CN1174076C - Luminous membrane and its preparing process - Google Patents
Luminous membrane and its preparing process Download PDFInfo
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- CN1174076C CN1174076C CNB001191314A CN00119131A CN1174076C CN 1174076 C CN1174076 C CN 1174076C CN B001191314 A CNB001191314 A CN B001191314A CN 00119131 A CN00119131 A CN 00119131A CN 1174076 C CN1174076 C CN 1174076C
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Abstract
The present invention relates to a luminous film composed of a transparent layer, a luminous layer containing a photoluminescent material, a reflective layer, a non-dry adhesive layer and a deformed paper. The activated silicate containing various ions, aluminate, a sulfide luminous material or other mixtures are used in a luminous material. The luminous film can be made in a mode that a film can be made from raw materials at every layer and are compounded by heating and through glue or can be made with a coating method in a mode that paint can also be made from the raw materials at every layer. The luminous film has the advantages of high luminous brightness, long persistence time, various color, good performance and convenient use.
Description
Technical field
The present invention relates to a kind of formation and manufacture method of light-accumulating photoluminescent film.
Background technology
Luminescent film is to use materials such as embedded photoluminescent material and resin to make film product, and it can make the form of band non-setting adhesive, can cut randomly stickup, uses simply, and is convenient, but widespread use is made the safe escape indication mechanism in the dark as display mark.Their luminosity of existing product is low, and time of persistence is short, is difficult to satisfy luminous whole night requirement.Luminescent film product shown in 4.3 joints among the German standard 67510-4, the 10min brightness value is 20mcd/m
2, 60min brightness value 2.8mcd/m
2, time of persistence 340min.The luminescent material that this series products uses is zinc sulphide one class, and its light fastness, weather resistance are relatively poor.After using for some time, brightness value descends.Because the sulfuration zinc luminescent decomposes under action of ultraviolet radiation gradually, sulphur is separated out and is made the luminescent material blackout.When estimating the photostabilization of luminescent material with high voltage mercury lamp radiation, high voltage mercury lamp radiation its briliancy decline 65% after 100 hours of sulfuration zinc luminescent; Shine its briliancy decline 99% after 300 hours, luminous hardly.The every performance of the described luminescent film of patent (ZL93213168.9) is unsatisfactory, and the luminescent material that it uses is the complex body of ZnS class and aluminate (as patent disclosure CN1053807A).By overlength (and initial luminance the is not high) twilight sunset of the high brightness and the aluminate of ZnS class luminescent material, it is not high that its briliancy of ZnS class luminescent material had been mentioned in our front, weather-proof in addition, shortcomings such as light fastness difference.Existing luminescent film glow color is single.
Summary of the invention
At the defective of above-mentioned prior art, the objective of the invention is with high briliancy, the diversified luminescent material of glow color, make the glorious degrees height, time of persistence is long, and glow color is colorful, and weathering resistance, photostabilization are good, shrinking percentage is low, and flexility is good, the luminescent film that use properties is good.
The present invention be by adopt novel different kinds of ions activated light-accumulating embedded photoluminescent material (to call luminescent material in the following text), various kinds of resin, subsidiary material etc. carry out big quantity research obtain best manufacture craft and the prescription achieve the above object.The luminescent film of manufacturing of the present invention is soft type, and its basic structure is: the luminescent layer and white or the light reflector layer that contain luminescent material.Be the performance (as: resistance to marring, wear resistance etc.) on reinforcing membrane surface, some film increases protective clear layer (hereinafter to be referred as transparent layer); Some luminescent film is for easy to use, can make to have non-setting adhesive bonding coat and off-style paper layer, and the thickness of its luminescent film is decided on purposes, and the preferred thickness of luminescent film is 0.03～3.5mm.
Luminescent layer is to be become by luminescent material, vector resin, softening agent, auxiliary agent, solution mixing system.Its thickness is decided on purposes, is generally 0.02～2.0mm, and its composition weight percent is:
Vector resin 20～95
Luminescent material 5～80
Softening agent 0～60
Auxiliary agent 0～30
Transparent layer: can use the universal transparent film, also can use transparent resin coating, its thickness is decided on purposes, is generally 0.005～0.5mm.Transparent resin coating is to make the coating coating with vector resin, softening agent, solvent, auxiliary agent to form, and its composition weight percent is:
Vector resin 10～100
Softening agent 0～70
Auxiliary agent 0～30
Reflector layer can be used white or light film or paper, also can use light color or whitewash coating, wherein reflector layer is best with white effect, its thickness is decided on purposes, be generally 0.01～1.5mm, paint coatings is to be mixed and made into the coating coating with vector resin, softening agent, auxiliary agent, solvent, color, filler to form, and its composition weight percent is:
Vector resin 10～98
Softening agent 0～60
Auxiliary agent 0～30
Pigment 2～80
Filler 0～40
Wherein vector resin is one or more the combination in polyvinyl chloride resin, acrylic resin, urethane resin, vibrin, chlorinated polypropylene, supervinyi chloride resin, Synolac, ethenoid resin, Resins, epoxy, polyamide resin, acrylic resin, isocyanate prepolymer, polyvinyl resin, EVA resin, SB resin, the nylon etc.
Softening agent is the common plastics softening agent as dibutyl phthalate (DBP), dioctyl phthalate (DOP) (DOP), dimixo-octyl phthalate (DIOP), butyl benzyl phthalate (BBP), dipropyl phthalate (DAP), di-sec-octyl phthalate (DCP), didecyl phthalate (DIDP), phthalic acid two (13) ester (DTDP), Dinonylphthalate (DNP), Octyl adipate (DOA), dioctyl sebacate (DOS), epoxy octyl stearate (ED3), epoxy soybean oil (ESO), epoxyoleic acid butyl ester (EBST), epoxy tetrahydro-2-ethylhexyl phthalate (EPS), triphenylphosphate (TCP), TXIB, the combination of one or more in the viscosity-depression agent (1300).
Auxiliary agent: ultraviolet absorbers, stablizer, flow agent, defoamer, fire retardant, oxidation inhibitor, coupling agent, anti-settling agent, lubricant are arranged; Use wherein one or more as required, wherein:
Ultraviolet absorbers: UV-326, UV-531, UV-9 etc.
Stablizer: liquid composite stabilizing agent barium/cadmium, barium/cadmium/zinc, calcium/zinc, dibutyl tin laurate, two lauric acid dioctyl tins, two toxilic acid list tin octylates etc.
Flow agent: as BYK-385, EFKA-30, EFKA-31, EFKA-34, EFKA-35 etc.
Defoamer: as DAPRO-NA1621, BYK303, EFKA-21, EFKA-22, methyl-silicone oil liquid etc.
Fire retardant: antimonous oxide, aluminium hydroxide etc.
Anti-settling agent: aerosil, PE wax etc.
Lubricant: Zinic stearas, barium stearate, stearic amide etc.;
Coupling agent: silane coupling agent, titanic acid ester, aluminic acid ester etc.;
1010,168, DLTP, SKY-1035 etc. oxidation inhibitor:;
Solvent: solvent is one or more mixing in dimethylbenzene, N-BUTYL ACETATE, ethylene glycol, ether, acetic acid, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, pimelinketone, butanone, dimethyl formamide, different your ketone that boils, look its resin and purposes, use wherein one or more.
Pigment and filler are: titanium dioxide, zinc sulfide white, zinc white, lime carbonate, barium sulfate, aluminium powder etc.
Separate-type paper: the general silicon paper that is coated with.
Non-setting adhesive is acrylic resin, rubber resin.
Transparent film is transparent PET film, PP film, PVC film, PE film.White or light film is white or light PET film, PP film, PVC film, PE film or paper, aluminium foil, tinfoil paper, aluminium plating film or paper, tin-plated coating film or paper, electrochemical aluminium film or paper etc.。
The used luminescent material of the present invention is different kinds of ions activated silicate, aluminate, sulfide luminescent material or its mixture, and its main expression and luminous twilight sunset color are as follows respectively:
1, the chemical constitution expression of different kinds of ions activated silicate luminescent material is:
αMO·βM’O·γSiO
2·δR：Eu
xLn
y
Wherein: M is the combination of one or more elements among Sr, Ca, Ba, the Zn;
M ' is the combination of one or more elements among Mg, Cd, the Be;
R is B
2O
3, P
2O
5In one or both combination of compounds;
Ln is the combination of one or more elements among Nd, Dy, Ho, Tm, La, Pr, Tb, Ce, Er, Mn, Bi, Sn, the Sb:
α, β, γ, δ, x, y are mole coefficient:
0.6≤α≤6；0≤β≤5；1≤γ≤9；
0≤δ≤0.7；0.00001≤x≤0.2；0≤y≤0.3。
Further experiment shows that in the preferred above-mentioned silicate luminescent material, the luminescent material of following 2 classes can be made the luminescent film of higher brightness, and main chemical constitution expression is:
1-1.(Sr
1-zCa
z)
2MgSi
2O
7：Eu
xLn
y
1-2.(Sr
1-zCa
z)
3MgSi
2O
8：Eu
xLn
y
Wherein: Ln is one or more element combinations among La, Ce, Dy, Tm, Ho, Nd, Er, Sb, the Bi;
Z is coefficient: 0≤z≤1;
X, y are mole coefficient: 0.0001≤x≤0.2; 0.0001≤y≤0.3.
The preferred long persistence luminescent silicate material of above-mentioned 2 classes is with the difference of z value, can send orchid, blue green, green, yellowish green, sodium yellow respectively, for example during z=0, sends out coloured light blue; During z=0.5, glow green.
2, the chemical constitution expression of different kinds of ions activated aluminate luminescent material is:
αMO·βAL
2O
3·γB
2O
3：Eu
xLn
y
Wherein: M is the combination of one or more elements among Mg, Ca, Sr, Ba, Zn, the Cd;
Ln is the combination of one or more elements among Nd, Dy, Ho, Tm, La, Ce, Er, Pr, the Bi;
α, β, γ, x, y are mole coefficient:
0.5≤α≤6；0.5≤β≤9；0.0≤γ≤0.3；
0.00001≤x≤0.25；0.00001≤y≤0.3。
Further experiment shows, preferred above-mentioned aluminate luminescent material, and the luminescent material of following 2 classes can be made the luminescent film of higher brightness, and main chemical constitution expression is:
2-1.MAl
2O
4：Eu
xLn
y
Wherein: Ln is the combination of one or more elements among La, Ce, Dy, Ho, Nd, the Er;
M is the combination of one or more elements among Sr, Ca, Mg, Ba, the Zn;
X, y are mole coefficient: 0.0001≤x≤0.25; 0.0001≤y≤0.3.
This material is with the difference of M, the glow color difference, during as M=Sr, for yellow-green colour luminous; During M=Ca, be blue violet light.
2-2.M
4Al
14O
25：Eu
xLn
y
Wherein: Ln is the combination of one or more elements among Pr, Ce, Dy, Ho, Nd, the Er;
M is the combination of one or more elements among Sr, Ca, Mg, Ba, the Zn;
X, y are mole coefficient: 0.0001≤x≤0.25; 0.0001≤y≤0.3.
3. the main chemical constitution expression of different kinds of ions activated sulfide luminescent material is:
3-1.(Ca
1-zSr
z)S：Eu
xLn
y
Wherein: Ln is the combination of one or more elements among Er, Dy, La, Tm, the Y;
Z is coefficient: 0≤z≤1;
X, y are mole coefficient: 0.00001≤x≤0.2; 0.00001≤y≤0.15.
This material is different with the z value, can present red, orange luminescence.
3-2.R
2O
2S：Eu
xLn
y
Wherein: R is the combination of one or more elements among Y, La, the Gd;
Ln is the combination of one or more elements among Er, Cr, Bi, Dy, Tm, Ti, Mg, Sr, Ca, Ba, the Mn;
X, y are mole coefficient: 0.00001≤x≤0.2; 0.00001≤y≤0.6.
The manufacturing of luminescent film of the present invention can be divided into luminescent layer, reflector layer, the manufacturing several steps of the non-drying glue layer of transparent layer band separate-type paper, then with this which floor in conjunction with the as a whole luminescent film that promptly gets, wherein reflector layer, transparent layer adopt ready-made film sometimes, need sometimes to make.The manufacture method of luminescent layer is a gordian technique of the present invention, below with the manufacture method of each layer of step-by-step instructions.
Luminescent layer: the manufacture method of luminescent layer is divided into two classes, first kind method: be with roll, extrude, the method for blowing, curtain coating makes luminescent layer; Second class methods: be to make luminous paint earlier, the technology that applies luminous paint on basement membrane is made luminescent layer.It uses proportion of raw materials (W%) as follows:
Vector resin 20～95
Softening agent 0～60
Auxiliary agent 0～30
Luminescent material 5～80
Solvent 0～60
The technical recipe (W%) of the first kind method of manufacturing luminescent film is as follows:
Vector resin 20～95
Softening agent 0～30
Auxiliary agent 0～30
Luminescent material 5～60
Manufacture craft: raw material ratio weighings on demand such as vector resin, softening agent, auxiliary agent, luminescent material are mixed, with roll, extrude, complete processing such as blowing, curtain coating makes certain thickness film, promptly gets luminescent layer.Its processing temperature is 130 ℃～270 ℃.
The technical recipe (W%) of second class methods of manufacturing luminescent film is as follows:
Vector resin 20～95
Softening agent 0～60
Solvent 0～60
Auxiliary agent 0～30
Luminescent material 5～80
The making of manufacture craft 1, coating: with the ratio weighing on demand of vector resin, softening agent, solvent, auxiliary agent and luminescent material, mix through high speed dispersor, three-roll grinder is ground to required fineness, makes luminous paint.2, luminescent layer moulding: luminous paint applies on basement membrane after deaeration, filtering, and luminescent layer is made in drying (room temperature～180 ℃) or thermoforming (100 ℃～270 ℃) again.
Reflector layer: reflector layer can also can be used light color or whitewash coating with white or light film or paper.Use white or light film or paper itself and luminescent layer are laminated with are one with being laminated with technology, or with white or light film or the paper base material making luminescent film as the coating luminous paint.Its technical recipe (W%) was as follows when reflector layer was white or light-coloured coating coating:
Vector resin 10～98
Softening agent 0～60
Solvent 0～60
Auxiliary agent 0～30
Pigment 2～80
Filler 0～40
The manufacture craft of reflector layer: 1, the making of coating: with the ratio weighing on demand of vector resin, softening agent, solvent, auxiliary agent and pigment, mix through high speed dispersor, three-roll grinder is ground to required fineness, makes coating.2, reflector layer moulding: coating applies on luminescent layer or basement membrane after deaeration, filtering, and reflector layer is made in drying (dry or dry under 30 ℃～180 ℃ conditions) or thermoforming (100 ℃～270 ℃) again.
Transparent layer: transparent layer can be used transparent film, also can use the Clear paint coating.Use transparent film with being laminated with technology itself and luminescent layer to be combined as a whole, or use transparent film to make luminescent film as the base material that applies luminous paint, its technical recipe (W%) was as follows when transparent layer was the Clear paint coating:
Vector resin 10～100
Softening agent 0～70
Solvent 0～90
Auxiliary agent 0～30
Manufacture craft is: 1, the making of coating: with the ratio weighing on demand of vector resin, softening agent, solvent, auxiliary agent, mix through high speed dispersor, three-roll grinder is ground to required fineness, makes Clear paint.2, transparent layer moulding: coating applies on luminescent layer or basement membrane after deaeration, filtering, and transparent layer is made in drying (dry or dry under 30 ℃～180 ℃ conditions) or thermoforming (100 ℃～270 ℃) again.
Non-drying glue layer: non-setting adhesive can use ready-made double sticky tape.Or what directly use is that the white or the light base material of band non-setting adhesive made luminescent film, also can be with directly or transfer method coating non-setting adhesive.
The method that luminescent film of the present invention is become one with transparent layer, luminescent layer, reflector layer is: 1, with glue or hot composite methods combining transparent layer, luminescent layer, reflector layer; 2, with coating processes each coating is applied successively, natural combination is an one in drying process.The coating order of its each layer when applying can be arbitrarily, only requires that luminescent layer gets final product in the centre.3, on the basement membrane of reflector layer or transparent layer, apply luminescent layer, transparent layer or reflector layer.The coating processes of mentioning among the present invention is that coating is evenly distributed in a kind of in coating, printing, the spraying of the method used on the basement membrane; More normally used basement membrane paper are separate-type paper, transparent film white or light film.
Further experiment shows the briliancy of luminescent film, the type of time of persistence and luminescent material, the content of luminescent material in whole luminous rete, the thickness of luminescent layer and the selection of vector resin are relevant, and other performance of luminescent film (as: weather resisteant energy, light fastness) is relevant with the selection of vector resin, auxiliary agent.
The luminescent film glorious degrees height that the present invention makes, time of persistence is long, glow color is colorful, good weatherability, shrinking percentage are low, and high its glorious degrees of briliancy film is as wherein: 1min is 1800mcd/m
2, 10min is 230mcd/m
2, 60min is 34mcd/m
2Reach 3000 minutes time of persistence.The briliancy 1min of its superelevation briliancy film can reach 4300mcd/m
2, 10min is 650mcd/m
2, 60min can reach 100mcd/m
2, reach 4800min time of persistence.And the glow color variation of luminescent film can be sent red, orange, yellow, yellowish green, green, blue green, blue, purple light.The weather resistance of its luminescent material, light fastness is splendid.Estimate the photostabilization of luminescent material with high voltage mercury lamp radiation.With luminescent film high voltage mercury lamp radiation its briliancy decline 2% after 100 hours that aluminate, silicate luminescent material are made, to shine after 300 hours, its briliancy descends 3%.
Embodiment
Its briliancy height of luminescent film compared with prior art of the present invention, time of persistence, and photostabilization, weathering resistance significantly improve, and glow color is various.Below further specify the luminescent film manufacture method with example:
Example one: this example is to use first kind method to make luminescent layer.
Vector resin polyvinyl chloride resin (III type resin) 40kg
Plasticizer phthalic acid dibutylester 20kg
Dioctyl phthalate (DOP) 10kg
Auxiliary agent stablizer (Ca-Zn is compound) 3.0kg
Luminescent material aluminate SrAl
2O
4: Eu
0.05, Dy
0.150kg
By the described starting material that take by weighing of prescription, other material adding height except that luminescent material to be stirred in the machine, high speed dispersion is even, adds luminescent material again and stirs, and jitter time will be lacked, and rotating speed is low.The former material that mixes is made the luminous rete that thickness is 200 μ m through calendering technology.With luminescent layer with white the PVC film through the overheated luminescent film that is combined into.Being laminated with non-setting adhesive with the method for transfer coating, promptly to get glow color be yellowish green luminescent film, and the performance of its twilight sunset is as follows:
| Time (min) | 1 | 5 | 10 | 60 |
| Briliancy (mcd/m 2) | 1015 | 259 | 135 | 18 |
| Time of persistence (min) | 2500 | |||
Example two: this example is to make luminescent layer with first kind method
Vector resin PP resin 78kg
Auxiliary agent dispersion agent: PP wax 1.5kg
Lubricant: Zinic stearas 0.5kg
Luminescent material silicate: Sr
2MgSi
2O
7: Eu
0.05, Dy
0.120kg
Manufacture craft: with PP resin, dispersion agent (PP wax), lubricant weighing in proportion, put into height and stir the stirring of machine high speed, treat that PP wax fusing back adds luminescent material, after mixing, send into blowing on the blow moulding machine, two-way stretch is to thickness 0.15mm, at the PP printing ink of one side with intaglio printing one deck white, thickness is 0.05mm, coats non-setting adhesive.This product glow color is blue look.Product can be made Watch dail plate, or gluing not, stamps various patterns as the Gift Package material.This film glorious degrees is as follows:
| Time (min) | 1 | 5 | 10 | 60 |
| Briliancy (mcd/m 2) | 230 | 80 | 45 | 6 |
| Time of persistence (min) | 1500 | |||
Example three: this example is to use second class methods to make luminescent film
The technical recipe (W%) that luminescent layer is made is as follows:
Vector resin acrylic resin liquid 35kg
Biuret 5kg
Auxiliary agent aerosil 2kg
Defoamer 0.3kg
Plasticizer phthalic acid dioctyl ester 7kg
Solvent xylene 3kg
Acetate butyl 2kg
Luminescent material strontium sulfide calcium: SrCaS:Eu
0.001, Y
0.00555.7kg
Execute real technology: the liquid starting material in will filling a prescription adds in the proportion container, stirs, and aerosil is slowly added the container high speed be uniformly dispersed, and it is standby that the adding luminescent material is made into luminous paint under whipped state.Add biuret before use and stir, placed 30 minutes.
Reflecting coating is a white, and (W%) is as follows for its technical recipe:
Vector resin acrylic resin 35kg
Biuret 5kg
Auxiliary agent aerosil 2kg
Defoamer: EFKA-30 0.3kg
Plasticizer phthalic acid dioctyl ester 7kg
Solvent xylene 3kg
Acetate butyl 2kg
Pigment titanium white R930 30kg
Implementing process: 1, the making of coating: with the ratio weighing on demand of acrylic resin liquid, aerosil, defoamer, dioctyl phthalate (DOP), solvent, titanium dioxide, mix through high speed dispersor, three-roll grinder is ground to required fineness, and it is stand-by to make whitewash.Adding biuret before use stirs and placed 30 minutes.
Be coated on through on the PET film of corona treatment preparing luminous paint, wet coat-thickness is 380 μ m, and dry back luminescent film light emitting layer thickness is 180～200 μ m.After treating the luminescent layer drying, be coated with white acrylic coating, the drying temperature of coating is 25 ℃, and be 24 hours time of drying, is laminated with double sticky tape, cuts packing, gets product.This technology is made the luminescent film burn red.The luminescent film surface scratch resistance can be good, well-pressed.Glorious degrees is as follows:
| Time (min) | 1 | 5 | 10 | 60 |
| Briliancy (mcd/m 2) | 119 | 21 | 10 | 1.2 |
| Time of persistence (min) | 240 | |||
Example four: use second class methods and make luminescent film
(W%) is as follows for the technical recipe of luminescent layer:
Vector resin urethane resin resin (50%) 60kg
Luminescent material sulphur oxygen yttrium Y
2O
2S:Eu
0.01, Ca
0.0539.5kg
Auxiliary agent flow agent EFKA-30 0.5kg
Defoamer EFKA-21 0.5kg
The reflector layer technical recipe:
Vector resin urethane resin resin (50%) 60kg
Pigment titanium white 39.5kg
Auxiliary agent flow agent Byk300 0.5kg
Luminous paint, reflecting layer coating manufacture craft are coated with coating machine luminous paint with example (3) on the PET film surface of crossing through corona treatment, the thickness of wet coating is 300 μ m, and oven dry is coated with white coating again.Coat non-setting adhesive and promptly get luminescent film, the glow color of this product is red.Can be used to make label, the pad pasting on the toy, fashionable dress Watch dail plate.
Glorious degrees is as follows:
| Time (min) | 0 | 1 | 10 | 60 |
| Briliancy (mcd/m 2) | 450 | 105 | 45 | 4 |
| Time of persistence (min) | 680 | |||
Example five:.This example is made luminescent film with second class methods.
Technical recipe:
Vector resin chlorinated polypropylene liquid 49.5kg
Luminescent material strontium aluminate SrAl
2O
4: Eu
0.05, Dy
0.125kg
Strontium silicate calcium magnesium Sr
1.5Ca
0.5MgSi
2O
7: Eu
0.05, Dy
0.125kg
Auxiliary agent defoamer 0.5kg
The same example of luminous paint manufacture craft (3) is printed directly on the white PVC pressure sensitive membrane with silk-screen printing technique, and drying promptly gets individual luminescent film.This technology is simple, and is easy to make.The glow color of luminescent film is a yellow-green colour,
The luminescent film briliancy is as follows:
| Time (min) | 1 | 5 | 10 | 60 |
| Briliancy (mcd/m 2) | 1340 | 450 | 260 | 26.8 |
| Time of persistence (min) | 3200 | |||
Example six: this example is made luminescent film with second class methods, and its technical recipe is that (W%) is as follows:
(1) luminescent coating (1) (2)
Vector resin PVC sticks with paste resin: PSH-10 50kg 50kg
PSM-31 50kg 50kg
Softening agent triphenylphosphate TCP 0kg 30kg
Dibutyl phthalate 20kg 10kg
Dioctyl phthalate (DOP) 40kg 20kg
Viscosity-depression agent 1300 2kg 2kg
Auxiliary agent barium cadmium stabilizer 3kg 3kg
Coupling agent titanic acid ester 0.5kg 0.5kg
Luminous pigment strontium aluminate SrAl
2O
4: Eu
0.05, D
0.1165.5kg 165.5kg
(2) reflector layer (1) (2)
Vector resin PVC sticks with paste resin: PSH-10 50kg 50kg
PSM-31 50kg 50kg
Plasticizer phthalic acid dibutylester 33.3kg 30kg
Dioctyl phthalate (DOP) 40kg 20kg
Viscosity-depression agent 1300 2kg 2kg
Auxiliary agent barium cadmium stabilizer 3kg 3kg
Coupling agent: aluminic acid ester 0.5kg 0.5kg
Fire retardant: antimonous oxide 0kg 23kg
Pigment titanium white 13kg 15kg
(3) protective clear layer
Vector resin polyvinyl chloride resin: PSH-10 100kg
Plasticizer phthalic acid dioctyl ester 30kg
Dibutyl phthalate 15kg
Viscosity-depression agent 1300 2kg
Auxiliary agent dibutyl tin laurate 3kg
UV-531 2kg
Manufacture craft is:
One, various coated coating preparations
1, the coating of transparent layer preparation
Liquid material in the prescription is added in the container, stir.Even adding polyvinyl chloride resin adds the back and improves stirring velocity under whipped state, becomes paste behind the several minutes, meets the requirements of fineness through the three-roll grinder grinding and is called blank the paste, is transparent layer coating.
2, luminescent layer coating preparation
Use 1 technology by the prescription of luminescent coating and make blank the paste, evenly add luminous pigment in scattered paste under whipped state, the beginning rotating speed is wanted slowly.Treat that luminous pigment adds the back and improves rotating speed, luminous pigment is uniformly dispersed get final product, attention material temperature≤40 ℃ in dispersion process.
3, reflecting layer coating preparation.
Use the part softening agent to make blank the paste by the white coating prescription with 1 technology, with softening agent allocate titanium dioxide, antimonous oxide is ground to the fineness that needs at three-roller and gets fire-retardant titanium dioxide slurry, and is stand-by.Take by weighing fire-retardant titanium dioxide slurry, the blank paste in proportion, with high-speed dispersion equipment it is mixed and promptly get white coating coating.
Each coating that two, will prepare filters vacuum defoamation.
Three, coating, thermoforming:
After applying Clear paint thermoforming, cooling and shaping earlier on the separate-type paper, behind the thermoforming of coating luminous paint, cooling and shaping on the Clear coating, the thermoforming of coating whitewash, cooling and shaping promptly get luminescent film on luminescent coating again, hot-forming temperature is 150～200 ℃, each layer thickness is respectively transparent layer 0.005mm, luminescent layer 0.2mm, white coating 0.13mm.Luminescent film is peeled away from separate-type paper, applied non-setting adhesive, cut and cover volume, packing becomes finished product.
This technology making luminescent film is tough and tensile, better weather is arranged, anti-opticity.Shrinking percentage is little, and flame retardant properties is good.
Performance index such as following table:
Claims (19)
1, a kind of luminescent film that contains embedded photoluminescent material is characterized by described luminescent film substantially by the luminescent layer that contains different kinds of ions activated embedded photoluminescent material, reflector layer, and the non-drying glue layer of band separate-type paper is formed the soft film of one;
Described luminescent layer is made of vector resin, embedded photoluminescent material, softening agent and auxiliary agent, and its weight percent consists of:
Vector resin 20～95
Luminescent material 5～80
Softening agent 0～60
Auxiliary agent 0～30
Described reflector layer can be white or light film or paper; Also can be light color or whitewash coating; Its weight percent consists of during for coating:
Vector resin 10～98
Softening agent 0～60
Auxiliary agent 0～30
White pigment 2～80
Filler 0～40
Described vector resin is: the combination of one or more in polyvinyl chloride resin, acrylic resin, urethane resin, vibrin, chlorinated polypropylene, supervinyi chloride resin, Synolac, ethenoid resin, Resins, epoxy, polyamide resin, acrylic resin, isocyanate prepolymer, polyvinyl resin, EVA resin, SB resin, the nylon;
Described softening agent is general plastic working softening agent;
Described auxiliary agent is one or more combination in ultraviolet absorbers, stablizer, flow agent, defoamer, fire retardant, oxidation inhibitor, coupling agent, anti-settling agent, the lubricant;
Described pigment, filler are titanium dioxide, zinc sulfide white, zinc white, lime carbonate, barium sulfate, aluminium powder;
Described light color or white films are PVC, PP, PE, synthetic glass, polycarbonate plastic film, aluminium foil, tinfoil paper, aluminium plating film, electrochemical aluminium film or paper;
Described embedded photoluminescent material is different kinds of ions activated silicate, aluminate, sulfide luminescent material and composition thereof;
The non-drying glue layer of described band separate-type paper is a self-adhesive pressure sensitive adhesive, and separate-type paper is the sealing coat of non-setting adhesive.
2, luminescent film as claimed in claim 1, it is characterized by the luminescent layer surface has the layer of transparent resin protective layer, and its thickness is 0.005～0.5mm.
3, luminescent film as claimed in claim 1, the thickness that it is characterized in that luminescent film is 0.03～3.5mm, the thickness of each layer is respectively: luminescent layer 0.02～2.0mm, reflector layer 0.01～1.5mm.
4, luminescent film as claimed in claim 1 is characterized in that the chemical constitution expression of described different kinds of ions activated silicate luminescent material is:
αMO·βM’O·γSiO
2·δR：Eu
xLn
y
Wherein: M is a kind of element among Sr, Ca, Ba, the Zn or the combination of multiple element;
M ' is the combination of one or more elements among Mg, Cd, the Be;
R is B
2O
3, P
2O
5In one or both combination of compounds;
Ln is the combination of one or more elements among Nd, Dy, Ho, Tm, La, Pr, Tb, Ce, Er, Mn, Bi, Sn, the Sb:
α, β, γ, δ, x, y are mole coefficient,
0.6≤α≤6；0≤β≤5；1≤γ≤9；
0≤δ≤0.7；0.00001≤x≤0.2；0≤y≤0.3。
5, different kinds of ions activated silicate luminescent material as claimed in claim 5 is characterized in that the main chemical constitution expression of luminescent material is:
(Sr
1-zCa
z)
2MgSi
2O
7：Eu
xLn
y
Wherein: Ln is one or more element combinations among La, Ce, Dy, Tm, Ho, Nd, Er, Sb, the Bi;
Z is coefficient: 0≤z≤1;
X, y mole coefficient: 0.0001≤x≤0.2; 0.0001≤y≤0.3.
6, different kinds of ions activated silicate luminescent material as claimed in claim 5 is characterized in that the main chemical constitution expression of luminescent material is:
(Sr
1-zCa
z)
3MgSi
2O
8：Eu
xLn
y
Z is coefficient: 0≤z≤1;
X, y mole coefficient: 0.0001≤x≤0.2; 0.0001≤y≤0.3.
7, luminescent film as claimed in claim 1 is characterized in that the main chemical constitution expression of described different kinds of ions activated aluminate luminescent material is:
αMO·βAL
2O
3·γB
2O
3：Eu
xLn
y
Wherein: M is the combination of one or more elements among Mg, Ca, Sr, Ba, Zn, the Cd;
Ln is the combination of one or more elements among Nd, Dy, Ho, Tm, La, Ce, Er, Pr, the Bi;
α, β, γ, x, y are mole coefficient,
0.5≤α≤6；0.5≤β≤9；0.0≤γ≤0.3；
0.00001≤x≤0.15；0.00001≤y≤0.2。
8, different kinds of ions activated aluminate luminescent material as claimed in claim 8 is characterized in that the main chemical constitution expression of luminescent material is:
MAl
2O
4：Eu
xLn
y
Wherein: Ln is the combination of one or more elements among La, Ce, Dy, Ho, Nd, the Er;
M is the combination of one or more elements among Sr, Ca, Mg, Ba, the Zn;
X, y are mole coefficient: 0.0001≤x≤0.25; 0.0001≤y≤0.3.
9, different kinds of ions activated aluminate luminescent material as claimed in claim 8 is characterized in that the main chemical constitution expression of luminescent material is:
M
4Al
14O
25：Eu
xLn
y
Wherein: Ln is the combination of one or more elements among Pr, Ce, Dy, Ho, Nd, the Er;
M is the combination of one or more elements among Sr, Ca, Mg, Ba, the Zn;
X, y are mole coefficient: 0.0001≤x≤0.25; 0.0001≤y≤0.3.
10, luminescent film as claimed in claim 1 is characterized in that the main chemical constitution expression of described different kinds of ions activated sulfide luminescent material is:
(Ca
1-zSr
z)S：Eu
xLn
y
Wherein: Ln is the combination of one or more elements among Er, Dy, La, Tm, the Y;
Z is a coefficient, 0≤z≤1;
X, y are mole coefficient: 0.00001≤x≤0.2; 0.00001≤y≤0.15.
11,, luminescent film as claimed in claim 1, it is characterized in that the main chemical constitution expression of described different kinds of ions activated sulfide luminescent material is:
R
2O
2S：Eu
xLn
y
Wherein: R is the combination of one or more elements among Y, La, the Gd;
Ln is the combination of one or more elements among Er, Cr, Bi, Dy, Tm, Ti, Mg, Sr, Ca, Ba, the Mn;
X, y are mole coefficient: 0.00001≤x≤0.2; 0.00001≤y≤0.6.
12, a kind of manufacture method that contains the luminescent film of embedded photoluminescent material is characterized in that making the luminescent layer that contains different kinds of ions activated embedded photoluminescent material, the non-drying glue layer of luminescent layer, reflector layer, band separate-type paper is become to be made into integration luminescent film then;
Use the raw material weight per distribution ratio to be when luminescent layer is made:
Vector resin 20～95
Softening agent 0～60
Auxiliary agent 0～30
Luminescent material 5～80
Solvent 0～60
Making method is divided into two classes: first kind method with raw material mix with roll, extrude, blowing, casting method makes luminescent layer, thickness is 0.02～2.0mm, processing temperature is 130～270 ℃, second class methods for raw material mix make luminous paint with the coating method make luminescent layer, thickness is 0.02～2.0mm, being 20～180 ℃ during the processing temperature drying process, is 100～270 ℃ during thermoforming process; Apply one deck resin coating in the one side with white or light-coloured coating then, or with heat or the compound one deck of glue white or light film or paper, thickness is 0.01～1.5mm, film and paper have non-drying glue layer sometimes; The last separate-type paper non-drying glue layer of on a side of reflector layer is compound, being with.
13, luminescent film method for making as claimed in claim 12, it is compound or to apply its thickness of layer of transparent layer be 0.005～0.5mm in a side of luminescent layer to it is characterized by described luminescent film.
14, luminescent film method for making as claimed in claim 12 is characterized by described luminescent layer proportioning raw materials and is:
Vector resin 20～95
Softening agent 0～30
Auxiliary agent 0～30
Luminescent material 5～60
Its manufacturing process is, raw material is mixed, with prolong pressure, extrude, the method for blowing, curtain coating makes, processing temperature is: 130～270 ℃.
15, as the method for making of claim 12 luminescent film, it is characterized by described luminescent layer is to apply on basement membrane with luminous paint to form, the raw material weight per distribution ratio that uses when making luminous paint:
Vector resin 20～95
Softening agent 0～60
Solvent 0～60
Auxiliary agent 0～30
Luminescent material 5～80
Its making method mixes raw material through high speed dispersor, three-roll grinder grinds makes coating, through deaeration, filter the back and apply, apply drying after heat moulding afterwards and form, processing temperature is 100～270 ℃ when being 20～180 ℃ of thermoforming process during for drying process.
16, as the method for making of luminescent film as described in the claim 12, it is characterized by described reflector layer is to be coated in luminescent layer with white or light-coloured coating simultaneously to form, and raw material weight per-cent is during making:
Vector resin 10～98
Softening agent 0～60
Auxiliary agent 0～30
Solvent 0～60
Pigment 2～80
Filler 0～40
Its making method mixes raw material through high speed dispersor, three-roll grinder grinds makes coating, this coating applies luminescent layer or basement membrane after deaeration, filtration, applying back drying or thermoforming forms, processing temperature for drying or 30～180 ℃, is 100～270 ℃ during thermoforming process during for drying process.
17, as the method for making of luminescent film as described in the claim 13, it is characterized by described transparent layer is to apply on luminescent layer or basement membrane and form with Clear paint, and the raw material weight per distribution ratio when its Clear paint is made is as follows:
Transparent resin 10～100
Softening agent 0～70
Solvent 0～90
Auxiliary agent 0～30
Its making method mixes raw material through high speed dispersor, three-roll grinder grinds makes coating, this coating applies luminescent layer or basement membrane after deaeration, filtration, applying back drying or thermoforming forms, processing temperature is: for drying or 30～180 ℃, be 100～270 ℃ during thermoforming process during drying process.
18, as claim 12,13,15,16,17 each as described in the luminescent film manufacture method, it is characterized by described coating processes for the coating, the printing, the spraying in a kind of;
19, as claim 15,17 each as described in the luminescent film manufacture method, it is characterized by described basement membrane is paper, separate-type paper, transparent film, white or light film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001191314A CN1174076C (en) | 2000-06-24 | 2000-06-24 | Luminous membrane and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001191314A CN1174076C (en) | 2000-06-24 | 2000-06-24 | Luminous membrane and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1331268A CN1331268A (en) | 2002-01-16 |
| CN1174076C true CN1174076C (en) | 2004-11-03 |
Family
ID=4587509
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001191314A Expired - Lifetime CN1174076C (en) | 2000-06-24 | 2000-06-24 | Luminous membrane and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1174076C (en) |
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2000
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| CN1331268A (en) | 2002-01-16 |
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Granted publication date: 20041103 |