CN103343486B - Preparation method of paper with magnetic characteristic and luminescent characteristic - Google Patents
Preparation method of paper with magnetic characteristic and luminescent characteristic Download PDFInfo
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- CN103343486B CN103343486B CN201310251081.8A CN201310251081A CN103343486B CN 103343486 B CN103343486 B CN 103343486B CN 201310251081 A CN201310251081 A CN 201310251081A CN 103343486 B CN103343486 B CN 103343486B
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Abstract
The invention discloses a preparation method of paper with magnetic characteristic and luminescent characteristic. Specific papers with magnetic characteristic and luminescent characteristic are produced through combining luminous inorganic strong magnetic characteristic material with common paper pulp. The prepared paper has not only a series of advantages of non-electric conductivity, high temperature resistance, excellent chemical performance and aging resistance of an inorganic material but also excellent mechanical property and less possibility of combustion; the thickness of the paper is reduced by 20-30% than the thickness of common paper under the same mechanical property; the prepared paper also has special characteristics of strong paramagnetism and red glow. The paper prepared by utilizing the method has the magnetic characteristics such as magnetic response and magnetic recording so as to be used for high anti-counterfeiting special paper products such as register papers, wrapping papers and calligraphic papers which require special identification. The method does not need special equipment in a papermaking process and is simple to operate and easy for industrial production; the paper has permanent magnetism, is unlikely to be demagnetized, has strong hidden property and is unlikely to counterfeit.
Description
Technical field
The present invention relates to a kind of manufacture method of paper, particularly a kind of preparation method with magnetic characteristic and characteristics of luminescence paper.
Background technology
Along with the development of science and technology, various personation puppet slightly product emerges in an endless stream.The special paper products such as bill, the packing of product, calligraphy, drawing can be adulterator and bring huge profit, therefore do not stint and utilize the new technology at various tip (such as computer graphical processing software, color printing, high accuracy scanning, digital printing etc.) to copy, make original false proof being easy to lose its distinctive crypticity.Therefore, the efficient anti-counterfeiting technology of the various new special of developmental research is needed badly.CN1609919 discloses label paster and its preparation method and application in a kind of anti false film, comprise surface and be printed on the millimeter paper layer (2) of anti-counterfeiting mark layer (1), the adhesive film (3) be coated on anti-counterfeiting mark layer (1), this adhesive film (3) has embossing (4).Overcome the shortcoming of existing label paster, and there is antiforge function completely, label after shaping.But prepared paster non-refractory, intensity difference.CN101381975 provides a kind of vitreous fibre showing light-transmissive in paper, additionally provides the preparation method of this vitreous fibre and the paper products containing this vitreous fibre.Described vitreous fibre is the synthetic fiber obtained through dry spinning or wet spinning the raw material comprising following composition: polyvinyl alcohol: 75 ?97%, shitosan: 1 ?15%, carboxymethyl cellulose: 0.5 ?10%.Equally, prepared paper non-refractory, anti-counterfeit durable weak effect.
Magnetized paper is compared with other record forms, great advantage is: in the magnetosphere that vision loses, have record useful in a large number, has the disguise of height, and carry, use particularly convenient, feedback rapidly (one inserts in machine, just has display or action in short a few second).From secret angle, its Application Areas will have and expand more, and such as production management, communication, operation are sold, antitheft explosion-proof etc.At present, prepare magnetized paper magnetic material used to be mostly ferrite and to comprise Fe
3o
4(Yang Xin. fiber lumen loading prepares magnetized paper research [D]. Southern Yangtze University, 2008.; Lee's seabee. the preparation of magnetic paper by in-situ method and magnetic property research [D]. Southern Yangtze University, 2008.), γ ?Fe
2o
3(Tang Aimin, Zhang Hongwei, Chen Gang etc. the fabrication & properties [J] of magnetic nano composite fibre and magnetized paper. South China Science & Engineering University's journal (natural science edition), 2009,37 (3): 75 ?80.), Mn
1 ?xzn
xfe
2o
4(in just, section jewel, Lv Jian. Cell Inner Filling prepares magnetized paper fiber [J]. Shanghai papermaking, 2008,39 (1): 32 ?35.) etc.And Ferrite Material resistance is less, not acid and alkali-resistance, can not printing opacity, and the Paper White Degree of preparation is relatively low, in printing etc., have certain restriction.CN102587215A discloses a kind of preparation method with magnetic characteristic paper, specifically the magnetic inorganic material of filling agent and the obtained paper with magnetic characteristic in the lumen of paper pulp fiber.Paper prepared by the method only has magnetic security feature, and antiforge function is single.CN102587194A discloses a kind of preparation method of high-strength magnetized paper, by adding the high temperature resistant amorphous material of inorganic non-metallic in paper, has prepared the paper with magnetic characteristic.The prepared high temperature resistant amorphous material preparation technology of inorganic non-metallic is simple, and have optics isotropic, chemical stability is excellent, non-conductive, good mechanical performance, and magnetic is strong.Adopt artificial wire drawing, avoid the generation of inorfil crystallization devitrification phenomenon in drawing process.Although the prepared paper strength of this patent of invention is high, still there is the shortcoming that antifalsification is single.
At present, for the paper of some specific uses, as RMB paper using, this paper, under the optical excitation of specific wavelength, can send specific light, as sent redness, yellow-green light etc. after ultraviolet excitation, considerably increases the anti-counterfeiting power of RMB.But anti-fake luminous materials most used is at present luminous organic material, be printed on the surface of bank note during use by means of only the method for printing, its complicated process of preparation, with high costs.And there is about namely having magnetic characteristic the paper of the characteristics of luminescence, and good mechanical performance, non-conductive, high temperature resistant, ageing-resistant, the report of the paper that anti-counterfeiting power is large is less.CN2695469 discloses a kind of light accumulating luminous paper, the surface spraying of import high-grade pure blank sheet of paper with gum has the luminescent layer of overlength afterglow luminescent properties, described luminescent layer is made up of Crystal varnish, diluent, curing agent, light-accumulated luminous powder, divides and be sprayed on the surface of pure white paper for four times after these four kinds of raw materials mix by a certain percentage.Paper prepared by the method exists and wears no resistance, light-storing material and the shortcoming such as paper bond strength is low.CN2856114 discloses a kind of cheque paper with light-accumulated luminous function, and its cross section is layer structure, and this layer structure is made up of paper bottom, light-storing material layer, purpose reference lamina, adhered layer and protective clear layer successively.Paper prepared by the method exists and wears no resistance, light-storing material and paper bond strength low, the shortcomings such as antifalsification is single.CN201546123U discloses a kind of luminescent paper that can excite fast, soot layer (2) is had additional between hypothallus (1) and luminescent material coating (3), and the thickness of luminescent material coating (3) is less than the thickness of soot layer, adopt the luminescent paper of this structure, by improving the light emitting efficiency of luminescent paper, under the excitating performance of self-luminescent material does not have vicissitudinous condition, realize the effect excited fast.Paper prepared by the method exist wear no resistance, antifalsification is single, complicated process of preparation.CN102174784A discloses a kind of light storage luminous anti-fraud paper and manufacture method thereof and application.It evenly applies light-accumulated luminous ink wherein with mode of printing in common paper, and described light-storing paint is phosphorescent zinc sulphide ZnS:Cu.Paper prepared by the method exist wear no resistance, light-storing material and the shortcoming such as paper bond strength is low, the luminescent material life-span is short, security feature is single.
Summary of the invention
The object of the invention is to the shortcoming overcoming above-mentioned prior art, provide a kind of non-conductive, acid and alkali-resistance, light transmission is good, high temperature resistant, anti-aging, has the preparation method of good magnetic characteristic and characteristics of luminescence paper simultaneously.
For reaching above object, technical scheme of the present invention is:
Comprise the following steps:
The first step: the preparation of inorganic strong magnetic characteristic material that can be luminous and process
1) first, according to mass fraction meter, by the GeO2 of 12 ~ 20%, the Al2O3 of 18 ~ 25%, the B2O3 of 8 ~ 12%, the Tb4O7 of 35 ~ 40%, the Eu2O3 of 3 ~ 5%, the Dy2O3 of 0.1 ~ 2%, the ZnO of 2 ~ 3%, the Na2SiF6 of 3 ~ 5%, the CeO2 of 0.2 ~ 0.5%, put into agate breast body mortar ground and mixed after the ZrO2 weighing of 0.3 ~ 0.5%, form batch;
2), secondly, be incubated 1 ~ 2 hour under 1380 ~ 1410 DEG C of glass melting temperatures after, put into paddle continuation stirring and found, in whipping process, temperature remains at 1380 ~ 1410 DEG C, obtains liquation;
3) then, until step 2) stir terminate after, take out paddle, liquation is cooled to 1350 DEG C, obtains melt;
4), then, in the copper mould poured into by melt, after melt solidification, make test rod, the annealing furnace after die sinking, test rod being put into 650 DEG C is cooled to room temperature;
5) then, the test rod obtained is put into wire drawing machine, heat and be drawn into the fiber that diameter is 20 ~ 30 μm, and at fiber surface coating softening sizing agent;
6) last, after the fiber being coated with softening sizing agent is dried moisture, cutting into length is 2 ~ 5mm fiber, namely prepare can be luminous inorganic strong magnetic characteristic material;
Second step: the preparation with magnetic characteristic and characteristics of luminescence paper
1) first, according to mass fraction meter, get inorganic strong magnetic characteristic material, 0.6% ~ 1.5% retention and drainage aid agent that the leaf wood oven dry stock of 1% ~ 3%, 5% ~ 10% can be luminous, surplus is distilled water;
Leaf wood oven dry stock is added in distilled water, uniform stirring, obtain stirring liquid A;
2) secondly, in stirring liquid A, add inorganic strong magnetic characteristic material that can be luminous, carry out uniform stirring, obtain stirring liquid B;
3) then, then add retention and drainage aid agent in stirring liquid B, carry out uniform stirring, obtain stirring liquid C;
4) then, stirring liquid B is moved to handsheet on handsheet machine, makes the scraps of paper of 0.1 ~ 0.3mm;
5) last, after the scraps of paper are dried, naturally cool and obtain there is magnetic characteristic and characteristics of luminescence paper.
After step 3) takes out paddle in the described first step, with the cooldown rate of 10 DEG C/min, liquation is cooled to 1350 DEG C.
The diameter of the test rod of described circle is 5mm.
In described second step, step 1) uniform stirring is stir in the mixer of 500 ~ 1000 turns/min.
Step 2 in second step) uniform stirring is for stir in 400 ~ 600 turns/min mixer.
In second step, step 3) uniform stirring for stir in 800 ~ 1500 turns/min mixer.
The described scraps of paper are formed after adopting the pressure of 4 ~ 6MPa squeezing 3 ~ 15min.
The scraps of paper are carried out dry, the dry baking oven for the scraps of paper being put into 105 ~ 110 DEG C is dry.
Described retention and drainage aid agent is one or more in CPAM, PEI, PEO.
Described softening sizing agent is by paraffin: vaseline: stearic acid: after the mass ratio weighing of water=1:1:1:30, after first paraffin, vaseline and stearic acid being melted, then add water, mix rear configuration and form.
Beneficial effect of the present invention is:
The present invention, by the compound of inorganic strong magnetic characteristic material that can be luminous and common paper pulp, has prepared the specialties simultaneously with magnetic characteristic and the characteristics of luminescence.Prepared paper not only has the series of advantages such as inorganic material is non-conductive, and heatproof is high, and chemical property is excellent, anti-aging, and prepared paper good mechanical performance, and inorganic fibers is combined firmly with paper fiber, nonflammable; Under identical mechanical property, the paper sheet thickness minimizing 20 ~ 30% that Thickness Ratio is common.Meanwhile, the property that prepared paper also shows strong paramagnetism and glows.The paper obtained according to preparation method of the present invention, because having the magnetic characteristic such as magnetic response, magnetic recording, can be used for check paper, wrapping paper, calligraphic paper etc. and needs the bright speciality paper goods of special identity card.The present invention does not need special equipment in paper preparation process, simple to operate, is easy to suitability for industrialized production; And magnetic is permanent, not easily demagnetization, disguised strong, not easily copied.
Accompanying drawing explanation
Fig. 1 is the luminescent spectrum figure with magnetic characteristic and characteristics of luminescence paper prepared by embodiment 1, and wherein abscissa is wavelength of transmitted light, and ordinate is emitted luminescence intensity;
Fig. 2 is the hysteresis curve with magnetic characteristic and characteristics of luminescence paper prepared by embodiment 1, and wherein abscissa is magnetic field intensity, and ordinate is the intensity of magnetization;
Fig. 3 be embodiment 1 prepare there is magnetic characteristic and characteristics of luminescence paper photo under a scanning electron microscope.
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention is described in detail.
Embodiment 1:
The first step: the preparation of inorganic strong magnetic characteristic material that can be luminous and process
1) first, according to mass fraction meter, by the GeO of 19%
2, the Al of 20%
2o
3, the B of 10%
2o
3, the Tb of 38%
4o
7, the Eu of 4%
2o
3, the Dy of 1%
2o
3, the ZnO of 3%, the Na of 4%
2siF
6, the CeO of 0.5%
2, the ZrO of 0.5%
2put into after agate breast body mortar ground and mixed is greater than 98% to the uniformity after weighing, form batch;
2) secondly, at 1410 DEG C, batch is added in platinum crucible, and be incubated 1 hour under 1410 DEG C of glass melting temperatures after, put into paddle continuation stirring and found 3 hours, in whipping process, temperature remains at 1410 DEG C;
3) then, after end to be mixed, take out paddle, with the cooldown rate of 10 DEG C/min, liquation is cooled to 1350 DEG C, and at 1350 DEG C of insulation 30min, obtain melt;
4) then, the melt founded is poured in the copper mould of 600 DEG C, after melt solidification, make the test rod that diameter is 5mm, after die sinking, test rod is put into the annealing furnace of 650 DEG C, after insulation 2h, cool to room temperature with the furnace;
5) then, the test rod obtained is put into wire drawing machine, be heated to 1350 DEG C, and test rod is drawn into the fiber that diameter is 20 ~ 30 μm, and at fiber surface coating softening sizing agent;
6) last, the fiber being coated with softening sizing agent is put into the baking oven of 110 DEG C, insulation 2h, after drying moisture, cutting into length is 2 ~ 5mm fiber, namely prepare can be luminous inorganic strong magnetic characteristic material;
Second step: the preparation with magnetic characteristic and characteristics of luminescence paper
1) first, get 5g over dry hardwood pulp, add in 500ml distilled water, in the mixer of 1000 turns/min, carry out stirring 50min, obtain stirring liquid A;
2) secondly, to obtain stirring in liquid A add that 10g produced can be luminous inorganic strong magnetic characteristic material, then stir 50min with 600 turns/min, obtain stirring liquid B;
3) then, then 1.5g retention and drainage aid agent CPAM(cationicpolyacrylamides is added, cationic polyacrylamide to obtaining stirring in liquid B), continue to stir 80min with 1500 turns/min, obtain stirring liquid C;
4) then, the stirring liquid C obtained is moved to handsheet on handsheet machine, after adopting the pressure squeezing 15min of 6MPa, form the scraps of paper of 0.1mm;
5) last, the scraps of paper are put into the baking oven of 105 DEG C, after dry 30min, naturally cool and obtain there is magnetic characteristic and characteristics of luminescence paper.
See accompanying drawing 1, have magnetic characteristic and the photoluminescence spectra of characteristics of luminescence paper under excitation wavelength is 378nm prepared by being, wherein abscissa is wavelength of transmitted light, and ordinate is emitted luminescence intensity.As seen from Figure 1, prepared paper, the strongest wavelength of transmitted light is 617.4nm, and intensity is close to 1200 units, and very weak at 580.2nm, 593.2nm, 656.2nm, 705.4nm place emitted luminescence intensity.
See accompanying drawing 2, have prepared by being magnetic characteristic and characteristics of luminescence paper ?hysteresis curve within the scope of 2000 ~ 3000Oe, as can be seen from the figure, prepared paper has certain paramagnetism.
See accompanying drawing 3, be prepared have magnetic characteristic and characteristics of luminescence paper 1K doubly under SEM photo, in as can be seen from the figure prepared paper, inorfil is combined closely with paper fibre, and presents and be uniformly distributed.
Embodiment 2:
The first step: the preparation of inorganic strong magnetic characteristic material that can be luminous and process
1) first, according to mass fraction meter, by the GeO of 14.5%
2, the Al of 25%
2o
3, the B of 11%
2o
3, the Tb of 37%
4o
7, the Eu of 3%
2o
3, the Dy of 2%
2o
3, the ZnO of 2%, the Na of 5%
2siF
6, the CeO of 0.2%
2, the ZrO of 0.3%
2put into after agate breast body ground and mixed is greater than 98% to the uniformity after weighing, form batch;
2) secondly, at 1410 DEG C, batch is added in platinum crucible, and be incubated 2 hours under 1410 DEG C of glass melting temperatures after, put into paddle continuation stirring and found 2 hours, in whipping process, temperature remains at 1410 DEG C;
3) then, after end to be mixed, take out paddle, with the cooldown rate of 10 DEG C/min, liquation is cooled to 1350 DEG C, and at 1350 DEG C of insulation 30min, obtain melt;
4) then, poured into by the melt founded in the copper mould of 600 DEG C, make the test rod that diameter is 10mm, after melt solidification, test rod is put into the annealing furnace of 650 DEG C by die sinking, cools to room temperature with the furnace after insulation 2h;
5) then, the test rod obtained is put into wire drawing machine, be heated to 1350 DEG C, and test rod is drawn into the fiber that diameter is 30 μm, and in time at fiber surface coating softening sizing agent;
6) last, the fiber being coated with softening sizing agent is put into the baking oven of 110 DEG C, insulation 2h, after drying moisture, cutting into length is 2 ~ 5mm, namely prepare can be luminous inorganic strong magnetic characteristic material;
Second step: the preparation with magnetic characteristic and characteristics of luminescence paper
1) first, get 4g over dry hardwood pulp, add in 400ml distilled water, in the mixer of 700 revs/min, carry out stirring 40min, obtain stirring liquid A;
2) secondly, to obtain stirring in liquid A add that 8g produced can be luminous inorganic strong magnetic characteristic fiber, then stir 40min with 500 turns/min, obtain stirring liquid B;
3) then, then 1.2g retention and drainage aid agent PEI(Polyetherimide is added, PEI in stirring liquid B), continue to stir 60min with 1000 turns/min, obtain stirring liquid C;
4) then, the stirring liquid C after stirring is moved to handsheet on handsheet machine, after adopting the pressure squeezing 11min of 5MPa, form the scraps of paper of 0.2mm;
5) last, the scraps of paper are put into the baking oven of 110 DEG C, after dry 20min, naturally cool and obtain there is magnetic characteristic and characteristics of luminescence paper.
Embodiment 3:
The first step: the preparation of inorganic strong magnetic characteristic material that can be luminous and process
1) first, according to mass fraction meter, by the GeO of 16%
2, the Al of 24%
2o
3, the B of 9.5%
2o
3, the Tb of 36%
4o
7, the Eu of 5%
2o
3, the Dy of 2%
2o
3, the ZnO of 2%, the Na of 5%
2siF
6, the CeO of 0.3%
2, the ZrO of 0.2%
2put into after agate breast body ground and mixed is greater than 98% to the uniformity after weighing, form batch;
2) secondly, at 1400 DEG C, batch is added in platinum crucible, and be incubated 2 hours under 1400 DEG C of glass melting temperatures after, put into paddle continuation stirring and found 2 hours, in whipping process, temperature remains at 1400 DEG C;
3) then, after end to be mixed, take out paddle, with the cooldown rate of 10 DEG C/min, liquation is cooled to 1350 DEG C, and at 1350 DEG C of insulation 30min, obtain melt;
4) then, poured into by the melt founded in the copper mould of 600 DEG C, make the test rod that diameter is 5mm, after melt solidification, test rod is put into the annealing furnace of 650 DEG C by die sinking, cools to room temperature with the furnace after insulation 2h;
5) then, the test rod obtained is put into wire drawing machine, be heated to 1350 DEG C, and test rod is drawn into the fiber that diameter is 20 ~ 30 μm, and in time at fiber surface coating softening sizing agent;
6) last, the fiber being coated with softening sizing agent is put into the baking oven of 110 DEG C, insulation 2h, after drying moisture, cutting into length is 2 ~ 5mm fiber, namely prepare can be luminous inorganic strong magnetic characteristic material;
Second step: the preparation with magnetic characteristic and characteristics of luminescence paper
1) first, get 3g over dry hardwood pulp, add in 300ml distilled water, in the mixer of 600 turns/min, carry out stirring 50min, obtain stirring liquid A;
2) secondly, to stir in liquid A add that 6g produced can be luminous inorganic strong magnetic characteristic fiber, then stir 20min with 600 turns/min, obtain stirring liquid B;
3) then, then 0.9g retention and drainage aid agent PEO(polyethylene glycol oxide is added in stirring liquid B), continue to stir 80min with 900 turns/min, obtain stirring liquid C;
4) then, the stirring liquid C after stirring is moved to handsheet on handsheet machine, after adopting the pressure squeezing 15min of 4MPa, form the scraps of paper of 0.1mm;
5) last, the scraps of paper are put into the baking oven of 105 DEG C, after dry 30min, naturally cool and obtain there is magnetic characteristic and characteristics of luminescence paper.
Embodiment 4:
The first step: the preparation of inorganic strong magnetic characteristic material that can be luminous and process
1) first, according to mass fraction meter, by the GeO of 17.4%
2, the Al of 19%
2o
3, the B of 12%
2o
3, the Tb of 40%
4o
7, the Eu of 3%
2o
3, the Dy of 1%
2o
3, the ZnO of 3%, the Na of 4%
2siF
6, the CeO of 0.3%
2, the ZrO of 0.3%
2put into after agate breast body ground and mixed is greater than 98% to the uniformity after weighing, form batch;
2) secondly, at 1380 DEG C, batch is added in platinum crucible, and be incubated 2 hours under 1380 DEG C of glass melting temperatures after, put into paddle continuation stirring and found 3 hours, in whipping process, temperature remains at 1380 DEG C;
3) then, after end to be mixed, take out paddle, with the cooldown rate of 10 DEG C/min, liquation is cooled to 1350 DEG C, and at 1350 DEG C of insulation 30min, obtain melt;
4) then, poured into by the melt founded in the copper mould of 600 DEG C, make the test rod that diameter is 5mm, after melt solidification, test rod is put into the annealing furnace of 650 DEG C by die sinking, cools to room temperature with the furnace after insulation 2h;
5) then, the test rod obtained is put into wire drawing machine, be heated to 1350 DEG C, and test rod is drawn into the fiber that diameter is 20 ~ 30 μm, and in time at sample fiber surface coating softening sizing agent;
6) last, the fiber being coated with softening sizing agent is put into the baking oven of 110 DEG C, insulation 2h, after drying moisture, cutting into length is 2 ~ 5mm fiber, namely prepare can be luminous inorganic strong magnetic characteristic material;
Second step: the preparation with magnetic characteristic and characteristics of luminescence paper
1) first, get 5g over dry hardwood pulp, add in 500ml distilled water, in the mixer of 1000 turns/min, carry out stirring 50min, obtain stirring liquid A;
2) secondly, to stir in liquid add that 10g produced can be luminous inorganic strong magnetic characteristic material, then stir 20min with 600 turns/min, obtain stirring liquid B;
3) then, then add 0.6g retention and drainage aid agent CPAM and PEI in stirring liquid B, continue to stir 80min with 8000 turns/min, obtain stirring liquid C;
4) then, the stirring liquid C after stirring is moved to handsheet on handsheet machine, after adopting the pressure squeezing 3min of 6MPa, form the scraps of paper of 0.1mm;
5) last, the scraps of paper are put into the baking oven of 110 DEG C, after dry 10min, naturally cool and obtain there is magnetic characteristic and characteristics of luminescence paper.
Embodiment 5:
The first step: the preparation of inorganic strong magnetic characteristic material that can be luminous and process
1) first, according to mass fraction meter, by the GeO of 18.5%
2, the Al of 20%
2o
3, the B of 11%
2o
3, the Tb of 39%
4o
7, the Eu of 4%
2o
3, the Dy of 2%
2o
3, the ZnO of 2%, the Na of 3%
2siF
6, the CeO of 0.2%
2, the ZrO of 0.3%
2put into after agate breast body ground and mixed is greater than 98% to the uniformity after weighing, form batch;
2) secondly, at 1390 DEG C, batch is added in platinum crucible, and be incubated 2 hours under 1390 DEG C of glass melting temperatures after, put into paddle continuation stirring and found 3 hours, in whipping process, temperature remains at 1390 DEG C;
3) then, after end to be mixed, take out paddle, with the cooldown rate of 10 DEG C/min, liquation is cooled to 1350 DEG C, and at 1350 DEG C of insulation 30min, obtain melt;
4) then, poured into by the melt founded in the copper mould of 600 DEG C, make the test rod that diameter is 5mm, after melt solidification, test rod is put into the annealing furnace of 650 DEG C by die sinking, cools to room temperature with the furnace after insulation 2h;
5) then, the test rod obtained is put into wire drawing machine, be heated to 1350 DEG C, and sample is drawn into the fiber that diameter is 20 ~ 30 μm, and in time at fiber surface coating softening sizing agent;
6) last, the fiber being coated with softening sizing agent is put into the baking oven of 110 DEG C, insulation 2h, after drying moisture, cutting into length is 2 ~ 5mm fiber, namely prepare can be luminous inorganic strong magnetic characteristic material;
Second step: the preparation with magnetic characteristic and characteristics of luminescence paper
1) first, get 4g over dry hardwood pulp, add in 400ml distilled water, in the mixer of 700 revs/min, carry out stirring 40min, obtain stirring liquid A;
2) secondly, to stir in liquid A add that 7g produced can be luminous inorganic strong magnetic characteristic fiber, then stir 30min with 500 revs/min, obtain stirring liquid B;
3) then, then add 1.0g retention and drainage aid agent CPAM, PEI and PEO in stirring liquid B, continue to stir 50min with 1100 turns/min, obtain stirring liquid C;
4) then, the stirring liquid C after stirring is moved to handsheet on handsheet machine, after adopting the pressure squeezing 10min of 5MPa, form the scraps of paper of 0.2mm;
5) last, the scraps of paper are put into the baking oven of 105 DEG C, after dry 20min, naturally cool and obtain there is magnetic characteristic and characteristics of luminescence paper.
Embodiment 6:
The first step: the preparation of inorganic strong magnetic characteristic material that can be luminous and process
1) first, according to mass fraction meter, by the GeO of 15%
2, the Al of 19.3%
2o
3, the B of 11%
2o
3, the Tb of 40%
4o
7, the Eu of 5%
2o
3, the Dy of 2%
2o
3, the ZnO of 3%, the Na of 4%
2siF
6, the CeO of 0.3%
2, the ZrO of 0.4%
2put into after agate breast body ground and mixed is greater than 98% to the uniformity after weighing, form batch;
2) secondly, at 1400 DEG C, batch is added in platinum crucible, and be incubated 1 hour under 1400 DEG C of glass melting temperatures after, put into paddle continuation stirring and found 3 hours, in whipping process, temperature remains at 1400 DEG C;
3) then, after end to be mixed, take out paddle, with the cooldown rate of 10 DEG C/min, liquation is cooled to 1350 DEG C, and at 1350 DEG C of insulation 30min, obtain melt;
4) then, poured into by the melt founded in the copper mould of 600 DEG C, make the test rod that diameter is 5mm, after melt solidification, test rod is put into the annealing furnace of 650 DEG C by die sinking, cools to room temperature with the furnace after insulation 2h;
5) then, the test rod obtained is put into wire drawing machine, be heated to 1350 DEG C, and test rod is drawn into the fiber that diameter is 20 ~ 30 μm, and in time at fiber surface coating softening sizing agent;
6) last, the fiber being coated with softening sizing agent is put into the baking oven of 110 DEG C, insulation 1h, after drying moisture, cutting into length is 2 ~ 5mm fiber, namely prepare can be luminous inorganic strong magnetic characteristic material;
Second step: the preparation with magnetic characteristic and characteristics of luminescence paper
1) first, get 5g over dry hardwood pulp, add in 500ml distilled water, in the mixer of 1000 turns/min, carry out stirring 50min, obtain stirring liquid A;
2) secondly, to stir in liquid A add that 8g produced can be luminous inorganic strong magnetic characteristic material, then stir 40min with 500 turns/min, obtain stirring liquid B;
3) then, then add 1.4g retention and drainage aid agent PEI and PEO to stirring liquid B, continue to stir 70min with 1200 revs/min, obtain stirring liquid C;
4) then, the stirring liquid C after stirring is moved to handsheet on handsheet machine, after adopting the pressure squeezing 7min of 6MPa, form the scraps of paper of 0.15mm;
5) last, the scraps of paper are put into the baking oven of 105 DEG C, after dry 30min, naturally cool and obtain there is magnetic characteristic and characteristics of luminescence paper.
Embodiment 7:
The first step: the preparation of inorganic strong magnetic characteristic material that can be luminous and process
1) first, according to mass fraction meter, by the GeO of 12%
2, the Al of 18%
2o
3, the B of 8%
2o
3, the Tb of 35%
4o
7, the Eu of 4%
2o
3, the Dy of 0.1%
2o
3, the ZnO of 2.5%, the Na of 4%
2siF
6, the CeO of 0.4%
2, the ZrO of 0.3%
2put into after agate breast body ground and mixed is greater than 98% to the uniformity after weighing, form batch;
2) secondly, at 1380 DEG C, batch is added in platinum crucible, and be incubated 2 hours under 1380 DEG C of glass melting temperatures after, put into paddle continuation stirring and found 3 hours, in whipping process, temperature remains at 1380 DEG C;
3) then, after end to be mixed, take out paddle, with the cooldown rate of 10 DEG C/min, liquation is cooled to 1350 DEG C, and at 1350 DEG C of insulation 30min, obtain melt;
4) then, poured into by the melt founded in the copper mould of 600 DEG C, make the test rod that diameter is 5mm, after melt solidification, test rod is put into the annealing furnace of 650 DEG C by die sinking, cools to room temperature with the furnace after insulation 1h;
5) then, the test rod obtained is put into wire drawing machine, be heated to 1350 DEG C, and test rod is drawn into the fiber that diameter is 20 ~ 30 μm, and in time at sample fiber surface coating softening sizing agent;
6) last, the fiber being coated with softening sizing agent is put into the baking oven of 110 DEG C, insulation 1h, after drying moisture, cutting into length is 2 ~ 5mm fiber, namely prepare can be luminous inorganic strong magnetic characteristic material;
Second step: the preparation with magnetic characteristic and characteristics of luminescence paper
1) first, get 5g over dry hardwood pulp, add in 500ml distilled water, in the mixer of 1000 turns/min, carry out stirring 50min, obtain stirring liquid A;
2) secondly, to stir in liquid A add that 8g produced can be luminous inorganic strong magnetic characteristic material, then stir 40min with 500 turns/min, obtain stirring liquid B;
3) then, then add 1.4g retention and drainage aid agent CPAM and PEI in stirring liquid B, continue to stir 70min with 1200 revs/min, obtain stirring liquid C;
4) then, the stirring liquid C after stirring is moved to handsheet on handsheet machine, after adopting the pressure squeezing 7min of 6MPa, form the scraps of paper of 0.15mm;
5) last, the scraps of paper are put into the baking oven of 105 DEG C, after dry 30min, naturally cool and obtain there is magnetic characteristic and characteristics of luminescence paper.
Embodiment 8:
The first step: the preparation of inorganic strong magnetic characteristic material that can be luminous and process
1) first, according to mass fraction meter, by the GeO of 20%
2, the Al of 22%
2o
3, the B of 12%
2o
3, the Tb of 35%
4o
7, the Eu of 3%
2o
3, the Dy of 0.5%
2o
3, the ZnO of 2.5%, the Na of 5%
2siF
6, the CeO of 0.5%
2, the ZrO of 0.5%
2put into after agate breast body ground and mixed is greater than 98% to the uniformity after weighing, form batch;
2) secondly, at 1410 DEG C, batch is added in platinum crucible, and be incubated 1 hour under 1410 DEG C of glass melting temperatures after, put into paddle continuation stirring and found 2 hours, in whipping process, temperature remains at 1410 DEG C;
3) then, after end to be mixed, take out paddle, with the cooldown rate of 10 DEG C/min, liquation is cooled to 1350 DEG C, and at 1350 DEG C of insulation 30min, obtain melt;
4) then, poured into by the melt founded in the copper mould of 600 DEG C, make the test rod that diameter is 5mm, after melt solidification, test rod is put into the annealing furnace of 650 DEG C by die sinking, cools to room temperature with the furnace after insulation 2h;
5) then, the test rod obtained is put into wire drawing machine, be heated to 1350 DEG C, and test rod is drawn into the fiber that diameter is 20 ~ 30 μm, and in time at sample fiber surface coating softening sizing agent;
6) last, the fiber being coated with softening sizing agent is put into the baking oven of 110 DEG C, insulation 1h, after drying moisture, cutting into length is 2 ~ 5mm fiber, namely prepare can be luminous inorganic strong magnetic characteristic material;
Second step: the preparation with magnetic characteristic and characteristics of luminescence paper
1) first, get 5g over dry hardwood pulp, add in 500ml distilled water, in the mixer of 1000 turns/min, carry out stirring 50min, obtain stirring liquid A;
2) secondly, to stir in liquid A add that 8g produced can be luminous inorganic strong magnetic characteristic material, then stir 40min with 500 turns/min, obtain stirring liquid B;
3) then, then add 1.4g retention and drainage aid agent CPAM in stirring liquid B, continue to stir 70min with 1200 revs/min, obtain stirring liquid C;
4) then, the stirring liquid C after stirring is moved to handsheet on handsheet machine, after adopting the pressure squeezing 7min of 6MPa, form the scraps of paper of 0.15mm;
5) last, the scraps of paper are put into the baking oven of 105 DEG C, after dry 30min, naturally cool and obtain there is magnetic characteristic and characteristics of luminescence paper.
It should be noted that, said GeO in the present invention
2, Al
2o
3, B
2o
3, Tb
4o
7, Eu
2o
3, Dy
2o
3, ZnO, Na
2siF
6, CeO
2, ZrO
2respectively by analytically pure germanium oxide, aluminium hydroxide, boric acid, terbium oxide, europium oxide, dysprosia, zinc oxide, prodan, cerium oxide, zirconia is introduced.
The present invention, by the compound of inorganic strong magnetic characteristic material that can be luminous and common paper pulp, has prepared the specialties simultaneously with magnetic characteristic and the characteristics of luminescence.Prepared paper not only has the series of advantages such as inorganic material is non-conductive, and heatproof is high, and chemical property is excellent, anti-aging, and prepared paper good mechanical performance, nonflammable; Under identical mechanical property, the paper sheet thickness minimizing 20 ~ 30% that Thickness Ratio is common.Meanwhile, the property that prepared paper also shows strong paramagnetism and glows.The paper obtained according to preparation method of the present invention, because having the magnetic characteristic such as magnetic response, magnetic recording, can be used for check paper, wrapping paper, calligraphic paper etc. and needs the false proof speciality paper goods of the bright height of special identity card.The present invention does not need special equipment in paper preparation process, simple to operate, is easy to suitability for industrialized production; And magnetic is permanent, not easily demagnetization, disguised strong, not easily copied.
Claims (10)
1. there is a preparation method for magnetic characteristic and characteristics of luminescence paper, it is characterized in that, comprise the following steps:
The first step: the preparation of inorganic strong magnetic characteristic material that can be luminous and process
1) first, according to mass fraction meter, by the GeO of 12 ~ 20%
2, the Al of 18 ~ 25%
2o
3, the B of 8 ~ 12%
2o
3, the Tb of 35 ~ 40%
4o
7, the Eu of 3 ~ 5%
2o
3, the Dy of 0.1 ~ 2%
2o
3, the ZnO of 2 ~ 3%, the Na of 3 ~ 5%
2siF
6, the CeO of 0.2 ~ 0.5%
2, the ZrO of 0.3 ~ 0.5%
2put into agate breast body mortar ground and mixed after weighing, form batch;
2), secondly, be incubated 1 ~ 2 hour under 1380 ~ 1410 DEG C of glass melting temperatures after, put into paddle continuation stirring and found, in whipping process, temperature remains at 1380 ~ 1410 DEG C, obtains liquation;
3) then, until step 2) stir terminate after, take out paddle, liquation is cooled to 1350 DEG C, obtains melt;
4), then, in the copper mould poured into by melt, after melt solidification, make test rod, the annealing furnace after die sinking, test rod being put into 650 DEG C is cooled to room temperature;
5) then, the test rod obtained is put into wire drawing machine, heat and be drawn into the fiber that diameter is 20 ~ 30 μm, and at fiber surface coating softening sizing agent;
6) last, after the fiber being coated with softening sizing agent is dried moisture, cutting into length is 2 ~ 5mm fiber, namely prepare can be luminous inorganic strong magnetic characteristic material;
Second step: the preparation with magnetic characteristic and characteristics of luminescence paper
1) first, according to mass fraction meter, get inorganic strong magnetic characteristic material, 0.6% ~ 1.5% retention and drainage aid agent that the leaf wood oven dry stock of 1% ~ 3%, 5% ~ 10% can be luminous, surplus is distilled water;
Leaf wood oven dry stock is added in distilled water, uniform stirring, obtain stirring liquid A;
2) secondly, adding described inorganic strong magnetic characteristic material that can be luminous to stirring in liquid A, carrying out uniform stirring, obtaining stirring liquid B;
3) then, then add retention and drainage aid agent in stirring liquid B, carry out uniform stirring, obtain stirring liquid C;
4) then, stirring liquid B is moved to handsheet on handsheet machine, makes the scraps of paper of 0.1 ~ 0.3mm;
5) last, after the scraps of paper are dried, naturally cool and obtain there is magnetic characteristic and characteristics of luminescence paper.
2. a kind of preparation method with magnetic characteristic and characteristics of luminescence paper according to claim 1, is characterized in that, step 3 in the described first step) take out after paddle, with the cooldown rate of 10 DEG C/min, liquation is cooled to 1350 DEG C.
3. a kind of preparation method with magnetic characteristic and characteristics of luminescence paper according to claim 1, is characterized in that, the diameter of described test rod is 5mm.
4. a kind of preparation method with magnetic characteristic and characteristics of luminescence paper according to claim 1, is characterized in that, step 1 in described second step) uniform stirring is stir in the mixer of 500 ~ 1000 turns/min.
5. a kind of preparation method with magnetic characteristic and characteristics of luminescence paper according to claim 1, is characterized in that, step 2 in second step) uniform stirring is for stir in 400 ~ 600 turns/min mixer.
6. a kind of preparation method with magnetic characteristic and characteristics of luminescence paper according to claim 1, is characterized in that, step 3 in second step) uniform stirring is for stir in 800 ~ 1500 turns/min mixer.
7. a kind of preparation method with magnetic characteristic and characteristics of luminescence paper according to claim 1, is characterized in that, the described scraps of paper are formed after adopting the pressure of 4 ~ 6MPa squeezing 3 ~ 15min.
8. a kind of preparation method with magnetic characteristic and characteristics of luminescence paper according to claim 1, is characterized in that, is carried out by the scraps of paper drying, the dry baking oven for the scraps of paper being put into 105 ~ 110 DEG C is dry.
9. a kind of preparation method with magnetic characteristic and characteristics of luminescence paper according to claim 1, is characterized in that, described retention and drainage aid agent is one or more in CPAM, PEI, PEO.
10. a kind of preparation method with magnetic characteristic and characteristics of luminescence paper according to claim 1, it is characterized in that, described softening sizing agent is by paraffin: vaseline: stearic acid: after the mass ratio weighing of water=1:1:1:30, after first paraffin, vaseline and stearic acid being melted, add water again, mix rear configuration and form.
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