CN1328313C - Long persistence luminous polypropylene composition and method of making the same - Google Patents
Long persistence luminous polypropylene composition and method of making the same Download PDFInfo
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- CN1328313C CN1328313C CNB2004100863750A CN200410086375A CN1328313C CN 1328313 C CN1328313 C CN 1328313C CN B2004100863750 A CNB2004100863750 A CN B2004100863750A CN 200410086375 A CN200410086375 A CN 200410086375A CN 1328313 C CN1328313 C CN 1328313C
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Abstract
The present invention provides a long persistence luminescent polypropylene composition and a preparation method thereof, which belongs to the field of luminescent plastic. The luminescent polypropylene composition of the present invention is prepared by polypropylene, light-accumulating luminescent materials and powdered rubber via melt blending, wherein the luminescent material is one or a plurality of compounds of a metasilicate system, an aluminate system and sulfide series light-accumulating luminescent materials. The luminescent polypropylene composition can be matched with powdered rubber with 50 to 200 nm of grain diameter and 60 wt% or more gel content, so the dispersed luminescent material in the polypropylene can be effectively avoided, the luminescent polypropylene composition reduces friction in manufacture procedures and increases the mechanical property and the luminescent property of the composition, and therefore, the luminescent polypropylene composition has the advantages of high brightness, good tenacity and nondiscolouring luminescence. With taking the polypropylene as 100 weight portions, the composition has 1 to 40 portions of the luminescent material and 1 to 10 portions of the powdered rubber. The composition of the present invention is suitable for manufacturing products which need luminescent effects and can carry out low-light level floodlighting without external light sources, and the composition has wide application ranges.
Description
Technical field
The present invention relates to a kind of luminescent plastics composition, say further, relate to a kind of long persistence luminous polypropylene composition and preparation method thereof.
Background technology
Polypropylene (PP) is the big kind plastics that have a large capacity and a wide range, and has good mechanical performance and processing characteristics, has obtained using widely in daily living article, traffic, machinery, industry such as electric.But PP does not have noctilucent function.People have noctilucent performance in order to make the PP plastics, mainly take two kinds of approach: a kind of is to apply luminous paint on plastics, paste and inlay twinkler, and another kind is exactly to add luminous filler in plastics.
On plastics, apply luminous paint, paste and inlay twinkler, be actually PP, add surface with lighting function as main structure body.This PP is not a luminescent plastics truly, and its complicated operating process, inefficiency, and manufacturing cost is higher, and weak effect, and the usage period is not long, thereby is difficult in actual applications promote.
The performance for preparing the development technique of luminous PP and phosphor by the method for filling luminous filler in plastics is closely related, traditional luminous PP adopts fluorescent material, as ZnS, CaS etc., but their poor stabilities, time of persistence is shorter, and work-ing life is not long yet.If will prolong time of persistence, must add a certain amount of radioelement, and bring environmental hazard around work can be given like this, therefore prohibited use by most of country at present.
The sixties in 20th century, SrAl
2O
4: Eu
2+After the twilight sunset phenomenon of material was found, people were to europium ion (Eu
2+) method that mainly concentrates on by adding the assisted activation ion and changing matrix structure of the research and development of activated aluminate class and silicates light-storing and emitting material improves the luminous intensity of material and prolong time of persistence.
Since the nineties in 20th century, this aluminates system or silicate systems light-storing and emitting material (are seen " light-storing and emitting material and goods thereof " third and fourth chapter, the Xiao Zhiguo chief editor, Chemical Industry Press's in October, 2002 publication) research changes the applied research stage over to by conceptual phase, this material has characteristics such as nontoxic, harmless, "dead", it is the environmental type material, particularly than zinc sulphide materials significant advantage is being arranged aspect the accumulation of energy and the characteristics of luminescence, its absorbing time is short, extinction 10～20min is more than the sustainable luminous 12h.By adopting this material, people develop luminescent ceramic, coating, printing ink, rubber, plastics, fiber, fabric etc. in succession.
The application light-storing and emitting material prepares the luminous high polymer material situ aggregation method, blending method etc.Situ aggregation method is usually used in carrying out the superpolymer of condensation polymerization, as nylon, polyester etc.When adopting blending method to prepare luminescent plastics, existing light-storing and emitting material with the process of the mixed processing of plastics in, because of each other friction, shearing action is stronger, make the lattice partial destruction easily, cause long-persistence luminous performance decrease; Also may cause simultaneously the variation of material color, make luminescent plastics variable color (because the hardness of luminescent material is big, make the post-treatment product appearance relatively poor, metachromatisms such as turing grey blackening is arranged) to cause that equally also luminous afterglow intensity descends further.The contriver of Chinese patent application CN130792A finds in research work, when making luminescent plastics with prior art, plastics are hard more, the effect of easy more generation blackout, therefore he has proposed a kind of scheme, promptly with resin luminescent material is coated earlier, make " masterbatch ", and then make light emitting articles with other resin compatible than " soft ".But will certainly make the course of processing complicated like this, and increase cost.
And because energy-saving luminous material is an inorganic materials, particle diameter is generally bigger, and difficulty good distribution in polypropylene matrix causes illumination effect bad.Disperse bad inorganic materials to make that the mechanical property of composition is not good simultaneously, as cause the declines such as impact property of composition more, thus the application scenario of having limited luminescent plastics.Therefore the luminescent plastics composition is for fear of serious following general of mechanical property in the prior art, and the umber of the luminescent material of its interpolation is all lower, is that 100 weight parts generally are no more than 5 parts in matrix plastic.
Summary of the invention
When adopting traditional blending method to prepare long persistence luminous polypropylene, destroy the crystalline network of luminescent powder material easily, make the luminescent material oxidation simultaneously, make long-persistence luminous degradation, the goods variable color of PP; The bad mechanical property that influences luminous polypropylene of dispersion of while phosphor.
The present invention is directed to above problems of the prior art, be intended to obtain a kind of luminous polypropylene that when having good luminous performance, has high tenacity and good appearance.
Therefore, the purpose of this invention is to provide a kind of have good luminous property and high tenacity and non-discoloring luminous polypropylene composition.
Another object of the present invention provides the preparation method of described luminous polypropylene composition.PP resin and luminescent material realize that disposable blend extrudes in this method, can increase work efficiency greatly, realize the good mixing dispersion effect simultaneously.
The contriver finds in the process of research luminescent plastics, is added in finely disseminated elasticity powdered rubber in the plastics and can helps to reduce shearing friction in the blend process, reduces the destruction of mechanical blending to the luminescent material lattice, prevents the oxidation of luminescent material; And assistance improves the dispersion of luminescent material in plastic substrate simultaneously.Make that luminescent material can be because of influencing its illumination effect in plastic substrate in processing and scattering problem.Owing to reduced the oxidation of luminescent material, can stop the metachromatism after goods are extruded simultaneously, make luminescent plastics have good appearance.And the adding of powdered rubber can also make the toughness of luminescent plastics be greatly enhanced, thereby the add-on of luminescent material is greatly enhanced, and is that 100 weight parts can reach more than 5 parts in the matrix polypropylene generally.
A kind of long persistence luminous polypropylene composition provided by the present invention includes the following component of blend: a. polypropylene; B. light-storing and emitting material; C. powdered rubber.
In the polypropene composition of the invention described above, described polypropylene comprises the disclosed various types of acrylic resins of prior art, comprises homo-polypropylene resin, Co-polypropylene resin etc.
The above polypropene composition of the present invention, wherein components b is one or more in silicate systems light-storing and emitting material of the prior art, aluminates system light-storing and emitting material, the sulfide series light-storing and emitting material.Be preferably in different kinds of ions activated silicate, the different kinds of ions activated aluminate one or more.Different kinds of ions activated silicate and aluminate among the present invention, (patentee: different kinds of ions activated silicate and the aluminate Luming technology Group Co., Ltd., Dalian city) is consistent with Chinese patent CN1120207C.
The chemical constitution expression that is multiple 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。
The chemical constitution expression of multiple 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。
The big more briliancy of the above light-storing and emitting material particle is high more, but can improve the frictional force in the course of processing, and too conference is unfavorable for the composition mechanical property; The little frictional force that can reduce in the processing of particle, but briliancy can decrease, and also too little particle also is unfavorable for disperseing.Help luminescent material to disperse, reduce friction, raising luminescent material add-on, improve composition flexible powdered rubber, owing to added among the present invention so the granular size of these light-storing and emitting materials is not remarkable to the influence of composition properties in the present invention in the prior art.But consider the problem of dispersed and cost, its median size can be preferably 10～40 μ m, more preferably 10～20 μ m.
The content of described components b is 100 parts by weight in component a polypropylene, is 1～40 part.The preferable range of its content is 10～30 parts.
The above polypropene composition of the present invention, wherein amount of component b is median size 50～200nm, is preferably 80～150nm; Gel content is 60% weight or higher, is preferably 80% weight or higher powdered rubber.This kind powdered rubber is preferably the rubber particles of equal phase structure.This kind powdered rubber is selected from a kind of or its mixing in butylbenzene powdered rubber and the carboxyl butylbenzene powdered rubber.
The powdered rubber of described amount of component b can adopt according to the inventor in the prepared fully vulcanized powder rubber of the Chinese patent ZL00816450.9 of on September 18th, 2000 application (is right of priority with Chinese patent application 99125530.5, priority date on December 3rd, 1999).Be preferably form of finely divided powder, mehtod styrene-butadiene rubber(SBR) and/or form of finely divided powder, mehtod carboxylic styrene-butadiene rubber.This kind fully vulcanized powder rubber gel content reaches 60% weight or higher, need not after the drying to get final product unrestricted flow with separant.Each particulate in this fully vulcanized powder rubber all is a homogeneous, and promptly single particulate all is a homogeneous on forming, and does not find layering in the particulate under the observation of existing microtechnique, divides the phenomenon that equates uneven phase.This fully vulcanized powder rubber gets by to the rubber latex cross-linking radiation rubber particles particle diameter being fixed.So the particle diameter of latex particle is consistent substantially in its median size and the rubber latex, the size scope of the latex particle that described rubber latex obtains when synthetic is the particle size range of gained fully vulcanized powder rubber particle, be generally 20～2000nm, preferred 30～1500nm, more preferably 50～500nm.
The powdered rubber of the above amount of component b can also adopt the prepared cross-linked powdered rubber of Chinese patent ZL00130386.4 in application on November 3rd, 2000 according to the applicant.Be preferably cross-linked powdery styrene-butadiene rubber(SBR) and/or cross-linked powdery carboxylic styrene-butadiene rubber.This kind cross-linked powdered rubber is a kind ofly (to have some rubber latexs between the rubber molecule certain cross can take place in the synthetic process with cross-linking type synthetic rubber latex, thereby make resulting rubber latex have certain crosslinking degree, be referred to as crosslinking-type rubber latex) be raw material, the powdered rubber that drying obtains.The particle diameter of latex particle is consistent substantially in its median size and the crosslinking-type rubber latex, and the size scope of the latex particle that crosslinking-type rubber latex obtains when synthetic is the particle size range of gained cross-linked powdered rubber particle, is generally 50～300nm.This cross-linked powdered rubber need not add separant and get final product unrestricted flow.Its gel content is consistent with gel content as the cross-linking type synthetic rubber latex of raw material, is 80% weight or higher, is preferably 85% weight or higher.Each particulate in this cross-linked powdered rubber all is a homogeneous, and promptly single particulate all is a homogeneous on forming, and does not find layering in the particulate under the observation of existing microtechnique, divides the phenomenon that equates uneven phase.
Described amount of component b powdered rubber also can be the mixing of the above fully vulcanized powder rubber and cross-linked powdered rubber.
The content of described amount of component b powdered rubber is 100 parts by weight in component a polypropylene, is 1～10 part.The preferable range of its content is 3～6 parts.
Polypropene composition of the present invention wherein also can include silicone oil and/or silicone in the component.Wherein silicone oil content is 0.1～1%wt of polypropylene weight, is preferably 0.1～0.5%wt; Silicone content is 0.1～1%wt of polypropylene weight, is preferably 0.1～0.5%wt.Silicone oil and silicone can improve the surface property of phosphor, and lubricated effect in wherein silicone also can play helps the dispersion of luminescent material and the frictional force in the reduction course of processing.
Can also include some auxiliary agents commonly used in the polypropylene course of processing such as toughener, fire retardant, nucleator, toughner, weighting agent, lubricant, look mother etc. in the composition of long persistence luminous polypropylene composition of the present invention, its consumption is conventional amount used, or adjusts according to practical requirements.
The preparation method of long persistence luminous polypropylene composition of the present invention comprises and will include the step of the component of described polypropylene, light-storing and emitting material, powdered rubber by melt blending, and makes long persistence luminous polypropylene composition.Normally each component is mixed, carry out melt blending then.
In the preparation method of the long persistence luminous polypropylene composition of the invention described above, described polypropylene comprises the disclosed various types of acrylic resins of prior art, comprises homo-polypropylene resin, Co-polypropylene resin etc.
At the powdered rubber described in the aforesaid method is median size 50～200nm, is preferably the powdered rubber of 80～150nm.Its gel content is 60% weight or higher, is preferably 80% weight or higher.This kind powdered rubber comprises a kind of or its mixing in butylbenzene powdered rubber and the carboxyl butylbenzene powdered rubber.This kind powdered rubber is preferably the rubber particles of equal phase structure.(with Chinese patent application 99125530.5 is right of priority to powdered rubber described in the inventive method Chinese patent ZL00816450.9 preferred above-mentioned, that the inventor applied on September 18th, 2000, priority date on December 3rd, 1999) cross-linked powdered rubber that the fully vulcanized powder rubber that is provided, and/or the inventor is provided in the Chinese patent ZL00130386.4 of application on November 3rd, 2000.
At the light-storing and emitting material described in the preparation method of the invention described above is in silicate systems light-storing and emitting material of the prior art, aluminates system light-storing and emitting material, the sulfide series light-storing and emitting material one or more.Be preferably in different kinds of ions activated silicate, the different kinds of ions activated aluminate one or more.。Its median size is preferably 10～40 μ m, more preferably 10～20 μ m.
Is 100 parts by weight at the consumption of luminescent material described in the aforesaid method in polypropylene, is 1～40 part, is preferably 10～30 parts.The powdered rubber consumption is 100 parts by weight in described polypropylene, is 1～10 part, is preferably 3～6 parts.
For the dispersion that is easy to luminescent material more being arranged and reducing frictional force in the course of processing, also can include silicone oil and/or silicone in the above component.Wherein silicone oil content is 0.1～1%wt of polypropylene weight, is preferably 0.1～0.5%wt; Silicone content is 0.1～1%wt of polypropylene weight, is preferably 0.1～0.5%wt.In this case, all components can be mixed the back melt blending, also can be earlier with luminescent material with mix with all the other components again after silicone oil and/or silicone mix, at last the material melt blending is prepared described luminous polypropylene composition.So more help silicone oil and/or silicone plays a role.Its concrete method may further comprise the steps:
1. with described light-storing and emitting material and silicone oil and/or the even blend of silicone, wherein silicone oil is 0.1～1%wt of polypropylene weight, is preferably 0.1～0.5%wt; Silicone is that 0.1～1%wt of polypropylene weight is preferably 0.1～0.5%wt;
2. the mixture that 1. step is obtained with comprise that the component of described polypropylene, powdered rubber makes long persistence luminous polypropylene composition by described component concentration melt blending.
Above step 1. the mixed of material can be carried out at normal temperatures, also carries out in the raising certain temperature.Temperature suitably improves, and can shorten the pretreated time, and general better suited temperature range is 30～80 ℃.
In the preparation process of long persistence luminous polypropylene composition of the present invention, material melt blending temperature is used blending temperature in the common polypropylene processing, can decide according to the polypropylene fusion temperature, should select not only guaranteeing the complete fusion of polypropylene matrix plastics but also can not make in the scope of its decomposition, be generally 160 ℃～240 ℃.In addition, according to the processing needs, can add some auxiliary agents commonly used in the polypropylene course of processing such as toughener, fire retardant, nucleator, toughner, weighting agent, lubricant, look mother etc. in the blend material in right amount, its consumption is conventional amount used, or adjusts according to practical requirements.
The blending equipment of mixing of materials in the preparation method of the invention described above (comprising the mixing of luminescent material and silicone oil, silicone) can adopt various mixing equipments used in the prior art, as stirrer, kneading machine etc.
Employed melt blending equipment is the general blending equipment in the rubber and plastic processing industry in the method for the invention described above, can be twin screw extruder, single screw extrusion machine, mill or Banbury mixer etc.
Add the accumulating type luminescent material in the long persistence luminous polypropylene composition of the present invention, and cooperate the adding powdered rubber simultaneously, can effectively improve the consistency of luminescent material in polypropylene, improve it and disperse, reduce the frictional force in the course of processing.Thereby can improve the add-on of luminescent material, make said composition that long fluorescent lifetime and higher brightness can in the dark be arranged, and do not have metachromatism; Also have good toughness simultaneously, and maintain higher intensity and rigidity.Through the PP composition of modification, processing characteristics is good, good fluidity, injection moulding easily.The resistance to impact shock of material is improved largely.
The good mechanical performance that long persistence luminous polypropylene composition of the present invention had, shock resistance are given prominence to, luminescent properties is good, nondiscoloration, nontoxic to human body, environment do not had advantage such as any pollution, be specially adapted to make the product of low-light (level) floodlighting in the time of need having significant illumination effect and need not have outer light source: as instrument, switch panel, socket panel, connector, telephone set, facsimile recorder, computer, household electrical appliance and sports cultural goods and amusement article or the like.Along with the attention of people to P.P., production safety, this series products will have huge market application foreground.Preparation method's technology of the present composition is simple, easy handling, is suitable for industrial applications.
Embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not subjected to the restriction of these embodiment, and scope of the present invention proposes in claims.
Embodiment 1～4:
With PP (polypropylene, 2401, the production of Beijing yanshan petrochemical company limited), vulcanize butylbenzene powdered rubber (VP-101 entirely, the Beijing Chemical Research Institute produces, particle diameter 80～110nm, gel content 80%wt), antioxidant 1010 (Switzerland vapour Ba Jiaji company), oxidation inhibitor 168 (Switzerland vapour Ba Jiaji company), calcium stearate (chemical plant, long positive farm, Beijing), (the Luming technology Group Co., Ltd., Dalian city's production of light-accumulating alkaline earth aluminate, trade mark PLO-6D, particle size range is 12～18 μ) put into low speed mixer and stir.Then mixture is passed through the twin screw extruder melt blending.The ZSK-40 twin screw extruder that the twin screw extruder that uses is produced for German WP company.Extrusion temperature is 160～240 ℃, and screw speed is 80～450rpm.Material is extruding pelletization after the twin screw extruder melt blending is even.The pellet of extruding is dried 6hr in 80 ℃ of constant temperature ovens, under 180～230 ℃ condition, be injected into the standard batten then, carry out the test of mechanical property and optical property.Concrete prescription sees Table 1, and wherein calcium stearate, antioxidant content are to account for the weight percentage of plastics gross weight, and other each component concentration is all in weight part.Results of property is as shown in table 1.
Embodiment 5
Earlier light-accumulating alkaline earth aluminate (with embodiment 1), silicone oil (chemical industry two factories in Beijing produce, trade mark 1000CP), silicone (Dow Corning produces, trade mark M201) are put into low speed mixer and stirred 3～5min, make each component thorough mixing even.In low speed mixer, make each component thorough mixing even again said mixture and polypropylene (with embodiment 1), form of finely divided powder, mehtod styrene-butadiene rubber(SBR) (with embodiment 1), oxidation inhibitor (with embodiment 1), calcium stearate (with embodiment 1) and (with embodiment 1) then.Then with the said mixture material by twin screw (ZSK-40, German WP company) melt blending.Extrusion temperature is 160～240 ℃, and screw speed is 80～450rpm.Material is extruding pelletization after the twin screw extruder melt blending is even.The pellet of extruding is dried 6hr in 80 ℃ of constant temperature ovens, under 180～230 ℃ condition, be injected into the standard batten then, carry out the test of mechanical property and optical property.Concrete prescription sees Table 1, and wherein silicone oil, silicone, calcium stearate, antioxidant content are to account for the weight percentage of plastics gross weight, and other each component concentration is all in weight part.Results of property is as shown in table 1.
Comparative example 1～2:
All the other components and condition are all with embodiment 1 except that not adding full sulfuration butylbenzene powdered rubber.Concrete prescription sees Table 1, and wherein calcium stearate, antioxidant content are to account for the weight percentage of plastics gross weight, and other each component concentration is all in weight part.Results of property is as shown in table 1.
The standard of the material for preparing in above embodiment and the Comparative Examples being carried out performance test is as follows:
Tensile strength, elongation at break: ASTM D638;
Flexural strength, modulus in flexure: ASTM D790;
Izod notched Izod impact strength: ASTM D256;
Luminescent properties test: adopt brightness to come the luminescent properties of exosyndrome material in the embodiment of the invention and the Comparative Examples.Concrete testing method is as follows: two 40W fluorescent tubes are positioned over print apart from light source 13cm place during test as light source, behind the irradiation 20min, test its luminous intensity with the MINOLTACS-100 chromascope in the darkroom.
Table 1
| Comparative example 1 | Comparative example 2 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| PP | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| VP101 | - | - | 5 | 3 | 6 | 9 | 6 |
| Luminescent material | 20 | 30 | 10 | 20.6 | 21.2 | 21.8 | 32 |
| Antioxidant 1010 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 | 0.2 |
| Oxidation inhibitor 168 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Calcium stearate | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.35 |
| Silicone oil | - | - | - | - | - | - | 0.2 |
| Silicone | - | - | - | - | - | - | 0.2 |
| Tensile strength (MPa) | 27.3 | 26.2 | 28.6 | 26.7 | 25.5 | 23.4 | 27.2 |
| Elongation at break (%) | 104 | 67 | 128 | 108 | 115 | 146 | 89 |
| Flexural strength (MPa) | 35.0 | 36.3 | 33.9 | 34.4 | 32.0 | 30.1 | 34.5 |
| Modulus in flexure (GPa) | 1.74 | 1.82 | 1.54 | 1.69 | 1.51 | 1.48 | 1.76 |
| Izod notched Izod impact strength J/m | 40.9 | 36.3 | 62.4 | 45.3 | 56.3 | 66.5 | 50.2 |
| Briliancy cd/m behind the 100s 2 | 1.78 | 2.51 | 1.07 | 1.80 | 1.85 | 1.78 | 2.50 |
| Briliancy cd/m behind the 200s 2 | 0.92 | 1.27 | 0.52 | 0.93 | 0.95 | 0.92 | 1.28 |
| Briliancy cd/m behind the 300s 2 | 0.58 | 0.83 | 0.33 | 0.58 | 0.60 | 0.61 | 0.84 |
| The goods colour-change | × | × | √ | √ | √ | √ | √ |
Annotate: *-variable color; √-nondiscoloration.
Can reach more than 12 hours the time of persistence of embodiment of the invention batten.
Comparative example 1 in the table 1 (luminescent material accounts for the about 16.6%wt of composition total weight) can compare with embodiment 2～4 (luminescent material accounts for the about 16.6%wt of composition total weight), and comparative example 2 (luminescent material accounts for the about 23.0%wt of composition total weight) can compare with embodiment 5 (luminescent material accounts for the about 23.0%wt of composition total weight).
The embodiment that lists from table 1 and the result of comparative example are as can be seen, when the luminescent material modified polypropene, add powdered rubber, can obviously change Drawing abillity, make the no considerable change before and after processing of polypropylene color, stopped not add the phenomenon of powdered rubber luminous polypropylene blackening before basically.In addition, in PP, add after the powdered rubber, the luminous intensity of material is not suffered a loss substantially even is strengthened to some extent, being added on of powdered rubber can improve the dispersion effect of luminescent material in the PP matrix to a certain extent, thereby help to improve the impact property of long-persistence luminous PP material, obtain good toughness.
Claims (13)
1. long persistence luminous polypropylene composition includes the following component of blend:
A. alkene 100 parts by weight in poly-
B. light-storing and emitting material 1～40 parts by weight
C. powdered rubber 1～10 parts by weight
Wherein said components b is one or more in silicate systems light-storing and emitting material, aluminates system light-storing and emitting material, the sulfide series light-storing and emitting material;
Wherein said amount of component b is median size 50～200nm, and gel content is 60% weight or higher powdered rubber, comprises a kind of or its mixing in butylbenzene powdered rubber and the carboxyl butylbenzene powdered rubber.
2. polypropene composition according to claim 1 includes the following component of blend:
A. alkene 100 parts by weight in poly-
B. light-storing and emitting material 10～30 parts by weight
C. powdered rubber 3～6 parts by weight.
3. polypropene composition according to claim 1, the median size of wherein said components b luminescent material are 10～40 μ m.
4. polypropene composition according to claim 3, the median size of wherein said components b luminescent material are 10～20 μ m.
5. polypropene composition according to claim 1, the luminescent material of wherein said components b are one or more in different kinds of ions activated silicate, the different kinds of ions activated aluminate.
6. polypropene composition according to claim 1, the powdered rubber of wherein said amount of component b are the rubber particles of equal phase structure.
7. polypropene composition according to claim 1, the median size of the powdered rubber of wherein said amount of component b are 80～150nm.
8. polypropene composition according to claim 1, the powdered rubber gel content of wherein said amount of component b is 80% weight or higher.
9. polypropene composition according to claim 1, the powdered rubber of wherein said amount of component b are one or more in fully vulcanized powder rubber and the cross-linked powdered rubber.
10. polypropene composition according to claim 1 wherein includes the silicone oil of polypropylene weight 0.1～1%wt and/or the silicone of polypropylene weight 0.1～1%wt.
11. polypropene composition according to claim 10, wherein said silicone oil are 0.1～0.5%wt of polypropylene weight, wherein said silicone is 0.1～0.5%wt of polypropylene weight.
12., comprise that the component that will include described polypropylene, light-storing and emitting material, powdered rubber makes described long persistence luminous polypropylene composition by the step of described component concentration by melt blending according to the preparation method of the described long persistence luminous polypropylene composition of one of claim 1～11.
13. the preparation method of polypropene composition according to claim 12 includes silicone oil and/or silicone in the wherein said component, may further comprise the steps:
1. with described luminescent material and silicone oil and/or the even blend of silicone, wherein silicone oil is 0.1～1%wt of polypropylene weight, and silicone is 0.1～1%wt of alkene weight in poly-;
2. the mixture that 1. step is obtained with comprise that the component of described polypropylene, powdered rubber makes long persistence luminous polypropylene composition by described component concentration melt blending.
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| CN101230164B (en) * | 2007-01-26 | 2011-11-30 | 中国石油化工股份有限公司 | Laser markable polyethylene composition and preparation method thereof |
| CN102382375A (en) * | 2010-09-03 | 2012-03-21 | 中国石油化工股份有限公司 | Special polypropylene material for automobile bumpers or upholsteries |
| CN102382369B (en) * | 2011-09-26 | 2013-06-12 | 广州市聚赛龙工程塑料有限公司 | Luminescent material special for street manhole cover and preparation method thereof |
| CN103965647A (en) * | 2014-05-04 | 2014-08-06 | 江苏华洋尼龙有限公司 | Luminous engineering plastic |
| CN109503948A (en) * | 2018-12-06 | 2019-03-22 | 轻工业部南京电光源材料科学研究所 | A kind of preparation method of energy-saving LED high thermal conductivity plastics |
| CN113845726B (en) * | 2021-10-25 | 2023-11-10 | 上海金发科技发展有限公司 | Luminous polypropylene material with good heat aging resistance appearance and preparation method thereof |
| CN114381065A (en) * | 2021-12-28 | 2022-04-22 | 重庆普利特新材料有限公司 | Long-afterglow luminous polypropylene composite material suitable for automotive interior parts and preparation method thereof |
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| CN1301792A (en) * | 1999-12-30 | 2001-07-04 | 大连路明科技集团有限公司 | Luminous plastic masterbatch and its production |
| CN1402752A (en) * | 1999-12-03 | 2003-03-12 | 中国石油化工集团公司 | Full vulcanized powdered rubber with controllable particle diameter, preparing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1402752A (en) * | 1999-12-03 | 2003-03-12 | 中国石油化工集团公司 | Full vulcanized powdered rubber with controllable particle diameter, preparing method thereof |
| CN1301792A (en) * | 1999-12-30 | 2001-07-04 | 大连路明科技集团有限公司 | Luminous plastic masterbatch and its production |
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