CN100343347C - Light-storage luminescent coating and luminous fibre therefor - Google Patents
Light-storage luminescent coating and luminous fibre therefor Download PDFInfo
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- CN100343347C CN100343347C CNB2005100076938A CN200510007693A CN100343347C CN 100343347 C CN100343347 C CN 100343347C CN B2005100076938 A CNB2005100076938 A CN B2005100076938A CN 200510007693 A CN200510007693 A CN 200510007693A CN 100343347 C CN100343347 C CN 100343347C
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- light
- accumulating
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Abstract
The present invention provides light storing type luminescent paint and a light storing type luminescent fiber substance coated with the paint. The paint comprises light storing powders which uses strontium aluminate as base material and has 30% to 45% of the weight of the paint, light refracting and reflecting powders with 10% to 15% of the weight of the paint, and carriers with 40% to 60% of the weight of the paint. The compounding of specific carrier components are utilized to generate favorable wetting property and strong adhesive force with the fiber matter, and after coating, the paint can be used for manufacturing various (night) luminescent fiber substances and luminescent products.
Description
Technical field
The present invention relates to a kind of light-accumulating (night) luminous paint, relate in particular to and absorb ultraviolet luminous energy a kind of daytime and store energy, night or luminous when dark, luminous paint at night that can be reflective simultaneously, this coating can be realized well wetting on the fibre object surface by forming.The invention still further relates to the luminescent fibre thing and the corresponding light emitting articles that are coated with this coating.
Background technology
So-called luminous paint, kind on the books has at present: reflected light type coating, but promptly contain the component of reflected light material in the coating, when rayed, can reflect and luminous, for example most traffic mark board all mainly uses this coating; Self-luminous paint is to have added fluor and produce illumination effect in coating; The light-accumulating luminous paint is added with light-accumulating powder in the coating, the sustainable light that holds when rayed is arranged discharges luminous energy when light during dark partially or dull thread and luminous voluntarily.
In these luminous paints, because the light-accumulating luminous paint is that to hold light earlier luminous again, it is luminous when dark, and the characteristics that brightness is big, luminescent lifetime is long are understood by people gradually and are accepted, developed the light-accumulating luminous paint that can be used for the enamel surface, its manufacturing processed need realize by sintering.But if change carrier, for example be used for fibre object (comprise yarn fabric, not fabric, paper etc.) surface applied, be subjected to the also not record of restriction of coating manufacturing technology.On the other hand, these coating substantially all are independent uses in the prior art, illumination effect (for example brightness and fluorescent lifetime) still is difficult to satisfy the application of some particular surroundingss, for example, when applied environment can not have illumination in the long period section, and also must or require to know this mark of demonstration or article, simple will be difficult to realize by a kind of coating.
The molecule of some material (or atom) is subjected to excite (as being absorbed photon by rayed) of outside energy, will produce the transition of electronics to the high energy position, be that molecule is in " excited state ", this moment, this electronics was in " astable " state, when it is returned to ground state (primary state), the energy of its acquisition just discharges with the form of light and heat, produces luminescence phenomenon, and this is known material luminescence mechanism.But the life-span of excited state molecule is very short, approximately has only 10
-7-10
-10About second, be difficult to use in practice, for solving this difficult problem, the relevant person once added the radioactive fluorescent material of a small amount of tool in the luminous base material in the industry, utilized its radioactive ray constantly to excite the electronics of ambient substance, reached constantly luminous purpose.But because radioactive substance harm environment, use in the world has been under an embargo.
For overcoming above-mentioned drawback, the insider is constantly exploring and is seeking solution route, a kind of luminescent powder that can be used for spraying also once appearred on the market, how be that base material is mixed with impurity copper and made with zinc sulphide, the mechanism of foundation is, in the base material of some materials, mix with certain impurity, as metallic impurity, can make the excited state molecule that is in " astable " become " quasi-steady " (or claiming meta) excited state molecule, after exciting of the external world stopped, these " quasi-steady " excited state molecules were not to return ground state immediately, but little by little return ground state in for some time, so just prolong the life-span of excited state molecule, that is prolonged the material fluorescent lifetime.But after tested, this luminescent powder is very low in the aura intensity that exciting of outside energy issues bright dipping, can recognize and also have only 30-60 minute between the surplus light time, and because the photochemical stability of sulfide is poor, easily aging, luminescent lifetime has only 1-2, and practical value is not high.
Summary of the invention
The objective of the invention is to development provides a kind of light-accumulating luminous paint, and this coating can be realized fine wetting on the fibre object surface, can directly be coated on the fibre object surface, does not need sintering promptly to can be made into various light-accumulating light emitting articles.
On this basis, the present invention also provides various light-accumulating luminescent fibre things, its surface coated this coating, can be used for being processed into the light-accumulating light emitting articles that uses for different occasions.
At first, the invention provides a kind of light-accumulating luminous paint, its composition comprises:
30-45% weight be the light-accumulating powder of matrix with the strontium aluminate, its fineness is more than 150 orders;
The reflective powder of the refractive power of 10-15% weight;
The carrier of 40-60% weight;
Each components contents sum is 100% weight, and the component of described carrier and weight ratio comprise:
Fineness is the PVC of 1-2nm powder 50-60 part, dioctyl phthalate (DOP) 20-25 part, dibutyl phthalate 15-20 part, epoxy ester 1-2 part, barium stearate 0.01-0.03 part, Zinic stearas 0.01-0.03 part, white oil 0.2-0.5 part; Perhaps,
Acrylic ester polymer 40-60 part, vinylformic acid-Sipacril 2739OF 20-30 part, triacryl three pyridine 2-3 parts, thinner 15-20 part, glycerine-urea 3-5 part;
This coating is that above-mentioned composition is mixed in proportion to stir and obtained in 2-6 hour.
Above-mentioned luminous paint of the present invention is particularly useful for the surface coated in various fibre object, utilize the composite of specific support component wherein and produce good wettability and extremely strong sticking power with fibre object, can be used to make various (night) luminescent fibre thing and light emitting articles, heavy duty service miner's luminous uniforms for worker for example, control of traffic and road personnel's caution clothes or luminous ornament, the navigation navigation mark, airport navigation apparatus and sign etc., also can be used to process various buoyant apparatus or vestlifejacket etc., can also make various field articles, for example Camp tent by the surface coated above-mentioned coating, field work clothes etc.
According to luminous paint provided by the invention, be to adopt with strontium aluminate (SrAl
2O
4) crystal is the light-accumulating powder that base material is made, comprise a spot of rare-earth oxide in this light-accumulating powder, as europium sesquioxide, thallium oxide, germanium oxide, gallium oxide etc., this light-accumulating powder be rare earth material and alkaline earth material under the high temperature more than 1500 ℃ through calcining the luminous bulk material that forms more than 10 hours, broken through pressing from both sides again, ball milling, sieving forms, and its fineness can reach the 100-400 order.The principle that its illumination effect is better than common fluorescent material is, common fluorescent material is subjected to ambient light and shines when exciting, electronics can experience from the ground state transition to excited state and return the process of ground state, this moment, unnecessary energy just discharged with the form of light, the external world excites and has stopped, luminously also just stopped, and the strontium aluminate material that contains rare-earth oxide is formed with some electronics " trap " at the crystallo-luminescence central periphery, the electronics that is in excited state is caught by these " traps " in returning the ground state process, these electronics still are in metastable condition, when the external world excite stop after, electronics dependence amount of heat in " trap " is jumped out " trap " gradually and is returned ground state and emit light, forms the luminous phenomenon of light-accumulating.The present invention is when having used this light-storing and emitting material, also used the reflective powder of the refractive power with refractive power reflection action, when applying coating is surperficial to fibre object, its upper and lower upper layer forms reflective in a large number, refractive power minute surface, when the electronics that is excited returns ground state, an energy part that discharges is discharged energy just by specular reflection or bounce back original position gradually, prolongs fluorescent lifetime more.It has been generally acknowledged that human eye visible brightness at night is 0.32mcd/m
2, according to national standard, the brightness requirement of this class luminescent material is 3mcd/m after 10 hours
2, and being coated on the fibre object surface, coating of the present invention makes the luminescent fibre thing, original intensity can reach 8000mcd/m
2, still can be after 10 hours greater than 10mcd/m
2
In actual production, light-accumulating powder can select for use fineness at 150-300 purpose raw material, and the reflective powder of refractive power can be selected fineness 100-400 purpose marzacotto powder or transparent glass powder for use.
Coating of the present invention has comprised three class main ingredients, be reflective powder of light-accumulating powder, refractive power and carrier, when obtaining required illumination effect by light-accumulating powder and the reflective powder of refractive power, carrier composition through special screening then helps and effectively adhering to of various fibre object and firm combining, and the selection that carrier is formed also can be different according to preparing coated fibres thing base material.According to preferred version of the present invention, PVC powder in the carrier is the nano level raw material that emulsion polymerization is made, its fineness is at 1-2nm, acrylic ester polymer generally can be the homopolymer or the multipolymer of methyl acrylate, ethyl propenoate, butyl acrylate and vinyl cyanide, this polymkeric substance preferably should satisfy solid content 38% ± 2%, and pH is 4-5; And vinylformic acid-Sipacril 2739OF as its solid content of thickening material general requirement 20% ± 2%, substantially be neutrality; Triacryl three pyridines are condensess of a polyamine species and low molecule epoxy compounds, and as linking agent, its condensation course can be exemplified as in this case:
H
2N(CH
2)
6NH
2+Cl-CH
2CHCHO-CH
2→CH
2CHO-CHCH
2NH(CH
2)
6CH
2CHO-CH
2+HCl；
Thinner among the present invention can be vinyl acetic monomer or N-BUTYL ACETATE, and glycerine and urea preferably are the equal proportion preparation basically.
The preparation process of this coating does not have particular requirement, get in proportion each raw material put into nonmetal material-compound tank stir 2-6 hour can be for the coating use.
When utilizing above-mentioned (night) of the present invention luminous paint to process various luminescent fibre thing, can adopt common coating apparatus, in prior at least one surface applied above-mentioned coating of passing through the fibre object of oven dry, draw together flat then, again this fibre object is dried, can become a kind of luminescent fibre thing, for processing or be sewn into the product that needs.
Different application needs and application places according to the finished product, fibre object can be common fabric or non-woven fabrics, also can be to have covered with paint, lacquer, colour wash, etc. the canvas of waterproof layer or the paper of different size (for example paper in the office of ivory board, kraft paper, common specification etc.), this luminescent fibre thing is made the alert flag on luminous clothes (for example working suit, vest etc.) or the clothes after can cutting, perhaps be made into life preserver, buoyant apparatus (safety buoy, vestlifejacket etc.) for example, navigation navigation mark, airport navigation apparatus and sign etc.The paper after one side is applied or the back side of cloth are coated with non-drying glue layer again and sealer are set and promptly becomes a kind of light (night) light emitting-type self-adhesive paper or non-drying adhesive tape of holding.According to the difference of the finished product and use occasion, the glue spread of luminous paint can be different, generally can control the every 4-5 square metre of described luminous paint of fibre object surface coated 1-1.5 kilogram, and coat-thickness can be 200-300nm, preferably at 250-300nm.
Above-mentioned luminescent paper or luminous cloth can also carry out various printings on the coating top layer except that can directly being processed into cited various luminous product, for example make and can realize noctilucent map, advertisement, label etc.Utilize the indefiniteness example of the light emitting articles that luminescent fibre thing of the present invention can make to have: luminous clothes or decoration have the clothes of this light-emitting caution, and for example underground work clothes, traffic administration personnel's warning clothing or caution are decorated, waterborne and airport navigation marker, life-saving (life-saving suit, safety buoy etc.), luminous map, luminous ornament are drawn (thing), luminous non-setting adhesive etc.
Coating of the present invention is through traffic safety product quality supervision inspection center of the Ministry of Public Security, carry out tests such as state, workability, appearance of film, sticking tire time of drying, sticking power, water tolerance, alkali resistance, high temperature and low-temperature performance, salt spray resistance, luminosity according to the enterprise technology condition, all shown good result.Manage inspection center's wear resistance detected result through the Ministry of Communications's traffic engineering and also meet the correlation technique requirement.So, various light emitting articles provided by the invention or product remove in actual applications has the luminosity height, outside the advantage of fluorescent lifetime length, also have strong adhesion, antistatic property is good, the folding superimposition is rubbed characteristics, all can have a good application prospect in road traffic, navigation and airport navigation even in the fields such as construction of military equipment (luminous military map or mark etc.).
Embodiment
The beneficial effect that describes realization of the present invention by the following examples in detail and produced is intended to help the reader to understand characteristics of the present invention better, should not be construed as the qualification to the scope of the present invention.
Embodiment 1
1, carrier is formed (weight part)
PVC powder (1-2nm) 60
Dioctyl phthalate (DOP) 20
Dibutyl phthalate 20
Epoxy ester 1
Barium stearate 0.02
Zinic stearas 0.02
White oil 0.2 (annotate: white oil is from the isolated a kind of distillate of white oil of camphor, claims Liquid Paraffin again)
Said components becomes coating vehicles after mixing, and is standby.
2, batching
SrAl
2O
4Eu light-accumulating powder (about 200 order fineness) 35%
100-400 purpose marzacotto powder 10%
Above-mentioned carrier 55%
Three kinds of components drop in proportion in the ceramic batch jar and fully stirred 3-4 hour, obtain described coating.
Embodiment 2
1, carrier is formed (weight part)
Methyl acrylate-ethyl acrylate copolymer (PAE) 50 (solid content 38 ± 2%, pH4-5)
Vinylformic acid-Sipacril 2739OF 20 (viscosity 7000-1000 centipoise)
Triacryl three pyridines 3
Vinyl acetic monomer 22
Glycerine-urea (1: 1) 5
Said components becomes coating vehicles after mixing, and is standby.
2, batching
SrAl
2O
4Eu light-accumulating powder (about 200 order fineness) 35%
100-400 purpose marzacotto powder 10%
Carrier 55%
Three kinds of components dropped in the ceramic batch jar fully stir about 5-6 hour in proportion, obtained described coating.
Embodiment 3
1, carrier is formed (weight part)
PVC powder (1-2nm) 55
Dioctyl phthalate (DOP) 25
Dibutyl phthalate 20
2 parts of epoxy esters
Barium stearate 0.01
Zinic stearas 0.02
White oil 0.5
Said components becomes coating vehicles after mixing, and is standby.
2, batching
SrAl
2O
4Eu light-accumulating powder (about 200 order fineness) 40%
100-400 purpose marzacotto powder 10%
Above-mentioned carrier 50%
Three kinds of components drop in proportion in the ceramic batch jar and fully stirred 5-6 hour, obtain described coating.
Embodiment 4
Fiber cloth material is involved on the cylinder of coating apparatus, through rollers roll the coating of embodiment 2 is coated the cloth surface, glue spread is controlled to be every square metre of 200-250 gram, coat-thickness 250-300nm, this cloth with dope layer is sent into dryer (about 30 meters/minute of transfer rate), control rolling after the 120-150 ℃ of oven dry, promptly become luminescent fibre cloth.Because coating is colourless substantially, the cloth that obtains shows primary colors substantially.
According to the antistatic property requirement in textile materials, the luminous cloth of this light-accumulating is carried out the surface ratio resistance detection, detected result: warp-wise 1.2 * 10
9, broadwise 5.2 * 10
9, show good antistatic effect.
Embodiment 5
Utilize the light-accumulating luminescent fibre cloth cutting of embodiment 4 to be sewn into the working suit and the working cap of heavy duty service, wear band when going into the well, can equally with common working suit wash at ordinary times for the workman.
This luminescent fibre cloth also can be made in the appropriate location of traffic administration personnel clothes, has eye-catching effect in the night duty.
Embodiment 6
Adopt 120g/m
2Paper, according to the method for embodiment 4 coating luminous paint at night, 100-120 ℃ of oven dry, the another side of paper coating non-setting adhesive is promptly made the luminous non-setting adhesive of light-accumulating, the surface of this dope layer also can apply transparent protective layer.
Embodiment 7
The luminous map of light-accumulating:
With the air brushing machine with the air brushing of map desired proportions on the luminescent fibre cloth of embodiment 4, or on the luminescent paper of embodiment 6, adopt transparent spray material to implement air brushing, promptly become luminous map at night after the drying.
The map surface that is compound in shaping by tackiness agent after the mylar scrub clean is protected, and drying gets final product.
Embodiment 8
The surface is scribbled on the non-woven fabrics of waterproof layer or the cylinder that canvas is involved in coating apparatus, through rollers roll the coating of embodiment 1 is coated the surface, glue spread is controlled to be every square metre of 250-300 gram, coat-thickness 280-300nm, this non-woven fabrics or canvas with dope layer is sent into dryer, rolling after 100-120 ℃ of oven dry promptly becomes the luminous cloth of light-accumulating.
Should be sewn on the safety buoy by size or the vestlifejacket skin by luminous cloth, and perhaps directly utilize this luminous cloth to make and be processed into safety buoy or vestlifejacket.
With above-mentioned night luminous canvas be processed into Camp tent, or be used for the part of Camp tent, night can be luminous automatically.
Claims (10)
1, a kind of light-accumulating luminous paint, its composition comprises:
30-45% weight be the light-accumulating powder of matrix with the strontium aluminate, its fineness is more than 150 orders;
The reflective powder of the refractive power of 10-15% weight;
The carrier of 40-60% weight,
Each components contents sum is 100% weight, and the component of described carrier and weight ratio comprise:
Fineness is the PVC of 1-2nm powder 50-60 part, dioctyl phthalate (DOP) 20-25 part, dibutyl phthalate 15-20 part, epoxy ester 1-2 part, barium stearate 0.01-0.03 part, Zinic stearas 0.01-0.03 part, white oil 0.2-0.5 part; Perhaps,
Acrylic ester polymer 40-60 part, vinylformic acid-Sipacril 2739OF 20-30 part, triacryl three pyridine 2-3 parts, thinner 15-20 part, glycerine-urea 3-5 part;
This coating is that above-mentioned composition is mixed in proportion to stir and obtained in 2-6 hour.
2, the described light-accumulating luminous paint of claim 1, wherein, the reflective powder of refractive power is fineness 100-400 purpose marzacotto powder or transparent glass powder.
3, a kind of light-accumulating luminescent fibre thing, its at least one surface coated the described light-accumulating luminous paint of claim 1.
4, the described light-accumulating luminescent fibre of claim 3 thing, wherein, the surface coated of every 4-5 square metre fibre object the described luminous paint of 1-1.5 kilogram.
5, the luminous non-setting adhesive of a kind of light-accumulating is to be base material with claim 3 or 4 described light-accumulating luminescent fibre things, a described luminous paint of surface coated of this base material, another surface coated non-drying glue layer.
6, a kind of clothes that can be luminous, it is made material and comprises claim 3 or 4 described light-accumulating luminescent fibre things.
7, a kind of life preserver, it utilizes claim 3 or 4 described light-accumulating luminescent fibre things to be made.
8, the luminous navigation articles for use of a kind of light-accumulating, it is to utilize claim 3 or 4 described light-accumulating luminescent fibre things to be made.
9, the described navigation articles for use of claim 8, it comprises offshore beacon or airport range marks goods.
10, a kind of open-air Camp tent, it utilizes claim 3 or 4 described light-accumulating luminescent fibre things to be made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100076938A CN100343347C (en) | 2005-02-07 | 2005-02-07 | Light-storage luminescent coating and luminous fibre therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100076938A CN100343347C (en) | 2005-02-07 | 2005-02-07 | Light-storage luminescent coating and luminous fibre therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1817984A CN1817984A (en) | 2006-08-16 |
| CN100343347C true CN100343347C (en) | 2007-10-17 |
Family
ID=36918194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100076938A Expired - Fee Related CN100343347C (en) | 2005-02-07 | 2005-02-07 | Light-storage luminescent coating and luminous fibre therefor |
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| CN (1) | CN100343347C (en) |
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| CN106049082B (en) * | 2016-06-27 | 2018-05-25 | 江苏新凯盛企业发展有限公司 | A kind of persistently light-accumulated luminous night runs Fashion and its preparation process |
| CN107100040A (en) * | 2017-07-03 | 2017-08-29 | 四川锦泓佳建筑装饰工程有限公司 | A kind of luminous ornament wallpaper |
| CN108179627A (en) * | 2017-12-28 | 2018-06-19 | 泉州迪特工业产品设计有限公司 | A kind of graphene dress materials and its manufacturing method |
| CN108374286A (en) * | 2017-12-28 | 2018-08-07 | 龙南县中利再生资源开发有限公司 | A kind of preparation method of rare earth luminescent fiber |
| CN109082185B (en) * | 2018-07-27 | 2021-01-08 | 南宁市高科交通设施有限公司 | Production method of environment-friendly anticorrosive wear-resistant luminous marking paint |
| CN109610235A (en) * | 2018-12-05 | 2019-04-12 | 中国制浆造纸研究院有限公司 | A kind of the maps with fluorescent colouring paper and its manufacturing method of high folding strength |
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| CN1313368A (en) * | 2000-03-13 | 2001-09-19 | 吴振华 | Light-accumulating luminous paint |
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|---|---|---|---|---|
| CN1313368A (en) * | 2000-03-13 | 2001-09-19 | 吴振华 | Light-accumulating luminous paint |
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