CN102981193B - For the film of molding, moulding article prepared therefrom and preparation method thereof - Google Patents
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- CN102981193B CN102981193B CN201210495544.0A CN201210495544A CN102981193B CN 102981193 B CN102981193 B CN 102981193B CN 201210495544 A CN201210495544 A CN 201210495544A CN 102981193 B CN102981193 B CN 102981193B
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Abstract
The invention provides a kind of goods, described goods comprise: polymeric layer, and it has first surface and second surface; Micro-lens arrays layer, it has first surface and second surface, the first surface of wherein said micro-lens arrays layer contacts with the first surface of described polymeric layer, and described micro-lens arrays layer comprises multiple predetermined radiation laser beam can being focused in described polymeric layer to make the lenticule of the appropriate section carbonization of polymeric layer; Binding layer, it has first surface and second surface, and wherein said binding layer has pore texture, and the first surface of described binding layer contacts with the second surface of described polymeric layer; And molding layer, described molding layer contacts with the second surface of described binding layer, be distributed with carbonized part in wherein said polymeric layer, described carbonized part is by being formed the appropriate section carbonization of described polymeric layer in focal position with described predetermined radiation laser beam.The present invention is also provided for film and its preparation method of preparing these goods.
Description
Technical field
The present invention relates to for the film of molding, moulding article prepared therefrom and preparation method thereof, more specifically, relate to a kind of film, moulding article prepared therefrom and preparation method thereof of the moulding article for the preparation of the image that floats with three-dimensional.
Background technology
Laser three-D floating image is the unique technology developed by 3M.It is a kind of technology utilizing emittance to record cubic floating cardon case in the membrane structure with microlens array.
At present, the bi-material that this technology uses more is: the microlens array film made by micro-duplication process, and the reflective membrane comprising glass microsphere is (with the Scotchlite of 3M company
tMproduct line and Confirm
tMproduct line is Typical Representative).Microlens array in these materials and glass microsphere are the critical optical components of three-dimensional imaging.The microlens array formed by micro-duplication process can be used for making colored floating image by substance transfer technique.Reflecting film material for making floating image at least comprises the material layers such as metal, metal oxide or the metal sulfide that one deck glass microsphere and one deck made by vacuum evaporation process usually, and this material layer generally has reflection action.
Such as, patent US6,288,842B1 describes the microlens sheet of one " exposure lens " type, that includes the single-layer and transparent microsphere being partially submerged into bonding coat (being generally polymeric material), for for the radiation wavelength of imaging in material layer and the optical wavelength for observing composograph, these microspheres are all transparent.And, material layer depositions in the rear surface of each microsphere, and typically only with a part of surface contact of each microsphere.In US Patent No. 2,326, describe in further detail this kind of thin slice in 634, its mainstream product is the Scotchlite8910 number of reflections structure of 3M company.
The microlens sheet that the another kind that patent US6,288,842B1 describe is suitable is " embedded lens " type thin slice, and wherein, microsphere lens are embedded in transparent protection external coating, and this coating typically is polymeric material.Material layer is then deposited over the behind of microsphere transparent spacer layer below, and wherein this transparent spacer layer is also made up of polymeric material.In US Patent No. 3,801, describe this kind of thin slice in 183 in detail, its mainstream product is the Scotchlite3870 series high strength grade glitter flakes of 3M.
These materials make the technique of the three-dimensional pattern that floats specifically: the laser energy of incidence is directed on light-scattering body, with the arbitrary heterogeneity homogenising will existed in light source.Then, catch these scattered lights by optical collimator and make it collimation, and equally distributed light is guided to divergent lens.Afterwards, from divergent lens, light is dispersed to microlens sheet.The luminous energy arriving microlens sheet is by the micro lens of each individuality in radiation-sensitive coating, and this radiation-sensitive coating can be the Al of vacuum evaporation, ZnS, Ag
50zn
50, Cr/Na
3alF
6the material layers such as/Al.This focus energy can change this radiation-sensitive coating to provide image, and the size of this image, shape and outward appearance depend on the interaction between light and radiation-sensitive coating.In the process, be in the materials such as Al or ZnS of focal position to be destroyed.Because can not reflection action be played, or because more easily by light therethrough, so these destroyed parts can be observed by reflection ray and transmitted ray.
Although utilize above-mentioned existing materials and process, laser three-D floating image technology is successfully applied at numerous areas such as passport security, but, existing have the film of microlens array structure and be not suitable for molding, reason is, the vacuum coating of metal/metal oxide/metal sulfide contained in film can not bear the High Temperature High Pressure at plastic-injection mouth place in moulding process, thus destroyed and break up in mould, and the associativity between described film and moulding material is not good, easily peels off.
A kind of goods of the image that floats with three-dimensional are provided in CN201210059844.4, described goods adopt polymeric layer as the carrier of image, by the appropriate section carbonization of polymeric layer being formed carbonized part with predetermined radiation laser beam in focal position, carbonized part and polymeric layer produce the contrast in color and present pattern, and this pattern can present macroscopic three-dimensional floating image polymeric layer under natural light.But associativity is not good between this goods and material of molding, molding can not be directly used in.
Therefore, need to provide a kind of can be used in preparing to float the film of moulding article of image and the moulding article of the image that floats with three-dimensional with three-dimensional.
Summary of the invention
The object of the present invention is to provide and a kind ofly can be used in preparing the film, moulding article prepared therefrom and preparation method thereof of moulding article of image of floating with three-dimensional, this film can bear the harsh conditions of molding, high bond strength is had with molding plastic cement, in moulding process, do not destroy material structure simultaneously, and then the three-dimensional image that floats clearly can be obtained.This 3-dimensional image is dynamic, rotate visual angle 3-dimensional image and can produce floating stereoeffect, owing to being the change of material intrinsic colour thus causing the change of contrast, therefore can not by retroreflecting light or transmitted light only with any ambient light as just can clearly observed under common ordinary light light conditions.
Particularly, according to an aspect of the present invention, provide a kind of film, described film comprises:
Polymeric layer, it has first surface and second surface;
Micro-lens arrays layer, wherein said micro-lens arrays layer contacts with the first surface of described polymeric layer, and described micro-lens arrays layer comprises multiple predetermined radiation laser beam can being focused in described polymeric layer to make the lenticule of the appropriate section carbonization of polymeric layer; With
Binding layer, described binding layer has pore texture and contacts with the second surface of described polymeric layer.
According to another aspect of the present invention, provide a kind of film for molding, described film comprises:
Polymeric layer, it has first surface and second surface;
Micro-lens arrays layer, wherein micro-lens arrays layer contacts with the first surface of polymeric layer, and micro-lens arrays layer comprises multiple predetermined radiation laser beam can being focused in described polymeric layer with the lenticule by corresponding polymer moieties carbonization; With
Binding layer, described binding layer contacts with the second surface of polymeric layer, and binding layer has pore texture,
Be distributed with carbonized part in wherein said polymeric layer, described carbonized part is by being formed the appropriate section carbonization of described polymeric layer in focal position with described predetermined radiation laser beam.
Particularly, according to a further aspect in the invention, provide a kind of goods, described goods comprise:
Polymeric layer, it has first surface and second surface;
Micro-lens arrays layer, wherein said micro-lens arrays layer contacts with the first surface of described polymeric layer, and described micro-lens arrays layer comprises multiple predetermined radiation laser beam can being focused in described polymeric layer to make the lenticule of the appropriate section carbonization of polymeric layer;
Binding layer, it has first surface and second surface, and wherein said binding layer has pore texture, and the first surface of described binding layer contacts with the second surface of described polymeric layer; With
Molding layer, described molding layer contacts with the second surface of described binding layer,
Be distributed with carbonized part in wherein said polymeric layer, described carbonized part is by being formed the appropriate section carbonization of described polymeric layer in focal position with described predetermined radiation laser beam.
According to another aspect again of the present invention, provide a kind of method manufacturing moulding article as above, described method comprises:
Micro-lens arrays layer is provided, and polymeric layer is set, this polymeric layer has first surface and second surface, wherein make the first surface of polymeric layer contact with described micro-lens arrays layer, described micro-lens arrays layer comprises multiple predetermined radiation laser beam can being focused in described polymeric layer to make the lenticule of the appropriate section carbonization of polymeric layer;
Arrange binding layer, this binding layer has first surface and second surface, and has pore texture, wherein makes the first surface of binding layer contact with the second surface of polymeric layer;
Irradiate lenticule with predetermined radiation laser beam, to make this radiation laser beam focus in described polymeric layer, carbonization is in the polymer moieties of the focal position of this radiation laser beam and forms carbonized part thus; With
The second surface of binding layer forms molding layer by molding.
According to another aspect more of the present invention, provide a kind of method manufacturing moulding article as above, described method comprises:
Micro-lens arrays layer is provided, and polymeric layer is set, this polymeric layer has first surface and second surface, wherein make the first surface of polymeric layer contact with described micro-lens arrays layer, described micro-lens arrays layer comprises multiple predetermined radiation laser beam can being focused in described polymeric layer to make the lenticule of the appropriate section carbonization of polymeric layer;
Arrange binding layer, this binding layer has first surface and second surface, and has pore texture, wherein makes the first surface of binding layer contact with the second surface of polymeric layer;
The second surface of binding layer forms molding layer by molding; With
Irradiate lenticule with predetermined radiation laser beam, to make this radiation laser beam focus in described polymeric layer, carbonization is in the polymer moieties of the focal position of this radiation laser beam and forms carbonized part thus.
The portion of material carbonization that goods of the present invention utilize laser light energy to make in polymeric layer, thus the change producing material color.Owing to being the change of material intrinsic colour thus causing the change of contrast, therefore only just can clearly can not observe with any ambient light by retroreflecting light or transmitted light.Owing to not adopting vacuum coating, described goods can stand the process conditions of such as High Temperature High Pressure in molding.And by use binding layer, improve with three-dimensional float image film and for molding material between bond strength.Thus the moulding article in conjunction with the firm and durable image that floats with three-dimensional can be obtained.
Accompanying drawing explanation
Fig. 1 is the structural representation of the film for molding according to one embodiment of the invention;
Fig. 2 is the structural representation of the film for molding according to another embodiment of the invention;
Fig. 3 is the structural representation of the film for molding according to another embodiment of the invention;
Fig. 4 is the schematic diagram with the moulding article structure of laser three-D floating image according to another embodiment of the present invention;
Fig. 5 is the schematic diagram with the moulding article structure of laser three-D floating image according to another embodiment of the present invention;
Fig. 6 is the schematic diagram (left: forward sight, right: backsight) of injection moulding sprue gate buffer structure when carrying out molding in one embodiment of the invention;
Fig. 7 is the moulding article according to an embodiment of the invention with laser three-D floating image;
Fig. 8 is the moulding article with laser three-D floating image according to an embodiment of the invention with matcoveredn;
Fig. 9 is the moulding article according to an embodiment of the invention with laser three-D floating image.
Embodiment
In the present invention, utilize laser or other emittance to make the portion of material carbonization in polymeric layer, thus produce the change of material color.Because caused the change of contrast by the change of this material intrinsic colour, the image of formation therefore only clearly can not can be observed with conventional environment light by retroreflecting light or transmitted light.For that have light background or transparent material, the dark images of carbonization has better contrast, thus also more easily observes.Because the present invention adopts the mechanism of carbonization variable color, therefore it can use polymkeric substance, such as resin, tackifier etc.As long as this polymkeric substance can be carbonized after absorbing enough energy, it can be utilized to coordinate glass microsphere or microlens structure and produce the high three-dimensional floating image of contrast.
Film for molding of the present invention comprises at least three layer of one micro-lens arrays layer, polymeric layer and binding layer usually.The structural representation of Fig. 1 display film for molding according to an embodiment of the invention, comprising micro-lens arrays layer 11, polymeric layer 12 and binding layer 13.
Wherein, described micro-lens arrays layer can be made up of identical polymkeric substance with described polymeric layer, and structurally forms same entirety, that is, they also can be made as same layer.The structural representation of Fig. 2 display film for molding according to an embodiment of the invention, comprising the microlens layer adopting micro-reproduction technology to make, micro-lens arrays layer in this film is made up of identical polymkeric substance with described polymeric layer, and form diaphragm 23 by techniques such as cast coat, extrusion molding, injection mouldings, in forming process, adopt mould to form microlens array shapes on surface 21, or the method such as shaping rear use hot pressing change surface 21 to microlens array shape.Another surface 22 of diaphragm 23 contacts with binding layer 24.In such an embodiment, polymeric layer and microlens layer are integrally formed, and are of identical composition.
Polymeric layer wherein can be made up of fluoropolymer resin or tackifier, and these tackifier or resin can be heat molten types, solvent type, water base, etc.The polymkeric substance used can be such as polyurethane, epoxy resin, phenolics, acryl resin, polyester, UV cured resin, Isooctyl acrylate monomer/butyl acrylate/acrylic acid (EHA/BA/AA) multipolymer, copolyester, or their combination.As long as polymkeric substance can absorbing laser or other emittance carbonization occurs after it is prepared into coating, can use.These polymkeric substance can be homopolymer or multipolymer.Described polymkeric substance is preferably water white or light, to improve the contrast of three-dimensional floating image.The thickness of polymeric layer depends on lenticular refractive index and diameter, must ensure that emittance passes through the focus after micro lens on polymeric layer.
In some embodiments, use commercially available product formation polymeric layer, such as commodity are called the aqueous polyurethane solution of R960, R961 and R1005, available from DSM company (DSM), commodity are called the water-based epoxy resin solution of XZ92533, available from DOW Chemical (DOW), and commodity are called the polyurethane-polyvalent alcohol water-borne dispersions of UXP2755, available from Beyer Co., Ltd (Bayer).
Crosslinking chemical can be added, to improve the adhesion between micro-lens arrays layer and polymeric layer.
This polymeric layer also can comprise the good adjuvant of specific source of radiation energy absorption, to strengthen color changeable effect to improve contrast and the sharpness of pattern.These exist with the state of pressed powder usually to the good adjuvant of specific source of radiation energy absorption, and need the reunion of being abolished powder by the mechanical dispersion process such as ball milling, sand milling, make being dispersed in polymeric layer of its fine uniform.For the radiation source of near-infrared band, a lot of inolrganic chemicals is better to this wave band absorptance, therefore these inolrganic chemicals can be joined in resin material with certain proportion, and with this resin materials of radiation source irradiates such as near-infrared band laser.Like this, be dispersed in the additive granules concurrent heat of radiation-absorbing energy consumingly in resin, thus cause the carbonization of surrounding resin material.This type of common material is as TiO
2, Sb
2o
3, ZnSBaSO
4, mica, the titania covered with mica, tin oxide or zirconia, Cu
3(PO
4)
2cu (OH)
2, carbon black, has the Sb of polyethylene support
2o
3, or their combination.In addition, market also has specially sell, as Merck company for the absorbing agent of near-infrared laser
deng.Certainly, for different radiation sources, should promote that material is to the absorption of emittance with corresponding absorbing agent.
Described lenticule can have the shape of spheroid, hemisphere or aspheres.In addition, described lenticule can partly be embedded in described polymeric layer.Micro-lens arrays layer preferably has can the refractive surface of imaging, to facilitate the formation of image.Usually, this is provided by curved surface.For the lenticule with curved surface, it preferably has uniform refractive index.For other material with graded index (GRIN), it does not need to form curved surface and carrys out refract light.Micro-lens surface can be sphere, also can be aspheric.As long as refractive surface forms real image, then lenticule can have any symmetry of such as cylinder or spheroid.Lenticule itself can be discrete form, such as circular flat-convex lenslet, circular biconvex lenslet, rod, microsphere, ball, or cylindrical lenslets.Form lenticular material and comprise glass, polymkeric substance, pottery, ore, crystal, the combination of semiconductor and these and other material.Also not discrete lenticular lens elements can be used.Thus, also can use by the lenticule copied or embossing (embossing) technique (shape wherein, changing sheet surface produces the repetition profile with imaging characteristic) is formed.
Suitable microlens material should be minimum to the absorption of visible ray, and make in the embodiment of polymeric layer imaging at use energy source, and this material also should present the minimum performance of the absorption of this energy source.No matter lenticule is discrete or copies, and no matter which kind of material of lenticule manufactures, and lenticular refractive power preferably makes the anaclasis of arrival refractive surface and focuses at lenticular opposite side.More specifically, light will focus on lenticular rear surface or focus on contiguous lenticular material.Lenticule preferably at the correct position place focused radiation light of polymeric layer, to form the real image reduced.
Although the lenticule that refractive index is greater than 1 can use in theory, the lenticule that visible ray and infrared light wavelength have the homogeneous refractive index between 1.5 and 3.0 is the most useful, and more preferably, this lenticule has the refractive index of 1.5 to 2.5.Although the lenticule of other size also can use, the diameter lenticule be between 15 microns to 275 microns is more suitable.For seeming the three-dimensional synthetic images leaving microlens layer relatively short distance (0-50mm), use to have and can obtain excellent image resolution ratio in above-mentioned scope compared with the lenticule of the diameter of small end, for seeming the 3-D view leaving microlens layer relatively remote (> 50mm), use larger-diameter lenticule can obtain excellent image resolution ratio.
Can expect the lenticule of various shape, such as microsphere, flat-convex, cylindrical, spheric or aspheric surface-shaped microlens, they can produce similar optical results when size is suitable.In US Patent No. 2,326,634 and US3,801, this class formation information more specifically can be found in 183, and this class formation can be found in the existing Scotchlite8910 series reflective fabric product of 3M and Scotchlite3290 series reflecting film product.Diaphragm 23 in film shown in Fig. 2 is the micro-lens surface of another suitable type.This structure include transparent flat-convex surface.Second surface 22 is plane substantially, and first surface 21 to have be hemispheroidal or the lenticular array of half aspheres substantially.Select the thickness of lenticular shape and basic unit, the collimated light incided on array is focused on below greatly near second surface.Such as, in US Patent No. 5,254, describe this kind of thin slice in 390, and in the 2600 serial sector card receivers of 3M, apply this kind of thin slice now.
In the technique making three-dimensional floating image, the laser of wavelength coverage from 400nm to 1200nm can be adopted to be used as radiation source.Also the laser of other wavelength coverage (such as 200 ~ 400nm and 1200 μm to 10 μm) can be adopted.The pulsewidth of Laser output is less than 30ns, and pulse energy regulates according to the difference of material.In addition, beam-expanding telescope and non-spherical lens can be used after laser instrument to make emittance reorientation.In addition, according to method of the present invention, irradiate and carry out one or many.Each irradiation time is a few femtosecond to tens nanoseconds.
Binding layer is between polymeric layer and injection molded layers, by the above-mentioned layer of material that both are bonded together securely.This layer material has hole, can be microcellular structure, can combine closely with polymeric layer, can also bear the plastic cement infiltration of melting wherein.Base materials employed hole can in the scope of 0.01 micron to 1.0 millimeters, such as, volume mean diameter can be had and be about 0.01 ~ 1 micron, preferably the micropore of 0.02 ~ 0.5 micron, also can be that there is size about 0.05 ~ 1 millimeter, the preferably base material of macroporosity of 0.1 ~ 0.5 millimeter.As this binding layer be applicable to material can be there is microcellular structure polymeric material if polyolefines is as tygon, polypropylene or its multipolymer, or there is the textile of suitable hole, the Teslin material of such as PPG company, excellent pool in-mould injection label paper, cloth etc.Use the Teslin material of PPG company in one embodiment, this material is a class dimensionally stable, has the polyolefin synthetic material of microcellular structure, and the size of micropore is in the scope of 0.01 ~ 1 micron.The instantiation of the Teslin material of PPG company can be SP600 or SP700 film, and the size of its micropore is in the scope of 0.02 ~ 0.5 micron.In some embodiments, the pure cotton grey cloth of pore-size in 100 ~ 300 micrometer ranges is used.In other embodiments, use pore-size for some tens of pm is as excellent pool (Yupo) the in-mold labels paper LBR of 50 microns.Preferred use tinted material is as binding layer.
In some embodiments, the thickness of binding layer can be 10 microns to 5 millimeters, is preferably 50 microns to 2 millimeters, is more preferably 100 microns to 1 millimeter.Thickness is too small easily damaged in injection moulding process; Thickness crosses the outward appearance that conference affects moulding article, and such as, for keeping moulding article intensity, moulding article itself needs to reach certain thickness, adds joint thickness and moulding article can be made more aobvious thick and heavy.
Except the essential structure with above-mentioned three layers, the film for molding of the present invention can also have extra play.Such as, protective seam can be set on micro-lens arrays layer.The structural representation of Fig. 3 display film for molding according to an embodiment of the invention, comprising micro-lens arrays layer 31, polymeric layer 32, binding layer 33, and protective seam 34.When adopting protective seam, can the higher glass microsphere of selective refraction rate, to guarantee that radiation source can focus on the polymeric layer of glass microsphere proximity through the refraction of glass microsphere.Refractive Index of Material for the protection of layer can in the scope of 1.3 ~ 1.8, such as, 1.3.Protective seam can be any thickness, as long as transparent to the radiation source adopted, and such as can in the scope of 5 microns to 1 millimeter.In one embodiment, the thickness of employing is 100 μm.The example that can be used for the material manufacturing protective seam comprises polyolefin, polyalkenyl halides, polyester, polycarbonate etc.; such as Polyvinylchloride (PVC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc.
The example of the preparation method of the film of the moulding article for the preparation of the image that floats with three-dimensional of the present invention is as follows.
Film as shown in Figure 1 comprises polymeric layer 12, is partially submerged into the microballoon layer 11 of polymeric layer 12 and binding layer 13.Its manufacturing process can be: first discrete micro-sphere material is dispersed in equably base material as on PET/PE compound substance, heating, make microballoon only a part embed in this compound substance, the obtained membraneous material containing microballoon layer, adopt the mode of cast coat afterwards, coated polymeric resin material, then laminating upper binding layer on the above-mentioned membraneous material containing microballoon layer, dry this material, finally PET/PE composite layer is removed.In order to make polymkeric substance and microballoon mutual bonding firmly and strengthen pattern effect, ratio in microballoon embedded polymer thing can be made 10% ~ 70%.The refractive index of microballoon can between 1.0 ~ 3.0, best with 1.5 ~ 2.5 effects; The diameter of microballoon is preferably at 15 μm ~ 275 μm, wherein best with the effect of 30 ~ 150 μm.The thickness of polymeric layer depends on refractive index and the diameter of microballoon, must ensure emittance focused on by microballoon after focus on polymeric layer.
Shown in Fig. 3 is another kind of membrane structure, and it comprises microballoon layer 31, polymeric layer 32, binding layer 33 and protective seam 34.The method for making of 31 ~ 33 layers is identical with upper example.Finally, the transparent polymeric layer that one deck shields can be coated with on the surface of microballoon layer, then make it solidify.Sealer can be any thickness, as long as transparent to the radiation source adopted.
Shown in Fig. 2 is a kind of structure comprising the microlens layer adopting micro-reproduction technology to make.This structure is minimum can only comprise two-layer.Its method for making is: the techniques such as satisfactory polymkeric substance cast coat, extrusion molding, injection moulding are formed diaphragm, in forming process, adopt mould to form microlens array shape on surface 21, or the method such as shaping rear use hot pressing changes surface 21 to microlens array shape, and laminating binding layer 24 on the surface 22.
The present invention also provides the moulding article with laser three-D floating image, comprising:
Polymeric layer, it has first surface and second surface;
Micro-lens arrays layer, wherein said micro-lens arrays layer contacts with the first surface of described polymeric layer, and described micro-lens arrays layer comprises multiple predetermined radiation laser beam can being focused in described polymeric layer to make the lenticule of the appropriate section carbonization of polymeric layer;
Binding layer, it has first surface and second surface, and wherein said binding layer has pore texture, and the first surface of described binding layer contacts with the second surface of described polymeric layer; With
Molding layer, described molding layer contacts with the second surface of described binding layer,
Be distributed with carbonized part in wherein said polymeric layer, described carbonized part is by being formed the appropriate section carbonization of described polymeric layer in focal position with described predetermined radiation laser beam.
An one embodiment as shown in Figure 4, comprises polymeric layer 42, micro-lens arrays layer 41, binding layer 43, and molding layer 44.
In another embodiment, provide a kind of moulding article with laser three-D floating image, as shown in Figure 5, comprise and form as a whole polymeric layer and micro-lens arrays layer 53, binding layer 54, and molding layer 55.Wherein the techniques such as satisfactory polymkeric substance cast coat, extrusion molding, injection moulding are formed diaphragm, in forming process, adopt mould to form microlens array shape on surface 51, or the method such as shaping rear use hot pressing changes surface 51 to microlens array shape, and on surface 52 laminating binding layer 54.
Polymeric layer in described moulding article, micro-lens arrays layer and binding layer are as noted before.
Molding layer is formed on binding layer by techniques such as injection mouldings.The material that can be used for being formed molding layer comprises any material that can be used for molding, include but not limited to polyolefin, polyester, polycarbonate etc., the example comprises acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate (PC), tygon (PE), polypropylene (PP), polystyrene (PS), and one or more potpourri in them, as the potpourri of ABS and PC.The thickness of molding layer can be selected as required, can in the scope of 0.5 ~ 5.0mm.Molding layer in this thickness range can keep more smooth outward appearance and stable mechanical property.
The present invention is also provided for the method preparing moulding article as above, and in one embodiment, described method comprises the steps: to provide micro-lens arrays layer; Polymeric layer is set; Binding layer is set; Carbonized part is formed in polymeric layer; With formation molding layer.
In another embodiment, described method comprises the steps: to provide micro-lens arrays layer; Polymeric layer is set; Binding layer is set; Form molding layer; Carbonized part is formed with in polymeric layer.
When preparing moulding article as above, the three-dimensional on the injection membrane surface image that floats can be formed by laser-induced thermal etching before injection moulding, also first injection membrane can be formed on plastics cast parts surface and then carry out laser-induced thermal etching.The performance of two kinds of methods to obtained product has no significant effect, and all can obtain injection membrane and be securely bonded goods on plastics cast parts surface, but comparatively speaking, and the three-dimensional that the method for first injection moulding after etching the obtains image that floats is more clear.
In one embodiment, first form three-dimensional floating image in the film, this film is prefabricated into required shape and size by cross cutting, is then fixed in die cavity, the injection moulding plastic of the image film that floats with three-dimensional through injection step formation.In another embodiment, first carry out injection step, after film forms molding layer, then carry out laser emission to form carbonized part in polymeric layer, thus obtain the moulding article with three-dimensional floating image.
Shooting Technique can adopt any mode in this area to carry out, such as, use screw injection molding machine or plunger-type injection molding machine etc.In one embodiment, Horizontal screw injection machine is used.
The size of injected sample can be selected as required, is not particularly limited.In one embodiment, the Outside Dimensions size of injected sample is within 40cm × 15cm × 2cm, and adopt Horizontal screw injection machine, injection machine pressure is 140 tons.
The condition of Shooting Technique can be selected according to used injected plastics material, and wherein injection pressure is within the scope of 70 ~ 200MPa, and injection temperature is within the scope of 170 ~ 320 DEG C, and pressurize scope is within the scope of 30 ~ 70MPa.Such as, when using ABS injection moulding, basic technological parameters is: injection pressure: 80 ~ 200MPa, injection temperature: 210 ~ 230 DEG C, pressurize scope: 30 ~ 70MPa.When using PP injection moulding, basic technological parameters is: injection pressure: 70 ~ 100MPa, injection temperature: 170 ~ 250 DEG C, pressurize scope: 30 ~ 70MPa.When using PC injection moulding, basic technological parameters is: injection pressure: 80 ~ 160MPa, injection temperature: 250 ~ 320 DEG C, pressurize scope: 40 ~ 70MPa.When using ABS+PC injection moulding, basic technological parameters is: injection pressure: 80 ~ 160MPa, injection temperature: 220 ~ 240 DEG C, pressurize scope: 40 ~ 70MPa.
Preferably, in order to keep the integrality of film in injection moulding process, and then guaranteeing that the three-dimensional image definition that floats is visible, high pressure-temperature sprue gate at a high speed should be avoided to be set to directly impact film in front or in side.In one embodiment, buffer structure such as conical sprue gate is increased when designing mould, to reduce the area at sprue gate, as shown in Figure 6, sprue gate is arranged perpendicular to pellicular front, is preferably perpendicular to pellicular front and is arranged on film edge place, such as, be arranged on the knuckle limit place of sidepiece perpendicular to pellicular front, can effectively avoid frontal impact film and reduce side impact force like this, thus prevent from occurring in the film impacting blackspot or film and to be thrust the defect split.
The present invention is further illustrated below by way of specific embodiment.
Embodiment
Embodiment 1
First layer of polyethylene film carried on the back on base at the paper that thickness is 20 μm, polyethylene film thickness is about 20 μm.Material is placed in 200 DEG C of baking ovens to heat, when tygon becomes semi-cured state, be 1.9 by refractive index, diameter is that the glass microsphere of 50 μm is sprinkling upon polyethylene surface uniformly, control poly state of cure to make glass microsphere embed poly volume to be about 30%, thus make glass microsphere diaphragm.Then adopt the mode of cast coat, be coated on by polymeric material on prefabricated glass microsphere diaphragm, this polymkeric substance adopts the R960 resin of DSM N. V. (principal ingredient is aliphatic polyurethane), and it does thick is 50 μm.Then laminating TeslinSP600 or the SP700 film available from PPG company as binding layer (its pore-size is in the scope of 0.02 ~ 0.5 micron), at the temperature of 60 ~ 100 DEG C, dry solidification is after 5 minutes, is taken off by glass microsphere surface paper substrate.
Afterwards, adopt pulse energy 6mJ and pulse width to be about the pulse laser of 10ns, its output wavelength is 1064nm (the DCR-3YAG Q-switched laser of such as Spectra-Physics company).After laser instrument, by 5X beam-expanding telescope and numerical aperture be 0.64 and focal length be that the non-spherical lens of 39mm makes energy reorientation.Light from non-spherical lens is directed to electronic XYZ platform.Be placed on platform by the above-mentioned thin slice made, irradiate glass microsphere exposed surface once or for several times, each irradiation time is about 10ns with laser, platform moves relative to light beam space three-dimensional according to the track of setting, can obtain three-dimensional floating image.The one layer of polymeric layer (R960 resin) that the film obtained by above processing step is comprised one deck lenticule (glass microsphere) array layer, contacts below this microlens layer and with this micro-lens arrays layer, and be distributed with the carbonized part caused by laser radiation beam in this polymeric layer, and binding layer Teslin film.
Then, the film cross cutting obtained above is prefabricated into the size of 40cm × 15cm × 2cm, then be fixed in die cavity, adopt toray PX10 plastic cement as injection moulding materials, this product is the potpourri (ratio 1: 4) of PC and ABS, adopt Horizontal screw injection machine, carry out injection moulding under the following conditions: injection machine pressure is 140 tons, injection pressure: 120MPa, injection temperature: 220 DEG C, pressurize scope: 60MPa, obtains the molding layer that thickness is about 3.0mm.Obtain the moulding article with three-dimensional floating image.
Can easily observe the three-dimensional floating image adopting above-mentioned material and technique to produce in common ambient light, but when retroreflecting light, this image is invisible.Fig. 7 shows the image effect presented when to observe the goods adopting above-mentioned material and technique to make in natural light environment.Particularly, the image effect obtained when these goods of right-angle view can be clear that from left hand view, wherein demonstrate and there is high sharpness and the floating image of contrast, and as can be seen from right part of flg, be closely linked between film and molding layer.
Embodiment 2
Make in the same manner as example 1 and realize the moulding article of three-dimensional floating image, difference is, the polymeric layer in embodiment 1 is replaced with respectively other modifications of DSM N. V. or unmodified polyurethane and copolymer resin thereof, as R961, R986, R974, R1005, R9660, R620, R972, E121, the resins such as E106, all obtain and have similar image effect, and film and the compact goods of molding layer.
Embodiment 3
Make the moulding article realizing three-dimensional floating image in the same manner as example 1, difference is, the potpourri of PC and ABS in embodiment 1 is replaced with ABS respectively, PC, or PP, all obtain and there is similar image effect, and film and the compact goods of molding layer.
Embodiment 4
Molding film is prepared with the method identical with described in embodiment 1, difference is to adopt refractive index to be 2.2, diameter is the glass microsphere of 50 μm, and after glass microsphere surface paper substrate is taken off, one deck polyvinyl chloride resin (PolyOnePVCGeon178) is coated with again on the surface of glass microsphere again by the method for cast coat, its refractive index is 1.3, and dry, and the dry thick of layer of PVC is 100 μm.
Three-dimensional floating image and molding layer is made afterwards with technique in the same manner as in Example 1 and parameter.Fig. 8 shows the image effect presented when to observe the goods adopting above-mentioned material and technique to make in natural light environment.Can see, obtain the floating image with more high-contrast, and the goods that film and molding layer are closely linked.
Embodiment 5
Make the moulding article realizing three-dimensional floating image in the same manner as example 1, difference is, sand is used to knit several 32*32, density 67*68, grammes per square metre is that the pure cotton grey cloth of white (its pore-size is in 100 ~ 300 micrometer ranges) of 120 grams/m replaces Teslin film.Fig. 9 shows the image effect presented when to observe the goods adopting above-mentioned material and technique to make in natural light environment.Particularly, the image effect obtained when these goods of right-angle view can be clear that from left hand view, wherein demonstrate and there is high sharpness and the floating image of contrast, and as can be seen from right part of flg, be closely linked between film and molding layer.
Embodiment 6
Make the moulding article realizing three-dimensional floating image in the same manner as example 1, difference is, use thickness is that excellent pool (Yupo) the in-mold labels paper LBR (its pore-size is 50 microns) of 80 microns replaces Teslin film.Obtain and there is similar image effect, and film and the compact goods of molding layer.
Embodiment 7-12
Repeat embodiment 1-6, but make three-dimensional floating image all after completion of the injection-moulding, other processes and parameter constant.Obtain the result similar to embodiment 1-6.
Embodiment 13
The near-infrared laser absorbing agent P252g of Degussa company is joined in the R961 resin 100g of DSM N. V., utilizes the ZrO of RetschPlanetary bowl mill PM100 and 7mm
2pearl disperses 2 hours under the speed of 500rpm.Utilize technique as described in example 1 above, aforementioned mixture is applied on prefabricated glass microsphere film, wet thick 120 μm, then the laminating Teslin film SP600 available from PPG company as binding layer or SP700 film, at the temperature of 60 ~ 100 DEG C, dry solidification is after 5 minutes, glass microsphere surface paper substrate is taken off, thus forms the membraneous material that can make the three-dimensional pattern that floats.
When making floating pattern, adopt the laser of 1064nm, and the output pulse width of this laser is about 10ns, its pulse energy is about 5mJ.Utilize the method for making pattern-making in embodiment 1 and after carrying out injection moulding, the three-dimensional that just can obtain having high definition is floated the moulding article of pattern.When other conditions are identical, when being added with absorbing agent P25, goods can present image effect more clearly.
Embodiment 14
By the near-infrared laser absorbing agent of Merck company
8002g joins in the R961 resin 100g of DSM N. V., utilizes the ZrO of RetschPlanetary bowl mill PM100 and 7mm
2pearl disperses 2 hours under the speed of 500rpm.Utilize technique as described in example 1 above, aforementioned mixture is applied on prefabricated glass microsphere film, wet thick 120 μm, then the laminating Teslin film SP600 available from PPG company as binding layer or SP700 film, at the temperature of 60 ~ 100 DEG C, dry solidification is after 5 minutes, glass microsphere surface paper substrate is taken off, thus forms the membraneous material that can make the three-dimensional pattern that floats.
When making floating pattern, adopt the laser of 1064nm, the output pulse width of this laser is about 10ns, and pulse energy is about 5mJ.Utilize the method for making pattern-making in embodiment 1 and after carrying out injection moulding, the three-dimensional that just can obtain having high definition is floated the moulding article of pattern.When other conditions are identical, be added with absorbing agent
when 800, goods can present image effect more clearly.
Embodiment 15
Near-infrared laser absorbing agent in embodiment 14 is replaced with the B101 (TiO of YuejiangTitanium company
2), the Sb of YuejiangTitanium company
2o
3, Merck company Lithopone30%l (ZnSBaSO
4), Merck company
825 (mica and (Sn/Sb) O
2), Merck company
8840 (Cu
3(PO
4)
2cu (OH)
2), Merck company
a208 (has the Sb of polyethylene support
2o
3) etc., other technological process and parameter constant, the goods of gained all can obtain similar image effect.
Embodiment 16
In the present embodiment, the microlens array surface adopting micro-reproduction technology to make is as micro-lens arrays layer.Adopt US Patent No. 5,254, the microlens structure diaphragm described in 390, diaphragm one side is microlens array structure, and another side is close to plane (hereinafter referred to as reverse side).The focal position of microlens structure is at adjacent opposing faces rear.At the R961 resin of coated on opposite surfaces DSM N. V., the laminating Teslin film SP600 available from PPG company as binding layer or SP700 film, and solidify.The thickness of resin bed is greater than the distance of lenticule focal position from reverse side, so as radiation source through Voice segment after microlens structure in this resin bed.
When adopting identical with embodiment 1 or embodiment 2 radiation source, the three-dimensional just can producing high-contrast is within this material floated pattern.
Above-described embodiment is only exemplary describes the present invention, but not for limiting the present invention.Know and it will be understood by those of skill in the art that when without departing from the spirit and scope of the present invention, any change do the embodiment of the present invention and change all fall within the scope of the invention.And protection scope of the present invention should be determined by appended claim.
Claims (53)
1. goods, described goods comprise:
Polymeric layer, it has first surface and second surface;
Micro-lens arrays layer, it has first surface and second surface, the first surface of wherein said micro-lens arrays layer contacts with the first surface of described polymeric layer, and described micro-lens arrays layer comprises multiple predetermined radiation laser beam can being focused in described polymeric layer to make the lenticule of the appropriate section carbonization of polymeric layer;
Binding layer, it has first surface and second surface, and wherein said binding layer has pore texture, and the first surface of described binding layer contacts with the second surface of described polymeric layer; With
Molding layer, described molding layer contacts with the second surface of described binding layer,
Be distributed with carbonized part in wherein said polymeric layer, described carbonized part is by being formed the appropriate section carbonization of described polymeric layer in focal position with described predetermined radiation laser beam.
2. goods according to claim 1, wherein said lenticule has the shape of spheroid, hemisphere or aspheres.
3. according to the goods of claim 1 or 2, wherein said lenticule is formed by any one being selected from following material: glass, polymkeric substance, pottery, ore, or their combination.
4., according to the goods of claim 1 or 2, wherein said lenticule is by Crystallization.
5., according to the goods of claim 1 or 2, wherein said lenticule is formed by semiconductor.
6., according to the goods of claim 1 or 2, wherein said lenticule has the refractive index of 1.5 to 3.0.
7., according to the goods of claim 1 or 2, wherein said micro lensed portion ground is embedded in described polymeric layer.
8. according to the goods of claim 1 or 2, wherein said micro-lens arrays layer is made up of identical polymkeric substance with described polymeric layer, and structurally forms same entirety.
9., according to the goods of claim 1 or 2, wherein said polymeric layer is formed by any one polymkeric substance be selected from following polymkeric substance: polyurethane, epoxy resin, phenolics, polyester, UV cured resin, Isooctyl acrylate monomer/butyl acrylate/acrylic copolymer, or their combination.
10., according to the goods of claim 1 or 2, wherein said polymeric layer is formed by acryl resin.
11. according to the goods of claim 1 or 2, and wherein said polymeric layer is formed by copolyester.
12. according to the goods of claim 1 or 2, and wherein said polymeric layer is formed by water white or light polymeric material.
13. according to the goods of claim 1 or 2, and the hole of wherein said binding layer is in the scope of 0.01 micron to 1.0 millimeters.
14. according to the goods of claim 1 or 2, and wherein said binding layer is made up of any one being selected from following material: polyolefin, and textile.
15. according to the goods of claim 1 or 2, and described goods also comprise protective seam, and it contacts with the second surface of micro-lens arrays layer.
16. according to the goods of claim 1 or 2, and wherein said polymeric layer also comprises the adjuvant for promoting the absorption to described predetermined radiation laser beam.
17. goods according to claim 16, wherein said adjuvant is selected from by TiO
2, Sb
2o
3, ZnSBaSO
4, mica, the titania covered with mica, tin oxide or zirconia, Cu
3(PO
4)
2cu (OH)
2, carbon black, or any one in the group of their combination composition.
18. goods according to claim 16, wherein said adjuvant is the Sb with polyethylene support
2o
3.
19. 1 kinds of films, described film comprises:
Polymeric layer, it has first surface and second surface;
Micro-lens arrays layer, it has first surface and second surface, the first surface of wherein said micro-lens arrays layer contacts with the first surface of described polymeric layer, and described micro-lens arrays layer comprises multiple predetermined radiation laser beam can being focused in described polymeric layer to make the lenticule of the appropriate section carbonization of polymeric layer; With
Binding layer, described binding layer has pore texture and contacts with the second surface of described polymeric layer.
20. films according to claim 19, are distributed with carbonized part in wherein said polymeric layer, and described carbonized part is by being formed the appropriate section carbonization of described polymeric layer in focal position with described predetermined radiation laser beam.
Film described in 21. claims 19 or 20, wherein said lenticule has the shape of spheroid, hemisphere or aspheres.
22. according to the film of claim 19 or 20, and wherein said lenticule is formed by any one being selected from following material: glass, polymkeric substance, pottery, ore, or their combination.
23. according to the film of claim 19 or 20, and wherein said lenticule is by Crystallization.
24. according to the film of claim 19 or 20, and wherein said lenticule is formed by semiconductor.
25. according to the film of claim 19 or 20, and wherein said lenticule has the refractive index of 1.5 to 3.0.
26. according to the film of claim 19 or 20, and wherein said micro lensed portion ground is embedded in described polymeric layer.
27. according to the film of claim 19 or 20, and wherein said micro-lens arrays layer is made up of identical polymkeric substance with described polymeric layer, and structurally forms same entirety.
28. according to the film of claim 19 or 20, and wherein said polymeric layer is formed by any one polymkeric substance be selected from following polymkeric substance: polyurethane, epoxy resin, phenolics, polyester, UV cured resin, Isooctyl acrylate monomer/butyl acrylate/acrylic copolymer, or their combination.
29. according to the film of claim 19 or 20, and wherein said polymeric layer is formed by acryl resin.
30. according to the film of claim 19 or 20, and wherein said polymeric layer is formed by copolyester.
31. according to the film of claim 19 or 20, and wherein said polymeric layer is formed by water white or light polymeric material.
32. according to the film of claim 19 or 20, and the hole of wherein said binding layer is in the scope of 0.01 micron to 1.0 millimeters.
33. according to the film of claim 19 or 20, and wherein said binding layer is made up of any one being selected from following material: polyolefin, and textile.
34. according to the film of claim 19 or 20, and described film also comprises protective seam, and it contacts with the second surface of micro-lens arrays layer.
35. according to the film of claim 19 or 20, and wherein said polymeric layer also comprises the adjuvant for promoting the absorption to described predetermined radiation laser beam.
36. according to the film of claim 35, and wherein said adjuvant is selected from by TiO
2, Sb
2o
3, ZnSBaSO
4, mica, the titania covered with mica, tin oxide or zirconia, Cu
3(PO
4)
2cu (OH)
2, carbon black, or any one in the group of their combination composition.
37. according to the film of claim 35, and wherein said adjuvant is the Sb with polyethylene support
2o
3.
The method of the goods of 38. 1 kinds of manufactures according to any one of claim 1-18, described method comprises:
Micro-lens arrays layer is provided, and polymeric layer is set, polymeric layer has first surface and second surface, micro-lens arrays layer has first surface and second surface, wherein make the first surface of polymeric layer contact with the first surface of micro-lens arrays layer, described micro-lens arrays layer comprises multiple predetermined radiation laser beam can being focused in described polymeric layer to make the lenticule of the appropriate section carbonization of polymeric layer;
Arrange binding layer, this binding layer has first surface and second surface, and has pore texture, wherein makes the first surface of binding layer contact with the second surface of polymeric layer;
Irradiate lenticule with predetermined radiation laser beam, to make this radiation laser beam focus in described polymeric layer, carbonization is in the polymer moieties of the focal position of this radiation laser beam and forms carbonized part thus; With
The second surface of binding layer forms molding layer by molding.
39. according to the method for claim 38, and the second surface that described method is also included in described micro-lens arrays layer arranges protective seam.
40. according to the method for claim 38 or 39, and described method also comprises and promotes that the adjuvant of the absorption to described predetermined radiation laser beam is added in described polymeric layer by being used for.
41. according to the method for claim 38 or 39, the laser of wherein said predetermined radiation laser beam to be wavelength be 400 to 1200nm.
42. according to the method for claim 38 or 39, and one or many is carried out in wherein said irradiation.
43., according to the method for claim 38 or 39, wherein use water white or light polymkeric substance to form described polymeric layer.
44. according to the method for claim 38 or 39, and the mould wherein for molding has buffer structure.
45. according to the method for claim 38 or 39, and the sprue gate wherein for molding is arranged perpendicular to pellicular front.
The method of the goods of 46. 1 kinds of manufactures according to any one of claim 1-18, described method comprises:
Micro-lens arrays layer is provided, and polymeric layer is set, polymeric layer has first surface and second surface, micro-lens arrays layer has first surface and second surface, wherein make the first surface of polymeric layer contact with the first surface of micro-lens arrays layer, described micro-lens arrays layer comprises multiple predetermined radiation laser beam can being focused in described polymeric layer to make the lenticule of the appropriate section carbonization of polymeric layer;
Arrange binding layer, this binding layer has first surface and second surface, and has pore texture, wherein makes the first surface of binding layer contact with the second surface of polymeric layer;
The second surface of binding layer forms molding layer by molding; With
Irradiate lenticule with predetermined radiation laser beam, to make this radiation laser beam focus in described polymeric layer, carbonization is in the polymer moieties of the focal position of this radiation laser beam and forms carbonized part thus.
47. according to the method for claim 46, and the second surface that described method is also included in described micro-lens arrays layer arranges protective seam.
48. according to the method for claim 46 or 47, and described method also comprises and promotes that the adjuvant of the absorption to described predetermined radiation laser beam is added in described polymeric layer by being used for.
49. according to the method for claim 46 or 47, the laser of wherein said predetermined radiation laser beam to be wavelength be 400 to 1200nm.
50. according to the method for claim 46 or 47, and one or many is carried out in wherein said irradiation.
51., according to the method for claim 46 or 47, wherein use water white or light polymkeric substance to form described polymeric layer.
52. according to the method for claim 46 or 47, and the mould wherein for molding has buffer structure.
53. according to the method for claim 46 or 47, and the sprue gate wherein for molding is arranged perpendicular to pellicular front.
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| KR102485162B1 (en) * | 2020-09-08 | 2023-01-06 | (주)세경하이테크 | Manufacturing method of Cellular phone decoration film with micro lens array applied Polycarbonate layer |
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| US3758193A (en) * | 1971-07-02 | 1973-09-11 | Minnesota Mining & Mfg | Infrared-transmissive, visible-light-absorptive retro-reflectors |
| CN1452726A (en) * | 2000-02-22 | 2003-10-29 | 3M创新有限公司 | Sheeting with composite image that floats |
| CN1802253A (en) * | 2003-06-11 | 2006-07-12 | 纳幕尔杜邦公司 | Joining of different thermoplastic polymers |
| CN102692660A (en) * | 2012-02-29 | 2012-09-26 | 3M中国有限公司 | Product capable of realizing 3D floating images and manufacturing method thereof |
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2012
- 2012-11-15 CN CN201210495544.0A patent/CN102981193B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3758193A (en) * | 1971-07-02 | 1973-09-11 | Minnesota Mining & Mfg | Infrared-transmissive, visible-light-absorptive retro-reflectors |
| CN1452726A (en) * | 2000-02-22 | 2003-10-29 | 3M创新有限公司 | Sheeting with composite image that floats |
| CN1802253A (en) * | 2003-06-11 | 2006-07-12 | 纳幕尔杜邦公司 | Joining of different thermoplastic polymers |
| CN102692660A (en) * | 2012-02-29 | 2012-09-26 | 3M中国有限公司 | Product capable of realizing 3D floating images and manufacturing method thereof |
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