CN100338171C - Long persistence luminous thermoplastic plastics composition and method of making the same - Google Patents

Long persistence luminous thermoplastic plastics composition and method of making the same Download PDF

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CN100338171C
CN100338171C CNB2004100863784A CN200410086378A CN100338171C CN 100338171 C CN100338171 C CN 100338171C CN B2004100863784 A CNB2004100863784 A CN B2004100863784A CN 200410086378 A CN200410086378 A CN 200410086378A CN 100338171 C CN100338171 C CN 100338171C
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China
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rubber
thermoplastic plastics
weight
powdered rubber
component
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CNB2004100863784A
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Chinese (zh)
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CN1769366A (en
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张师军
张薇
张丽英
尹华
吕明福
邵静波
张�浩
吕芸
王小兰
段淑清
李魁
陈力
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中国石油化工股份有限公司
中国石油化工股份有限公司北京化工研究院
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Abstract

The present invention provides a long persistence luminous thermoplastic plastic composition and a preparation method thereof, which belongs to the field of luminous plastic. The present invention makes use of light accumulation luminescent materials and powdered rubber with particle diameters of 30 to 600 nm which are matched with thermoplastic for melt blending. The present invention effectively avoids luminescent material dispersion in the thermoplastic plastic, reduces machining friction force and increases the impact property and the irradiance property of the composition, and therefore, the present invention obtains the thermoplastic plastic with large luminescent material addition level, high brightness, good toughness and no discoloring. With 100 weight portions of the thermoplastic plastic, the composition has 1 to 40 portions of luminescent material and 10 to 20 portions of powdered rubber. The composition of the present invention is suitable for manufacturing products which need lighting effects and can reduce irradiance floodlighting without external light sources and has wide application. The preparation method of the composition of the present invention has the advantages of simple process and easy operation and is suitable for industrialization application.

Description

A kind of long persistence luminous thermoplastic plastics composition and preparation method thereof
Technical field
The present invention relates to a kind of luminescent plastics composition, say further, relate to a kind of long persistence luminous thermoplastic plastics composition and preparation method thereof.
Background technology
Long persistence luminous thermoplastic plastics range of application on market is more and more wide at present.People mainly take two kinds of approach in order to make plastics have noctilucent performance: a kind of is to apply luminous paint on plastics, paste and inlay twinkler; Another kind is exactly to add luminous filler in plastics.
On plastics, apply luminous paint, paste and inlay twinkler, be actually plastics, add surface with lighting function as main structure body.These plastics are not 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 are difficult in actual applications promote.
Prepare the development technique of luminescent plastics and closely related, the traditional luminous PP employing fluorescent material of performance of phosphor by the method for in plastics, filling luminous filler, as ZnS, CaS etc.But their poor stabilities, time of persistence is shorter, and work-ing life is not long yet.The sixties in 20th century, utilize 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, Xiao Zhiguo chief editor, Chemical Industry Press publishes in October, 2002) research change the application stage over to by conceptual phase.This material has characteristics such as nontoxic, harmless, "dead", 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, and its absorbing time is short, and 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.Many long persistence luminous thermoplastics generally are to make through the melt blending extruding pelletization with thermoplastic resin with energy-saving luminous material.
As U.S. Pat 6,716,368 adopt the twin screw extruder of single screw extrusion machine or band side direction feeding device can make the luminous polycarbonate material that luminescent material weight is composition weight 0.01~2%.This luminous polycarbonate material can be used for making various injected articles.Wherein luminescent material is an aluminate luminescent material.Because this material hardness is big, after extruding, have variable color, cause outward appearance relatively poor.
U.S. Pat P6,692,659 adopt luminescent material and resin alloy to make light emitting composition, and wherein luminescent material is an aluminate, but its goods variable color outward appearance is bad.
Be to adopt luminescent material and resin alloy to make luminous masterbatch among the Chinese patent CN1301792A, prepare light emitting composition with resin alloy again.Wherein in order to ensure that mechanical property sneaks into a large amount of thermoplastic elastomers.Wherein luminescent material is an aluminate, on the technology with banburying, open the refining or boil, loaded down with trivial details time-consuming.
These patents can be prepared the thermoplastics with certain mechanical property and characteristics of luminescence.But under existing blend technology of preparing condition, the effect that energy-saving luminous material is rubbed in the course of processing, shears may be damaged lattice, causes luminous afterglow intensity to descend; 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.And because energy-saving luminous material is an inorganic materials, particle diameter is generally bigger, and difficulty good distribution in the thermoplastics 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
At above problems of the prior art, the present invention is intended to obtain a kind of luminescent plastics that has high tenacity and good appearance when having good luminous performance.
Therefore, the purpose of this invention is to provide a kind of have good luminous property and high tenacity and non-discoloring luminous thermoplastic plastics composition.
Another object of the present invention provides the preparation method of described luminous thermoplastic plastics composition.
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, reduces 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 matrix plastic generally.
A kind of long persistence luminous thermoplastic plastics composition provided by the present invention includes the following component of blend: a. thermoplastics; B. light-storing and emitting material; C. powdered rubber.
The above plastics composite of the present invention, wherein the thermoplastics of component a can be selected from the thermoplastics of any kind of in the prior art, gets final product so long as can carry out melt blending processing.Preferentially be selected from least a in the following plastics: polyethylene, polypropylene, polyvinyl chloride, polyester, polycarbonate, polymeric amide, polystyrene, acrylonitrile-butadiene-styrene (ABS) (ABS), acrylonitrile-styrene (AS) etc.
The above plastics composite 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 CN 1120207C.
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 thermoplastics, is 1~40 part.The preferable range of its content is 5~30 parts.
The above plastics composite of the present invention, wherein amount of component b is median size 30~600nm, is preferably 40~500nm, more preferably 50~150nm; 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, and it can be selected from butylbenzene powdered rubber, carboxyl butylbenzene powdered rubber, esters of acrylic acid powdered rubber, powder nbr rubber, carboxyl butyronitrile powdered rubber, butylbenzene pyrrole powdered rubber, silicon rubber, polybutadiene rubber, chloroprene rubber, the natural rubber etc. one or more.
The powdered rubber of described amount of component b can adopt the Chinese patent ZL00816450.9 that applies on September 18th, 2000 according to the inventor, and (with Chinese patent application 99125530.5 is right of priority, priority date on December 3rd, 1999) prepared fully vulcanized powder rubber, comprise at least a of following fully vulcanized powder rubber: form of finely divided powder, mehtod styrene-butadiene rubber(SBR), the form of finely divided powder, mehtod carboxylic styrene-butadiene rubber, the form of finely divided powder, mehtod paracril, the form of finely divided powder, mehtod carboxy nitrile rubber, form of finely divided powder, mehtod esters of acrylic acid class rubber, the form of finely divided powder, mehtod vinylpyridiene-styrene-butadiene rubber, fully sulfurized silicon rubber powder, the form of finely divided powder, mehtod polybutadiene rubber, the form of finely divided powder, mehtod chloroprene rubber, form of finely divided powder, mehtod natural rubber etc.This kind fully vulcanized powder rubber is meant that gel content reaches 60% weight or higher, is preferably 75% weight or higher, and need not with separant after the drying is free flowable rubber micro mist.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, comprises at least a of following cross-linked powdered rubber: cross-linked powdery styrene-butadiene rubber(SBR), cross-linked powdery carboxylic styrene-butadiene rubber, cross-linked powdery polybutadiene rubber, cross-linked powdery acrylonitrile butadiene, cross-linked powdery carboxy nitrile rubber, cross-linked powdery chloroprene rubber, cross-linked powdery esters of acrylic acid 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, 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 this cross-linked powdered rubber of 50~300nm and need 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 thermoplastics, is 1~20 part.The preferable range of its content is 1~15 part.
Thermoplastic plastics composite 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 thermoplastics weight, is preferably 0.1~0.5%wt; Silicone content is 0.1~1%wt of thermoplastics 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 in the thermoplastics course of processing some auxiliary agents commonly used such as toughener, fire retardant, nucleator, toughner, weighting agent, lubricant (polymer is cured etc.), look mother etc. in the composition of long persistence luminous thermoplastic plastics composition of the present invention, its consumption is conventional amount used, or adjusts according to practical requirements.
The preparation method of long persistence luminous thermoplastic plastics composition of the present invention, comprise the component that will comprise described thermoplastics, light-storing and emitting material, powdered rubber by the step of described component concentration, and make described long persistence luminous thermoplastic plastics composition by melt blending.Normally each component is mixed, carry out melt blending then.
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.
Can be selected from the thermoplastics of any kind of in the prior art at the thermoplastics described in the preparation method of the invention described above, get final product so long as can carry out melt blending processing.Preferentially be selected from least a in the following plastics: polyethylene, polypropylene, polyvinyl chloride, polyester, polycarbonate, polymeric amide, polystyrene, acrylonitrile-butadiene-styrene (ABS) (ABS), acrylonitrile-styrene (AS) etc.
At the powdered rubber described in the preparation method of the invention described above is median size 30~600nm, is preferably 40~500nm, more preferably the powdered rubber of 50~150nm.Its gel content is 60% weight or higher, is preferably 80% weight or higher.This kind powdered rubber is preferably the rubber particles of equal phase structure, and it can be selected from butylbenzene powdered rubber, carboxyl butylbenzene powdered rubber, esters of acrylic acid powdered rubber, powder nbr rubber, carboxyl butyronitrile powdered rubber, butylbenzene pyrrole powdered rubber, silicon rubber, polybutadiene rubber, chloroprene rubber, the natural rubber etc. one or more.The cross-linked powdered rubber that the fully vulcanized powder rubber that preferred above-mentioned, the inventor of powdered rubber in the inventive method is provided in the Chinese patent ZL00816450.9 of application on September 18th, 2000 (is right of priority with Chinese patent application 99125530.5, priority date on December 3rd, 1999) and/or the inventor are provided in the Chinese patent ZL00130386.4 of application on November 3rd, 2000.
Is 100 parts by weight at light-storing and emitting material consumption described in the preparation method of the invention described above in described thermoplastics, is 1~40 part, is preferably 5~30 parts.The powdered rubber consumption is 100 parts by weight in described thermoplastics, is 1~20 part, is preferably 1~15 part.
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 thermoplastics weight, is preferably 0.1~0.5%wt; Silicone content is 0.1~1%wt of thermoplastics 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 thermoplastic plastics 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 thermoplastics weight, is preferably 0.1~0.5%wt; Silicone is that 0.1~1%wt of thermoplastics weight is preferably 0.1~0.5%wt;
2. the mixture that 1. step is obtained with comprise that the component of described thermoplastics, powdered rubber makes long persistence luminous thermoplastic plastics 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 thermoplastic plastics composition of the present invention, the melt blending temperature of material be common thermoplastics its process separately in used blending temperature, can decide according to the thermoplastic molten temperature, should select not only guaranteeing the complete fusion of matrix plastic but also can not make in the scope of its decomposition.In addition, according to the processing needs, can in the blend material, add some auxiliary agents commonly used in the thermoplastics course of processing such as toughener, fire retardant, nucleator, toughner, weighting agent, lubricant, look mother etc. 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.
The employed melt blending equipment of material melt blending is the general blending equipment in the rubber and plastic processing industry in the preparation method of the invention described above, can be twin screw extruder, single screw extrusion machine, mill or Banbury mixer etc.
Add light-storing and emitting material in the long persistence luminous thermoplastic plastics composition of the present invention, and cooperate the adding powdered rubber simultaneously, can effectively improve the consistency of luminescent material in thermoplastics, 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; Simultaneously can also make composition have high toughness and good appearance.
The good mechanical performance that long persistence luminous thermoplastic plastics 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:
(Luming technology Group Co., Ltd., Dalian city produces with the light-accumulating alkaline earth aluminate, trade mark PLO-6D, particle size range is 12~18 μ), polypropylene (Yanshan Petrochemical production, the trade mark 2401), (the Sinopec Beijing Chemical Research Institute produces to vulcanize the butylbenzene powdered rubber entirely, VP101, median size is 80~100nm, about 80% weight of gel content), oxidation inhibitor (1010, Switzerland vapour Ba Jiaji) and calcium stearate (chemical plant, long positive farm, Beijing) make each component thorough mixing even in low speed mixer.Then with the said mixture material pass through twin screw (ZSK-40, German WP company), under 200~240 ℃ with the rotating speed melt blending extruding pelletization of 200~350r.p.m.The pellet of extruding is dried 9hr in 90 ℃ of constant temperature ovens, under 240~255 ℃ of injection temperatures, be injected into the standard batten then, carry out various Mechanics Performance Testings.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 parts by weight (polypropylene is 100 parts by weight).Testing standard and results of property are as shown in table 1.
Comparative example 1
Except not adding the fully vulcanized powder rubber, all the other conditions are all with embodiment 1.Wherein Ployethylene Wax, antioxidant content are to account for the weight percentage of plastics gross weight, and other each component concentration is all in parts by weight (polypropylene is 100 parts by weight).Concrete prescription, testing standard and results of property are as shown in table 1.
Embodiment 2~3:
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.Then with said mixture and polycarbonate (GE company, 141R), (the Sinopec Beijing Chemical Research Institute produces full propylene sulfide esters of gallic acid powdered rubber, VP301, median size is 80~110nm, gel content about 85%), oxidation inhibitor (with embodiment 1) and Ployethylene Wax (with embodiment 1) make each component thorough mixing even again in low speed mixer.Then with the said mixture material by twin screw (ZSK-40, German WP company), under 250~280 ℃ with the rotating speed melt blending extruding pelletization of 200~350r.p.m.The pellet of extruding is dried 9hr in 90 ℃ of constant temperature ovens, under 240~255 ℃ of injection temperatures, be injected into the standard batten then, carry out various Mechanics Performance Testings.Concrete prescription sees Table 1, and wherein silicone oil, silicone, Ployethylene Wax, antioxidant content are to account for the weight percentage of plastics gross weight, and other each component concentration is all in parts by weight (polypropylene is 100 parts by weight).Testing standard and results of property are as shown in table 1.
Comparative example 2
Except not adding the fully vulcanized powder rubber, all the other conditions are all with embodiment 2.Wherein silicone oil, silicone, Ployethylene Wax, antioxidant content are to account for the weight percentage of plastics gross weight, and other each component concentration is all in parts by weight (polycarbonate is 100 parts by weight).Concrete prescription, testing standard and results of property are as shown in table 1.
Embodiment 4:
Earlier light-accumulating alkaline earth aluminate (with embodiment 1), silicone oil (with embodiment 2), silicone (with embodiment 2) are put into low speed mixer and stirred 3~5min, make each component thorough mixing even.Then with said mixture and nylon (tafelberg petrochemical industry, trade mark Nylon6), (the Sinopec Beijing Chemical Research Institute produces to vulcanize butylbenzene pyrrole powdered rubber entirely, VP701, median size is 80~110nm, gel content about 82%), oxidation inhibitor (with embodiment 1) and Ployethylene Wax (with embodiment 1) make each component thorough mixing even again in low speed mixer.Then with the said mixture material by twin screw (ZSK-40, German WP company), under 240~270 ℃ with the rotating speed melt blending extruding pelletization of 200~350r.p.m.The pellet of extruding is dried 9hr in 90 ℃ of constant temperature ovens, under 240~255 ℃ of injection temperatures, be injected into the standard batten then, carry out various Mechanics Performance Testings.Concrete prescription sees Table 1, and wherein silicone oil, silicone, Ployethylene Wax, antioxidant content are to account for the weight percentage of plastics gross weight, and other each component concentration is all in parts by weight (polypropylene is 100 parts by weight).Testing standard and results of property are as shown in table 1.
Comparative example 3
Except not adding fully vulcanized powder rubber, silicone oil, silicone, all the other conditions are all with embodiment 3.Wherein Ployethylene Wax, antioxidant content are to account for the weight percentage of plastics gross weight, and other each component concentration is all in parts by weight (nylon 6 is 100 parts by weight).Concrete prescription, testing standard and results of property are 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 Embodiment 1 Comparative example 2 Embodiment 2 Embodiment 3 Comparative example 3 Embodiment 4
??PP ??100 ??100 ??- ??- ??- ??- ??-
??PC ??- ??- ??100 ??100 ??100 ??- ??-
??PA6 ??- ??- ??- ??- ??- ??100 ??100
Light-storing and emitting material ??20 ??20 ??5 ??5 ??30 ??10 ??10
??VP101 ??- ??9 ??- ??- ??- ??- ??-
??VP301 ??- ??- ??- ??1 ??10 ??- ??-
??VP701 ??- ??- ??- ??- ??- ??- ??10
Silicone ??- ??- ??0.2 ??0.2 ??0.2 ??- ??0.2
Silicone oil ??- ??- ??0.2 ??0.2 ??0.2 ??- ??0.2
Calcium stearate ??0.3 ??0.3 ??- ??- ??- ??- ??-
??PE-WAX ??- ??- ??0.3 ??0.3 ??0.3 ??0.1 ??0.1
Antioxidant 1010 ??0.15 ??0.15 ??0.1 ??0.1 ??0.1 ??0.1 ??0.1
Oxidation inhibitor 168 ??0.3 ??0.3 ??0.1 ??0.1 ??0.1 ??- ??-
Tensile strength MPa ??27.3 ??23.4 ??57.7 ??64.9 ??62.6 ??54.5 ??53.7
Elongation at break % ??104 ??146 ??53 ??89 ??141 ??25 ??86
Flexural strength MPa ??35.0 ??30.1 ??80.1 ??88.3 ??85.7 ??78.9 ??75.7
Modulus in flexure GPa ??1.74 ??1.48 ??2.48 ??2.35 ??2.37 ??2.18 ??2.03
Izod notched Izod impact strength J/m ??40.9 ??66.5 ??101 ??185 ??210 ??41.2 ??118.5
Briliancy cd/m behind the 100s 2 ??1.78 ??1.78 ??0.46 ??0.45 ??0.94 ??0.87 ??1.01
Briliancy cd/m behind the 200s 2 ??0.92 ??0.92 ??0.24 ??0.22 ??0.48 ??0.39 ??0.45
Briliancy cd/m behind the 300s 2 ??0.58 ??0.61 ??0.17 ??0.17 ??0.30 ??0.27 ??0.33
The goods colour-change ??× ??√ ??× ??√ ??√ ??× ??√
Annotate: *---variable color; √---nondiscoloration.
Can reach more than 12 hours the time of persistence of embodiment of the invention batten
The embodiment that lists from table 1 and the result of comparative example are as can be seen, when the luminescent material modified plastics, add powdered rubber, can obviously change Drawing abillity, make the no considerable change before and after processing of plastics color, stop not add the phenomenon of powdered rubber plastics blackening before basically.In addition, in thermoplastics, 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 plastic substrate to a certain extent, thereby help to improve the impact property of long persistence luminous thermoplastic plastics composition, obtain the luminous thermoplastic plastics composition of good toughness and briliancy.

Claims (16)

1. long persistence luminous thermoplastic plastics composition includes the following component of blend:
A. thermoplastics 100 parts by weight
B. light-storing and emitting material 1~40 parts by weight
C. powdered rubber 1~20 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 the powdered rubber of median size 30~600nm.
2. thermoplastic plastics composite according to claim 1 includes the following component of blend:
A. thermoplastics 100 parts by weight
B. light-storing and emitting material 5~30 parts by weight
C. powdered rubber 1~15 parts by weight.
3. thermoplastic plastics composite according to claim 1, wherein said thermoplastics are selected from least a in the following plastics: polyethylene, polypropylene, polyvinyl chloride, polyester, polycarbonate, polymeric amide, polystyrene, acrylonitrile-butadiene-styrene copolymer, acrylonitritrile-styrene resin.
4. thermoplastic plastics composite according to claim 1, the median size of wherein said components b light-storing and emitting material are 10~40 μ m.
5. thermoplastic plastics composite according to claim 4, the median size of the light-storing and emitting material of wherein said components b are 10~20 μ m.
6. thermoplastic plastics composite according to claim 1, the light-storing and emitting material of wherein said components b are one or more in different kinds of ions activated silicate, the different kinds of ions activated aluminate.
7. thermoplastic plastics composite according to claim 1, the powdered rubber of wherein said amount of component b are the rubber particles of equal phase structure.
8. thermoplastic plastics composite according to claim 1, the powdered rubber gel content of wherein said amount of component b is 60% weight or higher.
9. thermoplastic plastics composite according to claim 1, the powdered rubber gel content of wherein said amount of component b is 80% weight or higher.
10. thermoplastic plastics composite according to claim 1, the median size of the powdered rubber of wherein said amount of component b are 40~500nm.
11. thermoplastic plastics composite according to claim 1, the powdered rubber of wherein said amount of component b are selected from least a in the following powdered rubber: butylbenzene powdered rubber, carboxyl butylbenzene powdered rubber, esters of acrylic acid powdered rubber, powder nbr rubber, carboxyl butyronitrile powdered rubber, butylbenzene pyrrole powdered rubber, silicon rubber, polybutadiene rubber, chloroprene rubber, natural rubber.
12. thermoplastic plastics composite according to claim 1, the powdered rubber of wherein said amount of component b be in fully vulcanized powder rubber or the cross-linked powdered rubber one or more.
13. thermoplastic plastics composite according to claim 1 wherein includes the silicone oil of thermoplastics weight 0.1~1%wt and/or the silicone of thermoplastics weight 0.1~1%wt.
14. thermoplastic plastics composite according to claim 13, wherein said silicone oil are 0.1~0.5%wt of thermoplastics weight, wherein said silicone is 0.1~0.5%wt of thermoplastics weight.
15., comprise that the component that will comprise described thermoplastics, light-storing and emitting material, powdered rubber makes described long persistence luminous thermoplastic plastics composition by the step of described component concentration by melt blending according to the preparation method of the described long persistence luminous thermoplastic plastics composition of one of claim 1~14.
16. the preparation method of thermoplastic plastics composite according to claim 15 includes silicone oil and/or silicone in the wherein said component, may further comprise the steps:
1. with the silicone oil and/or the even blend of silicone of described light-storing and emitting material and described amount;
2. the mixture that 1. step is obtained with comprise that the component of described thermoplastics, powdered rubber makes long persistence luminous thermoplastic plastics composition by described component concentration melt blending.
CNB2004100863784A 2004-10-27 2004-10-27 Long persistence luminous thermoplastic plastics composition and method of making the same CN100338171C (en)

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