same, therefore omission explanation here.
(4) resin bed
The thickness of resin bed used in the present invention is so long as the kind of corresponding above-mentioned transparent resin etc., and volume hologram laminate of the present invention is become can then be not particularly limited with the scope of required wavelength reconstructing hologram picture.
1-2: volume hologram layer
Volume hologram layer used in the present invention then is described.Volume hologram layer used in the present invention is characterised in that, contains the optical polymerism compound, by forming interference fringe recording volume hologram.
This volume hologram layer below is described.
(1) interference fringe
As mentioned above, volume hologram layer used in the present invention is formed with interference fringe, and the cycle that is formed at the interference fringe of volume hologram layer can be certain in whole volume hologram layer, also can be different.When interference fringe has a plurality of different cycles, as the mode of the interference fringe that forms different cycles, can be the mode that forms according to the continuous variation of the cycle of interference fringe, can also be the mode that forms different interference fringes of cycle discontinuously.
The cycle that is formed at the interference fringe of the used volume hologram layer of the present invention can be identical with the cycle of the interference fringe that is formed at above-mentioned resin bed, perhaps can be also different.Wherein, be preferably formed among the present invention in the cycle of the interference fringe of above-mentioned resin bed different with the cycle of the interference fringe that is formed at the volume hologram layer.Thus, but by with the light reconstructing hologram picture of any one corresponding to wavelength of cycle of the interference fringe that is formed at above-mentioned resin bed and volume hologram layer.Therefore, can utilize a plurality of playback wavelength reconstructing hologram pictures, thereby make volume hologram laminate of the present invention can reproduce more bright hologram image.Illustrated, for the cycle of the interference fringe that the is formed at above-mentioned resin bed mode different with the cycle of the interference fringe that is formed at the volume hologram layer, with same as the mode of the interference fringe that is formed at resin bed in above-mentioned " 1-1. resin bed " item, therefore omit explanation here.
Illustrated that the concrete cycle that is formed at the interference fringe of the used volume hologram layer of the present invention is equivalent to the wavelength of visible region.
(2) optical polymerism compound
Then, the contained optical polymerism compound of above-mentioned volume hologram layer is described.Optical polymerism compound used in the present invention is so long as can carry out polyreaction by the light of irradiation regulation, can form interference fringe on the volume hologram layer and then be not particularly limited.Here, illustrated the same of optical polymerism compound used in the present invention and above-mentioned " manufacture method of A. volume hologram laminate ", therefore omission explanation here.
Illustrated that volume hologram layer of the present invention is owing to be to have write down volume hologram, therefore above-mentioned optical polymerism compound contains in the volume hologram layer as polymkeric substance.
(3) compound arbitrarily
The volume hologram layer that uses among the present invention also can contain compound arbitrarily except above-mentioned optical polymerism compound.Any compound used in the present invention can corresponding volume hologram laminate of the present invention purposes etc. suitably select.Here in the used any compound of volume hologram layer of the present invention and above-mentioned " manufacture method of A. volume hologram laminate " as illustrated the same of the used any compound of volume hologram layer, therefore omission explanation here.
1-3. volume hologram laminated section
Volume hologram laminated section used in the present invention is formed on the aftermentioned base material, be formed at mode on the above-mentioned base material as above-mentioned volume hologram laminated section among the present invention, can be to be disposed at above-mentioned base material side and the mode that forms, perhaps be disposed at above-mentioned base material side and the mode that forms according to above-mentioned resin bed side according to above-mentioned volume hologram layer side.
2. base material
Then, the base material that the present invention uses is described.The used base material of the present invention has the function that supports above-mentioned volume hologram laminated section.Here, explanation is the same in the used base material of the present invention and above-mentioned " manufacture method of A. volume hologram laminate ", therefore omission explanation here.
3. constitute arbitrarily
Volume hologram laminate of the present invention has above-mentioned volume hologram laminated section and base material at least, also can have other as required and constitute arbitrarily.Any formation used in the present invention is not particularly limited, and can use the purposes of corresponding volume hologram laminate of the present invention to have the formation of required function.
4. volume hologram laminate
The transmissivity of the preferred visible region of volume hologram laminate of the present invention shows the minimum projection wavelength more than 2.Its reason is, can make volume hologram laminate of the present invention can reproduce bright hologram image thus.
C. volume hologram transfer foil
Then, volume hologram transfer foil of the present invention is described.As mentioned above, volume hologram transfer foil of the present invention is characterised in that, have the invention described above volume hologram laminate, be formed on the above-mentioned volume hologram laminated section of above-mentioned volume hologram laminate and contain the hot sealing layer of thermoplastic resin.
With reference to accompanying drawing this volume hologram transfer foil of the present invention is described on one side on one side.Fig. 7 is the summary sectional view of expression volume hologram transfer foil one example of the present invention.As shown in Figure 7, volume hologram transfer foil 220 of the present invention is characterised in that, have the invention described above volume hologram laminate 210, be formed on the volume hologram layer 22 of above-mentioned volume hologram laminate 210 and contain the hot sealing layer 221 of thermoplastic resin.
According to the present invention, by using the volume hologram laminate of the invention described above, can obtain can transfer printing to be formed at cycle of the interference fringe of the above-mentioned volume hologram layer of above-mentioned volume hologram laminate and above-mentioned resin bed by control at random respectively, can be with the volume hologram transfer foil of the volume hologram of any wavelength reconstructing hologram picture.
Volume hologram transfer foil of the present invention has above-mentioned volume hologram laminate and above-mentioned hot sealing layer at least.
Next coming in order illustrate employed each formation of volume hologram transfer foil of the present invention.
1. volume hologram laminate
At first, the volume hologram laminate that uses among the present invention is described.The volume hologram laminate that uses among the present invention is the related volume hologram laminate of the invention described above.Therefore, explanation identical in volume hologram laminate used in the present invention and above-mentioned " the B. volume hologram laminate ".
Here, the used volume hologram laminate of the present invention has base material and volume hologram laminated section as mentioned above at least, in view of the purposes of volume hologram transfer foil, preferably has above-mentioned other formations in addition among the present invention.As other used formations of above-mentioned volume hologram laminate, can enumerate release layer and protective seam as the preferred formation of using among the present invention.
2. hot sealing layer
Then, the hot sealing layer that the present invention uses is described.Hot sealing layer used in the present invention contains thermoplastic resin, when using volume hologram transfer foil of the present invention that the volume hologram laminated section is transferred to transfer printing body, has the function that volume hologram laminated section and transfer printing body are engaged.Below explain hot sealing layer used in the present invention.
Thermoplastic resin used in the present invention engages volume hologram laminated section and transfer printing body so long as can be corresponding from volume hologram transfer foil transfer printing of the present invention the kind of the transfer printing body of volume hologram laminated section be arranged, and then is not particularly limited.Object lesson since with aftermentioned " E.Volume hologram laminate (the 2nd mode) " in explanation same, therefore omit explanation here.
Illustrated that thermoplastic resin used in the present invention can only be a kind, perhaps can be for more than 2 kinds.
The adjuvant that except above-mentioned thermoplastic resin, also can contain other in the hot sealing layer used in the present invention.Adjuvant used in the present invention for example can be enumerated spreading agent, filling agent, plastifier, antistatic agent etc.
The thickness of the hot sealing layer that the present invention is used is not particularly limited, according to use volume hologram transfer foil transfer printing of the present invention the kind etc. of transfer printing body of volume hologram laminated section suitably select, be preferably the scope of 0.3 μ m～50 μ m, the scope of preferred 0.5 μ m～25 μ m wherein usually.Its reason is, when thickness is thinner than above-mentioned scope, with the connectivity of transfer printing body might be not enough.When being thicker than above-mentioned scope, during by the folded portion of volume hologram transfer foil transfer printing volume hologram layer of the present invention, the temperature of heat hot seal becomes too high, might damage base material etc.
In addition, hot sealing layer used in the present invention can only be 1 layer, perhaps can be for more than 2 layers.The mode of hot sealing layer can be the mode of the hot sealing layer of the same composition of stacked use more than 2 layers as using among the present invention, perhaps can be the stacked mode of using the different hot sealing layers of forming.
3. constitute arbitrarily
Volume hologram transfer foil of the present invention has above-mentioned volume hologram duplexer and hot sealing layer at least, also can use other any formations as required.Any formation used in the present invention can corresponding volume hologram transfer foil of the present invention purposes, the formation of suitably selecting to possess required function is used.Wherein, any configuration example of preferably using of the present invention is as enumerating spacer, printed layers (style layer) or lettering layer (individual information numbering etc.).
D. volume hologram label
The volume hologram label that the present invention is used then is described.As mentioned above, volume hologram label of the present invention is characterised in that the volume hologram laminate with the invention described above, the knitting layer that is formed at the above-mentioned volume hologram laminated section of above-mentioned volume hologram laminate.
With reference to accompanying drawing this volume hologram label of the present invention is described on one side on one side.Fig. 8 is the skeleton diagram of expression volume hologram label one example of the present invention.As shown in Figure 8, volume hologram label 230 of the present invention is characterised in that, have the invention described above volume hologram laminate 210, be formed at the knitting layer 231 on the above-mentioned volume hologram laminated section 22 of above-mentioned volume hologram laminate 210.
According to the present invention, by using the volume hologram laminate of the invention described above, the cycle that is formed at the interference fringe of the above-mentioned volume hologram layer of above-mentioned volume hologram laminate and above-mentioned resin bed by control at random respectively can be obtained to paste, the volume hologram label of the volume hologram of bright hologram image can be reproduced with any wavelength.
Volume hologram label of the present invention has above-mentioned volume hologram laminate and above-mentioned knitting layer at least, also can have other formations as required.Next coming in order illustrate that used each of volume hologram label of the present invention constitutes.
1. volume hologram laminate
At first, the volume hologram laminate that the present invention uses is described.Volume hologram laminate used in the present invention is the related volume hologram laminate of the invention described above.Therefore, explanation identical in volume hologram layer laminates used in the present invention and above-mentioned " the B. volume hologram laminate ".
2. knitting layer
Knitting layer used in the present invention then is described.As the bonding agent that constitutes the used knitting layer of the present invention can be heat sealing agent, also with general pressure-sensitive adhesive.Here, cement used in the present invention can use the material of explanation in aftermentioned " E. volume hologram laminate (the 2nd the mode) " item, therefore omits explanation here.
The thickness of knitting layer is preferably in the scope scope interior, 5 μ m～100 μ m more preferably of 4 μ m～200 μ m.
E. volume hologram laminate (the 2nd mode)
The volume hologram laminate of the present invention's the 2nd mode then, is described.
The volume hologram laminate of the manner for base material top resin bed is set in, adjacent with this resin bed and at the folded volume hologram laminate that the volume hologram layer is arranged of above-mentioned layers on substrates, it is characterized in that, when being formed with volume hologram on above-mentioned resin bed, the part that is provided with resin bed of volume hologram laminate is different with the reproduction centre wavelength of the part that resin bed is not set.
Fig. 9 is the cross section mode chart of volume hologram laminate of the present invention, be laminated with part be arranged at resin bed 2 on the base material 1, adjacent to the volume hologram layer 3 on the above-mentioned base material 1 and on the resin bed 2 (Fig. 9 (a)) based on the volume hologram recording materials that contain free radical polymerization monomer and cationically polymerizable monomer.
Here, in above-mentioned Fig. 9 (a) example the adjacent mode of above-mentioned base material 1 and resin 2, but volume hologram laminate of the present invention is not to be defined in this correspondence, for example can also be the mode (Fig. 1 (b)) that forms undercoat 8 between base material 1 and resin bed 2.
Base material 1 can use polyethylene terephthalate that can support resin bed 2, volume hologram layer 3 etc.The thickness of base material is generally 2 μ m～200 μ m, is preferably in the scope of 10 μ m～50 μ m.
In addition, in aftermentioned volume hologram fitting body, can make base material bring into play function as diaphragm, and peelable removing.During as diaphragm performance function; the adaptation of base material and resin bed or volume hologram recording materials layer is necessary, can be to the surperficial embodiment such as the surface treatments such as corona treatment, ozone treatment, plasma, ionizing radiation processing, dichromic acid processing, grappling or primary coat processing of base material.For example can enumerate ammonia ester system, acrylic acid series, ethylene-vinyl acetate copolymer system, vinyl chloride-vinyl acetate copolymer system etc. as anchoring agent or silane coupling agent.In addition, be stripped from when removing, base material can be handled through the demoulding, also can across or be not provided with resin bed and volume hologram layer across protective seam.
Then, resin bed 2 is for having the resin bed of the transparency, and the part coating on base material forms resin solution and for example becomes pattern-like such as type and obtain.The resin that forms resin bed can be enumerated the material of explanation in above-mentioned " manufacture method of A. volume hologram laminate " item, can enumerate polymethylmethacrylate (PMMA) resin etc. especially.
When the resin that forms resin bed is plexiglass or polyvinyl acetate resins, vibrin etc., its detailed reason is not clear, but the reproduction centre wavelength that as seen makes the part that is laminated with resin bed 2 (base material 1/ resin bed 2/ volume hologram layer 3 ') in the volume hologram laminate is compared to the reproduction centre wavelength of the part of stacked resin bed not (base material/volume hologram layer 3 "), in the long wavelength side difference.Different degree is subjected to the influence of the weight-average molecular weight size of resin, and weight-average molecular weight is 5000～1000000, is preferably 5000～500000, is preferably at 10000～300000 o'clock especially, can make in long wave side more to reproduce the centre wavelength difference.Illustrated that the molecular weight of resin is a weight-average molecular weight of utilizing the polystyrene conversion of GPC (gel permeation chromatography) mensuration.
The difference of reproduction centre wavelength of reproduction centre wavelength and the part that is not provided with resin bed that is provided with the part of resin bed be at least 10nm above, be preferably more than the 15nm.Illustrated that its difference is 100nm to the maximum.
In addition, when the resin that forms resin bed is resin such as polyvinyl butyral resin or polyvinyl acetal resin, its detailed reason is also unclear, but with above-mentioned different, the reproduction centre wavelength of the part that is provided with resin bed is compared with the reproduction centre wavelength of the part of stacked resin bed not, as seen different at short wavelength side.The influence that is subjected to the weight-average molecular weight size of resin same as described above of different degree, weight-average molecular weight is 5000～1000000, is preferably 5000～500000, is preferably at 10000～300000 o'clock especially, can make in shortwave side more to reproduce the centre wavelength difference.
The difference of reproduction centre wavelength of reproduction centre wavelength and the part that is not provided with resin bed that is provided with the part of resin bed be at least 10nm above, be preferably more than the 15nm.Illustrated that its difference is 100nm to the maximum.
The centre wavelength of respectively reproducing that is provided with the part of resin bed and is not provided with the part of resin bed obtains the spectral transmission curve for using spectrophotometer (UV-2450 (strain) Shimadzu Seisakusho Ltd. system) to measure transmissivity, utilize following method to try to achieve by this spectral transmission curve with diffraction efficiency, half-peak breadth, use Fig. 4 to describe.
(diffraction efficiency)
Try to achieve the peak transmissivity A and the paddy transmissivity B of spectral transmission, calculate | B-A|/B (%).
(half-peak breadth)
Obtain half the left end (C) and the right-hand member (D) of spectral transmission curve of transmissivity (A+|B-A|/2) that adds the difference of upper valley transmissivity A and peak transmissivity B at peak transmissivity A, calculate half-peak breadth=| D-C| (nm).
(reproduction centre wavelength)
Half the wavelength (=C+|D-C|/2) that adds half-peak breadth when calculating half-peak breadth on the C that will try to achieve is as reproducing centre wavelength.
In resin bed 2, also can in the scope that does not influence above-mentioned playback wavelength difference, add for example antioxidant, ultraviolet light absorber, light stabilizer, thermal stabilizer, plastifier, lubricant, antistatic agent, fire retardant, filling agent etc.
Resin bed 2 following formation: utilize intaglio printing, serigraphy etc. to be coated on the resin solution that is dissolved with compositions such as above-mentioned resin in MEK, toluene, the ethyl acetate etc. on base material top, to reach dry film thickness on the base material be 0.1 μ m～10 μ m, be preferably 0.5 μ m～5 μ m, be preferably 0.5 μ m～3 μ m especially.
Illustrated that resin bed 2 can be according to adjacent with above-mentioned base material 1 and form, perhaps also can be according to being adjacent on the base material 1 with undercoat etc. other layers that form and forming.
Undercoat used in the present invention can corresponding volume hologram laminate of the present invention purposes suitably select to have the material of required function, be not particularly limited.
Then, as shown in Figure 9, on the resin bed 2 that is formed at base material 1, directly be not coated with and form volume hologram recording material layer by the middle layer.
The used volume hologram recording materials layer of the present invention is from containing the optical polymerism material, can write down the viewpoint of the high hologram image of contrast sets out, preferred also with free radical polymerization monomer and cationically polymerizable monomer, use with optical free radical polymerization initiator, light cationic polymerization initiators.
Here, for the used free-radical polymerised compound of the present invention, optical free radical polymerization initiator, cationically polymerizable compound, light cationic polymerization initiators, since identical with the material of the explanation of above-mentioned " manufacture method of A. volume hologram laminate ", explanation therefore omitted here.
The manufacture method of volume hologram laminate of the present invention then, is described.
Volume hologram laminate of the present invention is at first after the coating of ground, base material top forms resin bed, being adjacent to respectively be coated with the volume hologram recording materials layer that formation contains free radical polymerization monomer and cationically polymerizable monomer on the base material and on the resin bed, make duplexer.
(1) the gained duplexer is implemented etching processing.Etching processing is by at room temperature placing duplexer or heating duplexer down at 40～80 ℃ and carried out in 1～48 hour.Handle by this, in the layer of base material/resin bed/volume hologram recording materials layer constituted, the monomer in the volume hologram recording materials layer etc. moved in the resin bed.As described in embodiment 1, when the resin bed after the etching processing being carried out the IR analysis, confirm that free radical polymerization monomer or the cationically polymerizable monomer in the volume hologram recording materials layer moves in the resin bed.
(2) then, after duplexer enforcement etching processing, behind this volume hologram recording materials layer side driving fit hologram master, utilize laser radiation to carry out hologram exposure, make the volume hologram layer that has write down hologram from the base material side of duplexer.
The interference fringe that volume hologram will produce by the interference of light is as the different striped of diffraction efficiency, and optical polymerism is material immobilized, thus the recording holographic image.Therefore, in this operation as the method for recording volume type hologram, for example can enumerate from volume hologram and form base material side incident with substrate,, in above-mentioned volume hologram layer, make the method for these interference of light from volume hologram layer side incident object light with reference to light; Configuration hologram master on the volume hologram layer, from base material side incident light, thereby make this incident light and by the reflected light of above-mentioned hologram master reflection in the method for above-mentioned volume hologram layer internal interference etc.Wherein, the method for preferred above-mentioned use hologram master, recording volume type hologram simply thus.
(3) behind the exposure hologram, peel off the hologram master, at the stacked PET film of release surface.Then, descend heating after 5 minutes～120 minutes, at 50 ℃～150 ℃ duplexer with 500mJ/cm 2～5000mJ/cm 2Irradiation ultraviolet radiation.Heating treatment step thinks to make after hologram exposure the part of residual polymerizable monomer to spread once more, and other monomers are immobilized by heat treated-ultraviolet treatment with irradiation, make the operation of stable hologram.
Among the present invention, when using plexiglass or polyvinyl acetate resins to form resin bed, the part that resin bed is not set with volume hologram laminate is compared, and in the laminated portions of base material/resin bed/volume hologram layer, as seen reproduces centre wavelength in the long wavelength side difference.Its detailed reason is also unclear, after thinking that might to be the fringe period (interference fringe at interval) of observing the volume hologram layer by the electron microscope cross-section photograph of aftermentioned embodiment 1 than the fringe period (fringe period) of resin bed more amplify, the heating process generation monomer that utilizes above-mentioned (3) is from resin bed moving again to the volume hologram layer, the reproduction centre wavelength of the laminated portions of base material/resin bed/volume hologram layer is compared with the reproduction centre wavelength of the laminated portions of the substrate resin layer/volume hologram layer that is not provided with resin bed thus, in the long wavelength side difference.
In addition, when using polyvinyl butyral resin, polyvinyl acetal resin formation resin bed, on the laminated portions of the base material/resin bed of volume hologram laminate/volume hologram layer, reproduce centre wavelength and compare at short wavelength side different with the part that resin bed is not set.Its detailed reason is also unclear, think that polyvinyl butyral resin, polyvinyl acetal resin by the heating process of above-mentioned (3) moving of the monomer different with the PMMA resin bed are taken place, the reproduction centre wavelength of the laminated portions of base material/resin bed/volume hologram layer is compared with the reproduction centre wavelength of the laminated portions of the substrate resin layer/volume hologram layer that is not provided with resin bed, in the short wavelength side difference.
So, volume hologram laminate of the present invention can be made part and has and make the volume hologram laminate that reproduces the different part of centre wavelength.In addition, with the gained volume hologram laminate as master, driving fit volume hologram recording materials layer thereon, utilize the laser of single wavelength to attempt contact copying, reproduce the different part deepening of centre wavelength, can't ideally duplicate, can be made into the volume hologram laminate of false proof excellence.
Then, use Figure 10, Figure 12 that volume hologram transfer sheet material of the present invention is described.Figure 10 is the 1st volume hologram transfer with sheet material, is provided with cement layer 4 on the volume hologram layer 3 of the volume hologram laminate of Fig. 9.Cement layer 4 is the situation that adhesive phase or hot sealing layer, particularly Figure 10 have shown further stacked fissility sheet material 5 when making adhesive phase, makes the situation of volume hologram transfer label.When making hot sealing layer, fissility sheet material 5 can omit, and makes volume hologram transfer foil.
Figure 12 is the 2nd volume hologram transfer sheet material, on the volume hologram layer of the volume hologram laminate of Fig. 9, strippable the 2nd base material 7 is set, on resin bed 2 that exposes at the base material 1 of the volume hologram laminate of peeling off Fig. 9 and the volume hologram layer 3 cement layer 4 is set simultaneously.Cement 4 is adhesive phase or hot sealing layer, shows the situation of further stacked fissility sheet material 5 when making adhesive phase among Figure 12, makes the situation of volume hologram transfer label.When making hot sealing layer, fissility sheet material 5 can omit, and makes volume hologram transfer foil.
Bonding agent as the volume hologram transfer label can use acryl resin.Bonding agent can use ethyl acetate, toluene, MEK, butyl acetate etc. to make coating fluid as solvent, with dry film thickness 0.5 μ m～20 μ m coat on the fissility sheet material form adhesive phase after, be laminated on the volume hologram layer 3 with the fissility sheet material.As the fissility sheet material, except normally used peeling paper, also can use and utilize fluorine is that release agent, silicon-type release agent etc. are implemented demoulding processing and the film of acquisition to pet resin film, polypropylene resin film etc.
In addition, heat sealing agent as volume hologram transfer foil, be thermoplastic resin, material with heat sealability can be enumerated the ethylene-vinyl acetate copolymer resins as the resin that can be made into organic solvent solution formation hot sealing layer, polyamide, vibrin, polyvinyl resin, ethylene-acrylic acid isobutyl ester copolymer resins, butyral resin, polyvinyl acetate resins, the vinyl chloride vinyl acetate copolymerized resin, cellulose derivative, acryl resins such as plexiglass, the polyvinylether resin, urethane resin, polycarbonate resin, acrylic resin, epoxy resin, phenolics, SBS, SIS, SEBS, thermoplastic elastomer such as SEPS or reaction hot melt are resin etc.Organic solvent can be enumerated toluene, MEK etc., and utilisation point formula coating machine (comma coater), mould coating machine, intaglio plate coating machine etc. are formed on the volume hologram layer 3 with dry film thickness 2～10 μ m coating.
Use Figure 11, Figure 13 that volume hologram fitting body of the present invention is described.As shown in figure 11; volume hologram fitting body of the present invention is after peeling off above-mentioned volume hologram transfer shown in Figure 10 with the fissility sheet material 5 of sheet material; fitted on the lining body 6 by adhesive layer 4 sides, base material 1 is stripped from the protective seam of removing or left behind as the volume hologram layer.
In addition; the present invention shown in Figure 13 waits other volume hologram fitting bodies after above-mentioned volume hologram transfer shown in Figure 12 is peeled off with the fissility sheet material 5 of sheet material; fitted on the lining body 6 by cement layer 4 side, the 2nd base material 7 is stripped from the protective seam of removing or left behind as the volume hologram layer.
As the lining body 6 of volume hologram fitting body of the present invention, for example can enumerate transparent or opaque materials such as glass, plastics.Plastics can be enumerated vibrin such as vestolit, acryl resin, polystyrene resin, polyethylene terephthalate, and polycarbonate resin etc. are particularly suitable for making the situation of the card that is made of vibrin, sheet material, film.Volume hologram transfer can be pasted on sheet material on the pamphlets such as the card of sheet material, ID card of I.D., ticket checking and so on etc. or passport, in addition, also be suitable for making the certificate of the security personnel that show fire prevention, sterilization or fire prevention etc., health grade or be used to implement the certificate of this disposal.In addition, for the purposes that adhesive paper accreditation book seals, the object article are transparent and be tabular or 2 dimension curved surfaces, replaceable in principle one-tenth certificate substantially.And then, as pasting the object of volume hologram transfer, can be widely used in film or the sheet material that constitutes by paper, synthetic paper, synthetic resin, metal or have the article that obtain part by glass etc. with sheet material.In addition, also can utilize uniqueness that volume hologram has, can show three-dimensional characteristic etc., as the label utilization that is pasted on vehicle window, best buys etc. such as newspaper such as book or saddle stitching weekly or automobile.
Illustrated that the present invention is defined in above-mentioned embodiment.Above-mentioned embodiment is an example, has the identical formation with essence of technological thought put down in writing with claim scope of the present invention, plays same purpose effect person and be also contained in the technical scope of the present invention.
Embodiment
Below enumerate embodiment and specifically describe the present invention, the present invention is defined in following embodiment.
1-1. embodiment 1
(1) volume hologram forms the making with substrate
Polyethylene terephthalate (PET) film (Lumirror one 50T60, east beautiful (strain) system) as base material used thickness 50 μ m, using rod to be coated with machine is coated on the polymethylmethacrylate that is dissolved with weight-average molecular weight 15000 in the solvent on above-mentioned base material resin bed forms and reaches coating film thickness 2 μ m with coating fluid, be dried, thereby form resin bed.
Then, use dispenser on above-mentioned resin bed, directly to be coated with volume hologram layer formation and use coating fluid, reach dry film thickness 10 μ m, form the volume hologram layer with following composition.
(the volume hologram layer forms and uses coating fluid)
Polyvinyl acetate (PVA) 35 weight portions
(Denka SAKNOHOLSN-08H: the degree of polymerization 800; Electrochemical industry (strain) system)
1,6-hexanediol diglycidyl ether 25 weight portions
(Denacol EX-212; Nagase ChemteX (strain) system)
Two phenoxetol fluorenes diacrylates, 35 weight portions
(BPEFA: Osaka aerochemistry (strain) system)
Diaryl group iodized salt 4 weight portions
(PI2074; The Rhodia system)
2,5-two (4-diethylamino benzal base) cyclopentanone 1 weight portion
Methyl isobutyl ketone 100 weight portions
1-butanols 100 weight portions
(2) hologram is taken operation
Then, stacked hologram master on above-mentioned volume hologram layer is from base material side incident 80mJ/cm 2The laser of 532nm, recording volume type hologram.Behind the record, peel off the volume hologram master, with the PET film-stack of thickness 50 μ m on above-mentioned volume hologram layer.
(3) material mobile process
Then, heat above-mentioned resin bed and above-mentioned volume hologram layer.At this moment, heating condition be 100 ℃ following 10 minutes.
(4) postprocessing working procedures
Then, by irradiation ultraviolet radiation fixed volume hologram layer all sidedly, obtain volume hologram laminate.
1-2. embodiment 2
Use the material of weight-average molecular weight 35000 as polymethylmethacrylate, in addition utilize the method making volume hologram laminate identical with embodiment 1.
1-3. embodiment 3
Use the material of weight-average molecular weight 100000 as polymethylmethacrylate, in addition utilize the method making volume hologram laminate identical with embodiment 1.
1-4. embodiment 4
Replace polymethylmethacrylate to use the vibrin (Vylon270, Japan weaving society system) of weight-average molecular weight 40000, in addition utilize the method making volume hologram laminate identical with embodiment 1.
1-5. comparative example 1
Do not form resin bed, on base material, directly form the volume hologram layer, in addition utilize the method making volume hologram laminate identical with embodiment 1.
1-6. hologram record evaluating characteristics
Utilize spectrophotometer (UV-2450; (strain) Shimadzu Seisakusho Ltd. system) transmissivity of the volume hologram laminate of mensuration embodiment and comparative example acquisition is by spectral transmission curve calculation diffraction efficiency, half-peak breadth and reproduction centre wavelength.It is the results are shown in following table 1
The spectral transmission curve of embodiment 1～3 and comparative example 1 is shown in Figure 14.
Table 1
Half-peak breadth (nm) Diffraction efficiency (%) Reproduce centre wavelength (nm)
Embodiment 1 ??24 ??80 ??532
Embodiment 2 ??27 ??81 ??539
Embodiment 3 ??24 ??74 ??544
Embodiment 4 ??28 ??74 ??556
Comparative example 1 ??28 ??88 ??527
2-1. embodiment 5
(1) making of volume hologram laminate
Polyethylene terephthalate (PET) film (Lumirror one 50T60, east beautiful (strain) system) as base material used thickness 50 μ m, utilizing woodburytype to use the polymethylmethacrylate of weight-average molecular weight 100000 to be dissolved in resin bed in the methyl ethyl ketone solvent forms and uses coating fluid, coating forms resin bed and becomes pattern-like on above-mentioned base material, forms the resin bed through pattern formation of dry film thickness 2 μ m.
Then, use dispenser directly to be coated with volume hologram layer formation and use coating fluid, reach dry film thickness 10 μ m, form the volume hologram layer with following composition in above-mentioned resin bed mulberry.
(the volume hologram layer forms and uses coating fluid)
Polyvinyl acetate (PVA) (Denka SAKNOHOL SN-08H: the degree of polymerization 800; Electrochemical industry (strain) system) 35 weight portions
1,6-hexanediol diglycidyl ether (Denacol EX-212; Nagase ChemteX (strain) system) 25 weight portions
Two phenoxetol fluorenes diacrylates (BPEFA: Osaka aerochemistry (strain) system) 35 weight portions
Diaryl group iodized salt (PI2074; The Rhodia system) 4 weight portions
2,5-two (4-diethylamino benzal base) cyclopentanone 1 weight portion
Methyl isobutyl ketone 100 weight portions
1-butanols 100 weight portions
(2) etching procedure
The gained volume hologram laminate was at room temperature placed 24 hours, carried out etching processing.After the etching processing, utilize IR analytical equipment (Japanese beam split (strain) system FT/IR-610) to analyze resin bed, confirm to contain 1,6-hexanediol diglycidyl ether and two phenoxetol fluorenes diacrylates.
(3) hologram is taken operation
Stacked hologram master on the volume hologram layer of volume hologram laminate is from base material side incident 80mJ/cm 2The laser of 532nm, recording volume type hologram.Behind the record, peel off the volume hologram master, with the PET film-stack of thickness 50 μ m on above-mentioned volume hologram layer.
(4) heat treated-ultraviolet treatment with irradiation operation
Volume hologram laminate behind 100 ℃ of following heat treated hologram records is after 10 minutes, all sidedly irradiation ultraviolet radiation (3000mJ/cm 2), fixed hologram figure obtains the volume hologram layer.
Figure 15 dwindles the manifolding thing for 70% of the longitudinal section scanning electron microscope photo (15000 times) of the position of stacked resin bed in the gained volume hologram laminate.1 of Figure 15 be base material, 2 for resin bed, 3 for the volume hologram layer, on resin bed 2 with interval 116nm recording interference fringe, in addition, on volume hologram layer 3 with interval 186nm recording interference fringe.
Use spectrophotometer (UV-2450 for the part that forms through pattern of resin bed with without the part that pattern forms; (strain) Shimadzu Seisakusho Ltd. system) measures transmissivity, its result is shown in Figure 16 as the spectral transmission curve.
The reproduction centre wavelength of the spectral transmission curve (B) of the part that the reproduction centre wavelength of the spectral transmission curve (A) of the part that resin bed forms through pattern is 544nm, form without pattern is 527nm.
(for antifalsification)
Use dispenser that the volume hologram layer formation of above-mentioned record is coated on the PET film of thickness 50 μ m with coating fluid, reach dry film thickness 10 μ m, obtain duplexer, after sticking on this PET film as master the above-mentioned volume hologram laminate that has write down volume hologram from this volume hologram recording materials layer side, use the laser shooting volume hologram of 532nm, resin bed can't be taken hologram well through the part deepening that pattern forms.
2-2. embodiment 6
Except using the methyl ethyl ketone solution of polyvinyl acetal resin (S-LEC BH-6: weight-average molecular weight is about 92000, ponding chemistry society system) with coating fluid as resin bed, implement similarly to Example 5, obtain to have write down the volume hologram laminate of volume hologram.
Through the part of pattern formation and the part that forms without pattern, use spectrophotometer (UV-2450:(strain) Shimadzu Seisakusho Ltd.'s system for resin bed) measure transmissivity, Figure 17 represents the spectral transmission curve.
The reproduction centre wavelength of the spectral transmission curve (D) of the part that the reproduction centre wavelength of the spectral transmission curve (C) of the part that resin bed forms through pattern is 490nm, form without pattern is 527nm.
In addition, for antifalsification, similarly to Example 5, when the volume hologram laminate that has write down volume hologram was taken volume hologram as master, resin bed can't be taken hologram well through the part deepening that pattern forms.
2-3. embodiment 7
Except using with coating fluid the methyl ethyl ketone solution of polyvinyl acetate resins (weight-average molecular weight about 500000, ALDRICH system) as resin bed, implement similarly to Example 5, obtain to have write down the volume hologram laminate of volume hologram.
Part that forms through pattern for resin bed and the part that forms without pattern, use spectrophotometer (UV-2450:(strain) Shimadzu Seisakusho Ltd.'s system) measure transmissivity, the reproduction centre wavelength of the spectral transmission curve of the part that the reproduction centre wavelength of the part that resin bed forms through pattern is 554nm, form without pattern is 527nm.
In addition, for antifalsification, similarly to Example 5, when the volume hologram laminate that has write down volume hologram was taken volume hologram as master, resin bed can't be taken hologram well through the part deepening that pattern forms.
2-4. embodiment 8
Except using the methyl ethyl ketone solution of vibrin (Vylon 270: weight-average molecular weight 40000, Japan weaving society system) with coating fluid as resin bed, implement similarly to Example 5, obtain to have write down the volume hologram laminate of volume hologram.
Part that forms through pattern for resin bed and the part that forms without pattern, use spectrophotometer (UV-2450:(strain) Shimadzu Seisakusho Ltd.'s system) measure transmissivity, the reproduction centre wavelength of the spectral transmission curve of the part that the reproduction centre wavelength of the part that resin bed forms through pattern is 556nm, form without pattern is 527nm.
In addition, for antifalsification, similarly to Example 5, when the volume hologram laminate that has write down volume hologram was taken volume hologram as master, resin bed can't be taken hologram well through the part deepening that pattern forms.
2-5. embodiment 9
Utilize the binder solution of the following composition of coating on the volume hologram layer of the volume hologram laminate that dispenser makes in embodiment 5, reach dry back thickness 20 μ m, utilize baking oven to be dried, form adhesive phase.Then, stacked fissility sheet material on adhesive phase (SPPET (75 μ m), TOHCELLO (strain) system) obtains as the volume hologram transfer label of the present invention's the 1st volume hologram transfer with sheet material.
Acrylic adhesive (Nissetsu PE-118; Japan's calcium carbide industry (strain) system) 100 mass parts
Isocyanate-based crosslinking chemical (Nissetsu CK-101; Japan's calcium carbide industry (strain) system) 2 mass parts
Solvent (MEK/toluene/ethyl acetate=2/1/1 (mass ratio)) 60 mass parts
Peel off volume hologram transfer with behind the fissility sheet material of label, use manual stacked machine to stick on the PVC card of conduct lining body, obtain volume hologram fitting body of the present invention from the adhesive phase side.Obtaining the position that is provided with resin bed of volume hologram and the position that resin bed is not set makes reproduction centre wavelength be that pattern-like is different, designability excellence person.
2-6. embodiment 10
Utilize rod to be coated with machine at the PET film that is untreated { Lumirror-T60 (25 μ m); East beautiful (strain) system } the fissility protective seam of going up the following composition of coating forms with solution and reaches dry back thickness 1 μ m, utilizes baking oven to be dried, and obtains the duplexer of PET film/fissility protective seam.
Polymethylmethacrylate (weight-average molecular weight 100000) 97 mass parts
Tissuemat E (weight-average molecular weight 10000) 3 amount parts
Solvent (MEK/toluene/ethyl acetate=2/1/1 (mass ratio)) 60 mass parts
Volume hologram laminate (PET film/resin bed/volume hologram layer/PET film) before handling in (4) heat treated-ultraviolet treatment with irradiation operation of the volume hologram laminate manufacture method of use embodiment 5; the PET film of this volume hologram layer side is peeled off; aim at the fissility protection aspect of duplexer of the PET film/fissility protective seam of above-mentioned acquisition from this volume hologram layer side; after passing to 80 ℃ cylinder; irradiation ultraviolet radiation obtains the volume hologram laminate that is made of PET film/fissility protective seam/volume hologram layer/resin bed/PET film comprehensively.
After peeling off the PET film of resin bed side of gained volume hologram laminate; use rod to be coated with the hot sealing layer of machine following composition of coating on the resin bed of this volume hologram layer and part setting; reaching dry back thickness is 4 μ m; the use baking oven is dried, and obtains as the volume hologram transfer foil of being used sheet material by the present invention's the 2nd volume hologram transfer that the PET film/the fissility protective seam/volume hologram layer/resin bed/hot sealing layer constitutes.
Vibrin (Vylonal MD1985; (strain) system is spun by Japan) ... 100 mass parts
Solvent (water/isopropyl alcohol=1/1 (mass ratio)) ... 100 mass parts
Use hot pressing type device (V-08:Navitas society system) at 150 ℃ of transfer printing temperature, 0.5 second transfer printing time, pressure 125kgf/cm 2On down the gained volume hologram transfer foil being stressed to be stacked in PVC card as the lining body from hot sealing layer, peel off the PET film afterwards, obtain volume hologram fitting body by fissility protective seam/volume hologram layer/resin bed/hot sealing layer/PVC card formation.Obtaining the position that is provided with resin bed of volume hologram and the position that resin bed is not set makes reproduction centre wavelength be that pattern-like is different, designability excellence person.

Claims (21)

1. the manufacture method of a volume hologram laminate is characterized in that,
Comprise following operation:
Use volume hologram to form and use substrate, take operation at the hologram of volume hologram layer recording volume type hologram, described volume hologram forms the resin bed that contains resin and polymerizable compound that has base material, is formed on the described base material and contains the volume hologram layer of optical polymerism material and be positioned on the described base material and form in the mode that is contacted with on the described volume hologram layer with substrate;
Make described polymerizable compound shift to the substance transfer operation of described volume hologram layer;
Make the postprocessing working procedures of described polymerizable compound polymerization.
2. the manufacture method of volume hologram laminate according to claim 1 is characterized in that,
Described polymerizable compound shifts from described volume hologram layer and comes.
3. the manufacture method of volume hologram laminate according to claim 1 and 2, it is characterized in that, described optical polymerism material contains free-radical polymerised compound and cationically polymerizable compound, and described polymerizable compound is described cationically polymerizable compound.
4. volume hologram laminate, it has base material and volume hologram laminated section, described volume hologram laminated section comprises and is formed on the described base material and contains the optical polymerism compound and by forming the volume hologram layer that interference fringe has write down volume hologram, and the resin bed that contains transparent resin that forms in the mode that is contacted with described volume hologram layer, it is characterized in that, on described resin bed, be formed with interference fringe.
5. volume hologram laminate according to claim 4 is characterized in that, the cycle of interference fringe that is formed at described volume hologram layer is different with the cycle of the interference fringe that is formed at described resin bed.
6. according to claim 4 or 5 described volume hologram laminates, it is characterized in that the transmissivity in the visible region shows the minimum transmission peak wavelength more than 2.
7. volume hologram transfer foil, it is characterized in that, have each described volume hologram laminate in the claim 4～6, and be formed on the described volume hologram laminated section of described volume hologram laminate and contain the hot sealing layer of thermoplastic resin.
8. a volume hologram label is characterized in that, has each described volume hologram laminate in the claim 4～6, and is formed at the knitting layer on the described volume hologram laminated section of described volume hologram laminate.
9. volume hologram laminate, it is provided with resin bed on base material top, and adjacent on this resin bed and in that described layers on substrates is folded the volume hologram layer being arranged, it is characterized in that,
On described resin bed, be formed with volume hologram, and the part that is provided with resin bed in the volume hologram laminate is different with the reproduction centre wavelength of the part that resin bed is not set.
10. volume hologram laminate according to claim 9 is characterized in that, described resin bed and described base material adjacent.
11. volume hologram laminate according to claim 9 is characterized in that, is formed with undercoat between described resin bed and the described base material.
12. according to each described volume hologram laminate in the claim 9～11, it is characterized in that, the volume hologram layer is the volume hologram layer from the volume hologram recording materials that contain free radical polymerization monomer and cationically polymerizable monomer, and, in the volume hologram laminate, be formed with based on the volume hologram that moves from the polymerizable monomer of adjacent volume hologram recording materials at resin bed.
13. according to each described volume hologram laminate of claim 9～12, it is characterized in that, resin bed contains the resin that is selected from polymethylmethacrylate, polyvinyl acetate (PVA), vibrin, and, the reproduction centre wavelength of the part that is provided with resin bed in the volume hologram laminate is compared with the reproduction centre wavelength of the part that is not provided with resin bed, is in long wavelength side.
14. according to each described volume hologram laminate of claim 9～12, it is characterized in that, resin bed contains the resin that is selected from polyvinyl butyral resin, polyvinyl acetal resin, and, the reproduction centre wavelength of the part that is provided with resin bed of volume hologram laminate is compared with the reproduction centre wavelength of the part that resin bed is not set, and is in short wavelength side.
15., it is characterized in that the reproduction centre wavelength of the part that is provided with resin bed of volume hologram laminate is at least more than the 10nm with the difference of the reproduction centre wavelength of the part that resin bed is not set according to claim 13 or 14 described volume hologram laminates.
16. the manufacture method of volume hologram laminate is characterized in that,
After the coating of ground, base material top forms resin bed, form the volume hologram recording materials layer that contains free radical polymerization monomer and cationically polymerizable monomer adjacent to being coated with on the described resin bed and on described base material, afterwards the gained duplexer implemented following operation successively:
(1) implements etching processing, make polymerizable monomer in the described volume hologram recording materials layer shift to the operation of resin bed;
(2) be used to hologram exposure operation from the laser explosure of base material side;
(3) implement heat treated and ultraviolet treatment with irradiation, described polymerizable monomer is moved between resin bed and volume hologram recording materials layer, simultaneously with the immobilized operation of hologram,
At the volume hologram of described resin bed formation, make the part that is provided with resin bed in the described duplexer different simultaneously with the reproduction centre wavelength of the part that resin bed is not set based on the polymerizable monomer that moves from adjacent volume hologram recording material layer.
17. a volume hologram transfer sheet material is characterized in that, is provided with the cement layer on the volume hologram layer of each described volume hologram laminate in claim 9～11.
18. volume hologram transfer sheet material, it is characterized in that, the volume hologram layer of claim 9 or 11 described volume hologram laminates is provided with strippable the 2nd base material, simultaneously on the face behind the base material peeled off of described volume hologram laminate the cement layer is set.
19. according to claim 9 or 10 described volume hologram layer transfer printing sheet materials, it is characterized in that, the volume hologram transfer sheet material is that to make its cement layer be the volume hologram transfer foil of hot sealing layer, or the volume hologram transfer label that to make its cement layer be adhesive phase.
20. a volume hologram fitting body is characterized in that, accessory rights requires 17 described volume hologram transfers to be glued to the lining body with the cement layer side of sheet material, and base material is stripped from and is removed or residual and become the protective seam of volume hologram layer.
21. a volume hologram fitting body is characterized in that, accessory rights requires 18 described volume hologram transfers to be glued to the lining body with the cement layer side of sheet material, and the 2nd base material is stripped from and is removed or residual and become the protective seam of volume hologram layer.
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CN103923576A (en) * 2014-04-09 2014-07-16 太仓市其盛化纤厂 Color tape with anti-counterfeit detection function

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