CN1301792A - Luminous plastic masterbatch and its production - Google Patents

Luminous plastic masterbatch and its production Download PDF

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Publication number
CN1301792A
CN1301792A CN 99127572 CN99127572A CN1301792A CN 1301792 A CN1301792 A CN 1301792A CN 99127572 CN99127572 CN 99127572 CN 99127572 A CN99127572 A CN 99127572A CN 1301792 A CN1301792 A CN 1301792A
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combination
elements
luminous
luminescent material
different kinds
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CN1120207C (en
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肖志国
熊楚耀
刘欣
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Dalian Luming Science and Technology Group Co Ltd
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Dalian Luming Science and Technology Group Co Ltd
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Abstract

Luminous plastic masterbatch is produced with carrier resin, light accumulating luminous material, polymer wax and other material, and through the technological process including mixing miling, extrusion pulverizing, and granulating. It has evenly distributed luminous material and is compatible with various resin, the coating of luminous material by carrier resin results in high water-resistance, no contact of luminous material with metal, and thus no backening defect. Luminous products with the luminous masterbatch will have high luminous intensity, pure color and high smoothness.

Description

Luminous plastic masterbatch and method for making thereof
What the present invention relates to is the plastic products luminous used masterbatch and method for making thereof in man-hour that adds, and particularly has the plastic matrix and the method for making thereof of lighting function.
Because the appearance of light-storing and emitting material, many plastics that have lighting function are constantly come into market.Many luminous rigid plastics goods receive an acclaim as electric switch, socket, telephone casing, clock and watch shell, various ornaments, art ware etc.These are plastic products luminous generally be with light-storing and emitting material with resin through mixing, tie rod, pelletizing, make and carry out molding behind the plastic pellet that contains luminescent material and form, or directly form with luminescent material and plastic milling molding.Since existing light-storing and emitting material with the process of plastics hybrid process in, rubbed, under the effect of various power such as shearing, make the lattice partial destruction, cause the decline of luminous twilight sunset, in addition, because light-storing and emitting material and these metal ions of metallic contact also make luminous twilight sunset descend.Thereby influential to being processed into the goods color, particularly influence the intensity of its luminous twilight sunset.In addition, the resin that has (as PVC, PS, AS etc.) is a heat-sensitive resin, and bad granulation directly adds luminescent powder, bad again dispersion, so its goods illumination effect is bad.
At the defective that above prior art can't overcome, the present invention is intended to luminescent material is carried out useful processing, makes its effect that does not produce burnt hair, blackout, and can be fused mutually with other plastics.
The contriver finds that in research work when making luminescent plastics with prior art, plastics are hard more, the effect of easy more generation blackout.The basic point of technical scheme of the present invention is with the resin than " soft " luminescent material to be coated earlier, makes " masterbatch ", and this masterbatch can be granular, also can be powdery, and this masterbatch can be made light emitting articles with other resin compatibles.
Vector resin (i.e. " soft " resin) can also can be used the macromolecular oligomer of solid with the superpolymer of some alkene.For example PE (polyethylene), PP (polypropylene, random or rule are arranged), PBD (polyhutadiene), EVA (ethene-vinyl acetate interpolymer), PVC (polyvinyl chloride), CPE (chlorinatedpolyethylene), CSPE (chlorosulfonated polyethylene), PS (polystyrene), ACR (acrylic resin) class, butadiene-acrylonitrile rubber, SBS (styrene-butadiene-styrene), BS (styrene-butadiene copolymer) class etc. can use separately, also can use by mixture, wherein better with EVA, PP, PE, SBS, BS and composition thereof.The prerequisite condition of the selection of vector resin be make luminescent material can uniform distribution wherein, do not influence the character of plastics and good with the used resin intermiscibility of plastics.Can luminescent material is dispersed in the vector resin, need to use macromolecule wax, commonly used be PE wax and random PP wax.The adding of this wax not only can make luminescent material be dispersed in the vector resin, but also the effect of lubricating and making the plastics light can be arranged.When making luminous masterbatch, also add a little whiteruss or white oil sometimes.The used light-storing and emitting material of the present invention is different kinds of ions activated silicate, aluminate, sulfide and composition thereof, and its main chemical constitution expression and luminous twilight sunset color are 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 luminous plastics mother granule 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
Ln is the combination of one or more elements 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≤3.0.
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；0.0001≤γ≤0.3；
0.00001≤x≤0.15；0.00001≤y≤0.2。
Further experiment shows, preferred above-mentioned aluminate luminescent material, and the luminescent material of following 2 classes can be made the luminous plastics mother granule 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≤0.15; 0.0001≤y≤0.2.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 a 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; 00001≤y≤0.2.
When luminous plastic masterbatch of the present invention was made, its composition of raw materials (W%) was:
Vector resin 12.0-90.0%
Light-storing and emitting material 10.0-88.0%
Macromolecule wax 0-10.0%
In order to increase adhesivity, add small amount of liquid paraffin or white oil, the time spent, its amount was 0.1-2.5%.The manufacture craft of luminous plastic masterbatch is: with raw material ratio weighings on demand such as vector resin, luminescent material, macromolecule wax; in mixer, mix; insert the mixing roll manufacturing of heating; some kind is by the manufacturing of heating of extruding pelletization machinery, and processing temperature is carried out according to not coexisting 50-350 ℃ of vector resin.Make luminous masterbatch by the head discharging, some masterbatch need cut into dices by cooling and traction material bar to blank place and make luminous master batch.
With this luminous masterbatch can with many resins mix and.Can with other resins in carry out processed finished products, without any need for other auxiliary agent.The resin that fragility and hardness are very big can't resolve the problem of the easy blackening of the granulation course of processing.In addition, for fabricated product, luminous masterbatch add-on still seldom, in goods the vector resin add-on also seldom, it is to the not significantly influence of mechanical property of goods.Main is that this luminous masterbatch has prevented the deepening of luminescent material in the course of processing, so the color and luster of luminous masterbatch and plastics thereof is attractive in appearance and luminescent properties is all fairly good.As with luminous masterbatch and bulk resin and directly with the mixing luminescent plastics grain that contains the luminescent material same ratio or plastic products luminous of making of luminescent material and bulk resin, according to the vector resin difference, the former exceeds 10-300% than the latter's luminous afterglow intensity
Below be described further with example:
Example 1
The manufacturing of luminous master batch.Composition of raw materials is:
Vector resin LLDPE 1.1kg
Strontium aluminate luminous material SrAl 2O 4: Eu 0.05Dy 0.10.9kg
Macromolecule wax PE wax 0.2kg
Liquid wax 0.01kg
Raw material is mixed in mixer, add in the plastics extruder hopper.Heat up and control forcing machine material to drive head unit megadyne temperature degree at 115-200 ℃, reach the extruded stock bar of can starting shooting after the material melting temperature, the head discharging is cut into equigranular through cooling, traction, material bar to dicing machine, promptly gets luminous plastic masterbatch.
Make the luminescent plastics that contains luminescent material 5% and 10% respectively with this luminous masterbatch and ABS resin, contrast as following table with strontium aluminate luminous material is direct and its briliancy of ABS resin mixing granulator:
Figure A9912757200101
Example 2 luminous plastic masterbatch manufacturings.Composition of raw materials is: vector resin: LLDPE 0.5kg EVA 0.5kg macromolecule wax: PE wax 0.2Kg strontium silicate calcium luminescent material (Sr 0.5Ca 0.5) 2MgSi 2O 7: Eu 0.04Nd 0.21.0Kg method for making is with example 1, the luminous twilight sunset of this luminous masterbatch is blue green, can be used for high-pressure polyethylene goods vector resin: PS 0.5kg strontium aluminate luminous material SrAl 2O 4: Eu 0.05Dy 0.011.4Kg macromolecule wax PE wax 0.2Kg whiteruss 0.01Kg method for making is with example 1, it is luminous that this luminous master batch twilight sunset is yellow-green colour, can be used as the polystyrene plastic goods
Example 4 luminous plastic masterbatch manufacturings.Composition of raw materials:
(1) (2) vector resin: LLDPE 0.4 0.4 EVA 0.6 0.6 strontium aluminate luminous material SrAl 2O 4: Eu 0.05Dy 0.11.0 0.2 0 two kinds of masterbatch method for makings of 1.0 macromolecule wax PE waxes are with example 1, made luminous masterbatch is mixed and made into light emitting articles by luminescent material content 10% with ABS resin, and its briliancy is:
Figure A9912757200111
Example 5 luminous plastic masterbatch manufacturings.Composition of raw materials is: vector resin polymethylmethacrylate 1.0kg sulfurated lime luminescent material CaS:Eu 0.01Tm 0.0051.0Kg macromolecule wax PE wax 0.2Kg method for making such as example 1, masterbatch and ACR resin are made the luminous twilight sunset of plastic pellet and are taken on a red color luminous.
Example 6 plastic master batch productions.Composition of raw materials: vector resin EVA 0.5kg strontium aluminate luminous material SrAl 2O 4: Eu 0.05Dy 0.11.5Kg macromolecule wax PE wax 0.2Kg method for making such as example 1, the luminous master batch that manufactures is mixed and made into light emitting articles by luminescent material content 10% and ABS resin.Contain same ratio luminescent material with direct usefulness and the mixing luminous twilight sunset of making light emitting articles of ABS resin is compared as follows:
Figure A9912757200121

Claims (12)

1, a kind of plastic matrix is characterized in that a kind of plastic matrix with lighting function,
Wherein contain:
Vector resin 12.0-90.0%
Light-storing and emitting material 10.0-88.0%
Macromolecule wax 0-10.0%
Its described vector resin is superpolymer and solid macromole oligomer thereof, is the mixture of one or more oligopolymer among PE, random PP, EVA, PBD, PVC, CPE, PS class, ACR class, butadiene-acrylonitrile rubber class, SBS, the BS; Described light-storing and emitting material is different kinds of ions activated silicate, aluminate, sulfide or its mixture, and described macromolecule wax is PE, PP waxy body.
2, luminous plastic masterbatch as claimed in claim 1 is characterized in that also containing in the plastic matrix whiteruss or white oil 0.1-2.5%.
3, luminous plastic masterbatch 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 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;
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。
4. different kinds of ions activated silicate luminescent material as claimed in claim 3 is characterized in that main chemical constitution expression is:
(Sr 1-zCa z) 2MgSi 2O 7: Eu xLn yWherein Ln is the combination of one or more elements among La, Ce, Dy, Tm, Ho, Nd, Er, Sb, the Bi;
Z is a coefficient, 0≤z≤1;
X, y are mole coefficient, 0.0001≤x≤0.2; 0.0001≤y≤0.3.
5. different kinds of ions activated silicate luminescent material as claimed in claim 3 is characterized in that main chemical constitution expression is:
(Sr 1-zCa z) 3MgSi 2O 8: Eu xLn yWherein Ln is the combination of one or more elements among La, Ce, Dy, Tm, Ho, Nd, Er, Sb, the Bi;
Z is a coefficient, 0≤z≤1;
X, y are mole coefficient, 0.0001≤x≤0.2; 0.0001≤y≤0.3.
6. luminous plastic masterbatch as claimed in claim 1 is characterized in that the chemical constitution expression of described different kinds of ions activated aluminate luminescent material is:
α MO β Al 2O 3γ B 2O 3: Eu xLn yWherein 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≤5；0.5≤β≤9；0.0001≤γ≤0.3；
0.00001≤x≤0.15；0.00001≤y≤0.2。
7. different kinds of ions activated aluminate luminescent material as claimed in claim 6 is characterized in that main chemical constitution expression 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≤0.15; 0.0001≤y≤0.2.
8. different kinds of ions activated aluminate luminescent material as claimed in claim 6 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.
9. luminous plastic masterbatch 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.
10, luminous plastic masterbatch 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:
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≤0.2.
11, luminous plastic masterbatch as claimed in claim 1 is characterized in that described vector resin is one or both mixtures among EVA, the PE; Described macromolecule wax is a PE wax.
12, a kind of manufacture method of luminous plastic masterbatch according to claim 1 is characterized by its raw material is mixed, by mixing roll or forcing machine, and processing temperature 50-350 ℃, through pulverizing or pelletizing makes.
CN 99127572 1999-12-30 1999-12-30 Luminous plastic masterbatch and its production Expired - Lifetime CN1120207C (en)

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Cited By (14)

* Cited by examiner, † Cited by third party
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CN1328352C (en) * 2004-10-27 2007-07-25 中国石油化工股份有限公司 Long persistence luminous polyamide composition and method of making the same
CN1328313C (en) * 2004-10-27 2007-07-25 中国石油化工股份有限公司 Long persistence luminous polypropylene composition and method of making the same
CN100338171C (en) * 2004-10-27 2007-09-19 中国石油化工股份有限公司 Long persistence luminous thermoplastic plastics composition and method of making the same
CN100348690C (en) * 2004-10-27 2007-11-14 中国石油化工股份有限公司 Luminous polyethylene terephthalate compostition and its preparation method
CN100348662C (en) * 2004-10-27 2007-11-14 中国石油化工股份有限公司 High-brilliance high-ductility polycarbonate composition and its preparation method
CN100491462C (en) * 2006-03-09 2009-05-27 中国石油化工股份有限公司 Irradiant polystyrene composition and preparing method thereof
WO2011032358A1 (en) * 2009-09-16 2011-03-24 大连路明发光科技股份有限公司 Plastic light-converting fluorescent granules and use thereof
US8313843B2 (en) 2001-10-29 2012-11-20 Samsung Mobile Display Co., Ltd. Light-emitting polymer composition and organic EL display device using the same
CN103013499A (en) * 2011-09-20 2013-04-03 金朝阳 Luminescence composition, preparation method and applications thereof
CN103148438A (en) * 2013-01-16 2013-06-12 张海峰 Light-emitting/transmitting plastic lampshade and manufacture method thereof
CN106189170A (en) * 2016-08-30 2016-12-07 汕头市繁盛塑料机械制造有限公司 A kind of luminous plate and preparation method thereof
CN107603078A (en) * 2017-10-30 2018-01-19 宜宾运通塑料助剂有限公司 Luminous antibiotic plastic and preparation method thereof
CN108752747A (en) * 2018-06-25 2018-11-06 卿建勋 A kind of high after-glow brightness self-lighting dog nail and preparation method thereof
CN108892862A (en) * 2018-06-06 2018-11-27 全椒祥瑞塑胶有限公司 A kind of preparation method of long-acting moisture-resistant luminous plastics mother granule

Cited By (15)

* Cited by examiner, † Cited by third party
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US8313843B2 (en) 2001-10-29 2012-11-20 Samsung Mobile Display Co., Ltd. Light-emitting polymer composition and organic EL display device using the same
CN1328313C (en) * 2004-10-27 2007-07-25 中国石油化工股份有限公司 Long persistence luminous polypropylene composition and method of making the same
CN100338171C (en) * 2004-10-27 2007-09-19 中国石油化工股份有限公司 Long persistence luminous thermoplastic plastics composition and method of making the same
CN100348690C (en) * 2004-10-27 2007-11-14 中国石油化工股份有限公司 Luminous polyethylene terephthalate compostition and its preparation method
CN100348662C (en) * 2004-10-27 2007-11-14 中国石油化工股份有限公司 High-brilliance high-ductility polycarbonate composition and its preparation method
CN1328352C (en) * 2004-10-27 2007-07-25 中国石油化工股份有限公司 Long persistence luminous polyamide composition and method of making the same
CN100491462C (en) * 2006-03-09 2009-05-27 中国石油化工股份有限公司 Irradiant polystyrene composition and preparing method thereof
WO2011032358A1 (en) * 2009-09-16 2011-03-24 大连路明发光科技股份有限公司 Plastic light-converting fluorescent granules and use thereof
CN102020819A (en) * 2009-09-16 2011-04-20 大连路明发光科技股份有限公司 Plastic light-conversion fluorescent granules and application thereof
CN103013499A (en) * 2011-09-20 2013-04-03 金朝阳 Luminescence composition, preparation method and applications thereof
CN103148438A (en) * 2013-01-16 2013-06-12 张海峰 Light-emitting/transmitting plastic lampshade and manufacture method thereof
CN106189170A (en) * 2016-08-30 2016-12-07 汕头市繁盛塑料机械制造有限公司 A kind of luminous plate and preparation method thereof
CN107603078A (en) * 2017-10-30 2018-01-19 宜宾运通塑料助剂有限公司 Luminous antibiotic plastic and preparation method thereof
CN108892862A (en) * 2018-06-06 2018-11-27 全椒祥瑞塑胶有限公司 A kind of preparation method of long-acting moisture-resistant luminous plastics mother granule
CN108752747A (en) * 2018-06-25 2018-11-06 卿建勋 A kind of high after-glow brightness self-lighting dog nail and preparation method thereof

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