Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of noctilucent stone paper, to overcome the above-mentioned defect that prior art exists.
For solving the problems of the technologies described above, noctilucent stone paper of the present invention is by the component of following weight part, forms through mixing, plasticizing, curtain coating and calendering:
Graft modification Rare-earth Long Persistence Luminescent Phosphor powder 5 ~ 10 parts,
Linear low density polyethylene 15 ~ 20 parts,
Chlorinatedpolyethylene 5 ~ 10 parts,
65 ~ 80 parts, the bar-shaped calcium carbonate of silane-modified lightweight,
2,5-dimethyl-2,5-bis(t-butylperoxy) hexane 0.2 ~ 0.6 part,
Nano-aluminum hydroxide 1 ~ 3 part,
Three (2-chloroethyl) phosphoesterase 30 .5 ~ 1.5 part,
Dioctyl phthalate (DOP) 3 ~ 6 parts,
Nano zine oxide 0.4 ~ 0.8 part,
Triazine-425 0.1 ~ 0.3 parts,
P-octylphenyl salicylate 0.1 ~ 0.3 part,
Sorbitan monostearate (span60) 0.5 ~ 1.5 part.
Described graft modification Rare-earth Long Persistence Luminescent Phosphor powder is prepared by the following method:
At 80 DEG C, be sprayed in Rare-earth Long Persistence Luminescent Phosphor powder with monoalkoxy lipid acid titanic acid ester 0.03 ~ 0.05 weight part of volume ratio 1:1 Witco 70 dilution, high-speed stirring 30 minutes, spray into by vinyl acetate and peroxidation neodecanoic acid-1 again, 1-dimethyl-3-hydroxybutyl ester is by weight the functional monomer 0.3 ~ 0.5 part of 1:0.01 mixing, continue high-speed stirring 30 minutes, finally add optical absorbing agent 1 ~ 3 part, fully mix.
Described Rare-earth Long Persistence Luminescent Phosphor powder can adopt this area conventional products, preferably adopts and prepares with the following method:
300 object powders are ground to form by after Strontium carbonate powder 4 ~ 6 parts, aluminium sesquioxide 2 ~ 4 parts, europiumsesquioxide 0.1 ~ 0.3 part, Dysprosium trioxide 0.2 ~ 0.6 part, boric acid 0.4 ~ 0.8 part fully mixing, then electric furnace is put into, roasting after powder-compacting is compressed, per minute heats up about 10 DEG C, rise to 1520 DEG C ~ 1580 DEG C, be incubated power-off after 8 ~ 10 hours, naturally cooling, then calcining matter ground to form the Rare-earth Long Persistence Luminescent Phosphor powder about 1500 orders;
Described optical absorbing agent is the 1-ethyl-3-(2-sulfonic benzo methyl containing 0.5wt%) methanol solution of the chloro-miaow Evil carbon cyanine dye of-3 '-ethyl-5,6-bis-; 1-ethyl-3-(2-sulfonic benzo methyl)-3 '-ethyl-5,6-bis-chloro-miaow Evil carbon cyanine dye structural formula is as follows:
Described linear low density polyethylene: code name LLDPE density 0.92 ~ 0.93, melt index MI0.6 ~ 0.8;
Described nano zine oxide preferable particle size 30-80nm; The preferred 40-80nm of nano-aluminum hydroxide;
The molecular formula of triazine-425 is 2-(2 '-hydroxyl-4 '-Xin alkoxyl phenyl)-4,6-bis-(2 〞, 4 〞-3,5-dimethylphenyl)-1,3,5-s-triazine.
The bar-shaped calcium carbonate of described silane-modified lightweight, the bar-shaped calcium carbonate of lightweight of preferred γ-aminopropyl triethoxysilane modification, such as adopt modification with the following method: at 80 DEG C, be sprayed on the bar-shaped calcium carbonate of lightweight of 100 weight parts equably with γ-aminopropyl triethoxysilane 3 ~ 5 weight part of 1:1 dehydrated alcohol dilution, high-speed stirring 30 minutes.
The bar-shaped calcium carbonate of described lightweight, preferred diameter 0.5 ~ 3 μm, length 10 ~ 30 μm, such as adopt and prepare with the following method:
By 0.1m
3the MgCl of 0.1mol/L
26H
2o solution and 0.1m
3the NaOH solution reaction of 0.12mol/L is prepared into Mg (OH)
2gel, with deionized water wash Mg (OH)
2with the AgNO of 1N in gel to filtrate
3solution inspection is without white flocs unit.Then by Mg (OH)
2gel adds water and breaks into the slurry that weight concentration is 10%.Add the sodium-acetate of 0.068kg, then put into the 1m that condenser is housed
3enamel reaction still in, reflux 5 hours, obtains needle-like Mg (OH)
2.
By needle-like Mg (OH)
2by deionized water filtration, washes clean.Then by needle-like Mg (OH)
2break into deionized water the slurry that weight concentration is 5%, passing into containing volumetric concentration is 20%CO
2gas carbonization, carbonization obtains needle-like MgCO when pH is 7.1
3, with sem observation needle-like MgCO
3length is 3 μm, and length-to-diameter ratio is 10:1.By needle-like MgCO
3slurries filtration obtains solid content 45.0% needle-like MgCO
3filter cake 17.3kg.
By above-mentioned needle-like MgCO
3filter cake 13kg joins the Ca (OH) that 3 tons of weight concentrations are 10%
2in slurry, passing into containing volumetric concentration is 26%CO
2gas carbonization, temperature during carbonization is 32 DEG C, when carbonization is 6.9 to pH, carbonization terminates, add 0.5 kilogram of sodium carbonate again, insulation is stirred 3 hours at 50 DEG C, bar-shaped fine particle calcium carbonate slurries filtration is obtained the bar-shaped fine particle calcium carbonate filter cake 0.57 ton of solid content about 60%, adopt reduction vaporization dry, then grinding obtains the bar-shaped calcium carbonate that mean length is 30 μm.
The present invention also provides a kind of preparation method of above-mentioned noctilucent stone paper, comprises the steps:
Graft modification Rare-earth Long Persistence Luminescent Phosphor powder is joined in linear low density polyethylene, then adds chlorinatedpolyethylene and the bar-shaped calcium carbonate of silane-modified lightweight, high-speed mixing 30 minutes at 140 DEG C; Add 2 again, 5-dimethyl-2,5-bis(t-butylperoxy) hexane, nano-aluminum hydroxide, three (2-chloroethyl) phosphoric acid ester, dioctyl phthalate (DOP), nano zine oxide, triazine-425, p-octylphenyl salicylate, sorbitan monostearate continue high-speed mixing 30 minutes, then 165 ~ 175 DEG C of Plasticator plasticizings are sent into, 160 ~ 175 DEG C of forcing machine curtain coatings, 165 ~ 175 DEG C of four axle rolling press is rolled into the noctilucent stone paper of about 0.1mm, after cooling, again through 25 DEG C, rolling packaging after relative humidity 60% left-right balance.
Noctilucent stone paper take high molecular polymer as substrate material, carry out composite modified to calcium carbonate, and add graft modification Rare-earth Long Persistence Luminescent Phosphor powder and other additives, utilize the macromolecule interfacial principles of chemistry and macromolecule modified feature, after special process process, adopt that mixed with polymers, filler are composite modified, polymkeric substance and filler plastify, extrude curtain coating, calendering formation technique makes noctilucent stone paper.Noctilucent stone paper can be applicable to road sign, the lines that road traffic is built; The deinsectization of agroforestry is can be used for after landscape design, luminescent paper coated with adhesive; Boundary of natural disaster hazardous location etc.
Embodiment
Embodiment 1
One, noctilucent stone paper component:
The linear low density polyethylene 15 parts of graft modification Rare-earth Long Persistence Luminescent Phosphor powder 5 parts, melt index MI0.6, chlorinatedpolyethylene 10 parts, 65 parts, the bar-shaped calcium carbonate of silane-modified lightweight, 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane 0.2 part, nano-aluminum hydroxide 1 part, three (2-chloroethyl) phosphoesterase 30 .5 part, dioctyl phthalate (DOP) 3, nano zine oxide 0.4 part, triazine-4250.1 parts, p-octylphenyl salicylate 0.1 part, sorbitan monostearate 1.5 parts.
Two, noctilucent stone paper preparation technology is divided into following steps:
Join in linear low density polyethylene by graft modification Rare-earth Long Persistence Luminescent Phosphor powder, reenter and add chlorinatedpolyethylene, the bar-shaped calcium carbonate of silane-modified lightweight high-speed mixing 30 minutes at 140 DEG C, add nano-aluminum hydroxide, three (2-chloroethyl) phosphoric acid ester, dioctyl phthalate (DOP), nano zine oxide, 2, 5-dimethyl-2, 5-bis(t-butylperoxy) hexane, triazine-425, p-octylphenyl salicylate, sorbitan monostearate continues high-speed mixing 30 minutes, then 165 DEG C of Plasticator plasticizings are sent into, 175 DEG C of forcing machine curtain coatings, 165 DEG C of four axle rolling press is rolled into the stone paper of about 0.1mm, after cooling, again through 25 DEG C, rolling packaging after relative humidity 60% left-right balance.
Three, the RE luminous powder, preparation method thereof of graft modification:
A. 300 object powders are ground to form by after Strontium carbonate powder 4 parts, aluminium sesquioxide 4 parts, europiumsesquioxide 0.1 part, Dysprosium trioxide 0.6 part, boric acid 0.4 part fully mixing, then electric furnace is put into, roasting after powder-compacting is compressed, per minute heats up about 10 DEG C, rise to 1520 DEG C, be incubated power-off after 10 hours, naturally cooling, then calcining matter ground to form the luminescent powder about 1500 orders;
B. by the luminescent powder of a process at 80 DEG C, be sprayed in luminescent powder by the monoalkoxy lipid acid titanic acid ester 0.03 part of 1:1 Witco 70 dilution, 30 minutes are stirred with homogenizer, spray into by vinyl acetate and peroxidation neodecanoic acid-1 again, 1-dimethyl-3-hydroxybutyl ester presses the functional monomer 0.5 part of 1:0.01 weight ratio mixing, continue homogenizer and stir 30 minutes, finally add optical absorbing agent 1 part, fully mix.
Four, the bar-shaped calcium carbonate preparation method of silane-modified lightweight: at 80 DEG C, is sprayed at equably on 100 parts of bar-shaped calcium carbonate of lightweight with the γ-aminopropyl triethoxysilane 3 parts of 1:1 Witco 70 dilution, stirs 30 minutes with homogenizer.
The bar-shaped calcium carbonate of lightweight can be prepared as follows: by 0.1m
3the MgCl of 0.1mol/L
26H
2o solution and 0.1m
3the NaOH solution reaction of 0.12mol/L is prepared into Mg (OH)
2gel, with deionized water wash Mg (OH)
2with the AgNO of 1N in gel to filtrate
3solution inspection is without white flocs unit.Then by Mg (OH)
2gel adds water and breaks into the slurry that weight concentration is 10%.Add the sodium-acetate of 0.068kg, then put into the 1m that condenser is housed
3enamel reaction still in, reflux 5 hours, obtains needle-like Mg (OH)
2.
By needle-like Mg (OH)
2by deionized water filtration, washes clean.Then by needle-like Mg (OH)
2break into deionized water the slurry that weight concentration is 5%, passing into containing volumetric concentration is 20%CO
2gas carbonization, carbonization obtains needle-like MgCO when pH is 7.1
3, with sem observation needle-like MgCO
3length is 3 μm, and length-to-diameter ratio is 10:1.By needle-like MgCO
3slurries filtration obtains solid content 45.0% needle-like MgCO
3filter cake 17.3kg.
By above-mentioned needle-like MgCO
3filter cake 13kg joins the Ca (OH) that 3 tons of weight concentrations are 10%
2in slurry, passing into containing volumetric concentration is 26%CO
2gas carbonization, temperature during carbonization is 32 DEG C, when carbonization is 6.9 to pH, carbonization terminates, add 0.5 kilogram of sodium carbonate again, insulation is stirred 3 hours at 50 DEG C, bar-shaped fine particle calcium carbonate slurries filtration is obtained the bar-shaped fine particle calcium carbonate filter cake 0.57 ton of solid content about 60.%, adopt reduction vaporization dry, then grinding obtains the bar-shaped calcium carbonate that mean length is 30 μm.
Embodiment 2
One, noctilucent stone paper component:
Graft modification Rare-earth Long Persistence Luminescent Phosphor powder 7.5 parts, linear low density polyethylene 17.5 parts, melt index MI0.7, chlorinatedpolyethylene 7.5 parts, 72 parts, the bar-shaped calcium carbonate of silane-modified lightweight, 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane 0.3 part, nano-aluminum hydroxide 2 parts, three (2-chloroethyl) phosphoric acid ester 1 part, dioctyl phthalate (DOP) 4.5 parts, nano zine oxide 0.5 part, triazine-4250.2 parts, p-octylphenyl salicylate 0.3 part, sorbitan monostearate 0.5 part.
Two, noctilucent stone paper preparation technology is divided into following steps:
Graft modification Rare-earth Long Persistence Luminescent Phosphor powder is joined in linear low density polyethylene, add chlorinatedpolyethylene again, the bar-shaped calcium carbonate of silane-modified lightweight high-speed mixing 30 minutes at 140 DEG C, add nano-aluminum hydroxide, three (2-chloroethyl) phosphoric acid ester, dioctyl phthalate (DOP), nano zine oxide, 2, 5-dimethyl-2, 5-bis(t-butylperoxy) hexane, triazine-425, p-octylphenyl salicylate, sorbitan monostearate continues high-speed mixing 30 minutes, then 175 DEG C of Plasticator plasticizings are sent into, 170 DEG C of forcing machine curtain coatings, 165 DEG C of four axle rolling press is rolled into the stone paper of about 0.1mm, after cooling, again through 25 DEG C, rolling packaging after relative humidity 60% left-right balance.
Three, the RE luminous powder, preparation method thereof of graft modification:
A. 300 object powders are ground to form by after Strontium carbonate powder 6 parts, aluminium sesquioxide 2 parts, europiumsesquioxide 0.3 part, Dysprosium trioxide 0.2 part, boric acid 0.8 part fully mixing, then electric furnace is put into, roasting after powder-compacting is compressed, per minute heats up about 10 DEG C, rise to 1580 DEG C, be incubated power-off after 8 hours, naturally cooling, then calcining matter ground to form the luminescent powder about 1500 orders;
B. by the luminescent powder of a process at 80 DEG C, be sprayed in luminescent powder by the monoalkoxy lipid acid titanic acid ester 0.05 part of 1:1 Witco 70 dilution, 30 minutes are stirred with homogenizer, spray into by vinyl acetate and peroxidation neodecanoic acid-1 again, 1-dimethyl-3-hydroxybutyl ester presses the functional monomer 0.3 part of 1:0.01 weight ratio mixing, continue homogenizer and stir 30 minutes, finally add optical absorbing agent 3 parts, fully mix.
Four, the bar-shaped calcium carbonate preparation method of silane-modified lightweight: at 80 DEG C, is sprayed at equably on the bar-shaped calcium carbonate of lightweight of 100 parts with the γ-aminopropyl triethoxysilane 4 parts of 1:1 Witco 70 dilution, stirs 30 minutes with homogenizer.
Preparation method is identical with embodiment 1 for lightweight bar-shaped calcium carbonate.
Embodiment 3
One, noctilucent stone paper component:
Graft modification Rare-earth Long Persistence Luminescent Phosphor powder 10 parts, linear low density polyethylene 20 parts, melt index MI0.8, chlorinatedpolyethylene 10 parts, 80 parts, the bar-shaped calcium carbonate of silane-modified lightweight, 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane 0.4 part, nano-aluminum hydroxide 3 parts, three (2-chloroethyl) phosphoric acid ester 1.5 parts, dioctyl phthalate (DOP) 6 parts, nano zine oxide 0.6 part, triazine-4250.3 parts, Tyox B 0.3 part, p-octylphenyl salicylate 0.3 part, sorbitan monostearate 1.5 parts.
Two, noctilucent stone paper preparation technology is divided into following steps:
Graft modification Rare-earth Long Persistence Luminescent Phosphor powder is joined in linear low density polyethylene, add chlorinatedpolyethylene again, the bar-shaped calcium carbonate of silane-modified lightweight high-speed mixing 30 minutes at 140 DEG C, add nano-aluminum hydroxide, three (2-chloroethyl) phosphoric acid ester, dioctyl phthalate (DOP), nano zine oxide, 2, 5-dimethyl-2, 5-bis(t-butylperoxy) hexane, triazine-425, p-octylphenyl salicylate, sorbitan monostearate continues high-speed mixing 30 minutes, then 170 DEG C of Plasticator plasticizings are sent into, 170 DEG C of forcing machine curtain coatings, 170 DEG C of four axle rolling press is rolled into the stone paper of about 0.1mm, after cooling, again through 25 DEG C, rolling packaging after relative humidity 60% left-right balance.
Prepared by three, graft modification Rare-earth Long Persistence Luminescent Phosphor powder:
A. 300 object powders are ground to form by after Strontium carbonate powder 5 parts, aluminium sesquioxide 3 parts, europiumsesquioxide 2 parts, Dysprosium trioxide 0.4 part, boric acid 0.6 part fully mixing, then electric furnace is put into, roasting after powder-compacting is compressed, per minute heats up about 10 DEG C, rise to 1550 DEG C, be incubated power-off after 9 hours, naturally cooling, then calcining matter ground to form the luminescent powder about 1500 orders;
B. by the luminescent powder of a process at 80 DEG C, be sprayed in luminescent powder by the monoalkoxy lipid acid titanic acid ester 0.04 part of 1:1 Witco 70 dilution, 30 minutes are stirred with homogenizer, spray into by vinyl acetate and peroxidation neodecanoic acid-1 again, 1-dimethyl-3-hydroxybutyl ester presses the functional monomer 0.4 part of 1:0.01 weight ratio mixing, continue homogenizer and stir 30 minutes, finally add optical absorbing agent 2 parts, fully mix
Four, the bar-shaped calcium carbonate preparation method of silane-modified lightweight: at 80 DEG C, is sprayed at equably on the bar-shaped calcium carbonate of lightweight of 100 parts with the γ-aminopropyl triethoxysilane 5 parts of 1:1 Witco 70 dilution, stirs 30 minutes with homogenizer.
Preparation method is identical with embodiment 1 for lightweight bar-shaped calcium carbonate.
Comparative example 4
The rare earth material luminescent powder of Chinese patent CN200310107697.4 invention is adopted to prepare noctilucent stone paper:
One, noctilucent stone paper component:
Rare earth material luminescent powder 10 parts, linear low density polyethylene 20 parts, melt index MI0.8, chlorinatedpolyethylene 10 parts, 80 parts, the bar-shaped calcium carbonate of silane-modified lightweight, 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane 0.4 part, nano-aluminum hydroxide 3 parts, three (2-chloroethyl) phosphoric acid ester 1.5 parts, dioctyl phthalate (DOP) 6 parts, nano zine oxide 0.6 part, triazine-4250.3 parts, Tyox B 0.3 part, p-octylphenyl salicylate 0.3 part, sorbitan monostearate 1.5 parts.
Two, noctilucent stone paper preparation technology is divided into following steps:
Rare earth material luminescent powder joins in linear low density polyethylene, add chlorinatedpolyethylene again, the bar-shaped calcium carbonate of silane-modified lightweight high-speed mixing 30 minutes at 140 DEG C, add nano-aluminum hydroxide, three (2-chloroethyl) phosphoric acid ester, dioctyl phthalate (DOP), nano zine oxide, 2, 5-dimethyl-2, 5-bis(t-butylperoxy) hexane, triazine-425, p-octylphenyl salicylate, sorbitan monostearate continues high-speed mixing 30 minutes, then 170 DEG C of Plasticator plasticizings are sent into, 170 DEG C of forcing machine curtain coatings, 170 DEG C of four axle rolling press is rolled into the stone paper of about 0.1mm, after cooling, again through 25 DEG C, rolling packaging after relative humidity 60% left-right balance.
Three, the bar-shaped calcium carbonate preparation method of silane-modified lightweight: at 80 DEG C, is sprayed at equably on the bar-shaped calcium carbonate of lightweight of 100 parts with the γ-aminopropyl triethoxysilane 5 parts of 1:1 Witco 70 dilution, stirs 30 minutes with homogenizer.
Preparation method is identical with embodiment 1 for lightweight bar-shaped calcium carbonate.
Testing method: adopt the method for Chinese patent CN1616595A to detect stone luminescent paper luminescent properties, the method with reference to national sector standard QB/T3805-1999 " polyvinyl chloride wallpaper " detects other performances of paper.
Table one
Measure can judge from practical application: noctilucent stone paper of the present invention reaches the effect of invention, is a kind of novel environmentfriendly products.