CN102585423A - Photochromic high-polymer composition - Google Patents
Photochromic high-polymer composition Download PDFInfo
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- CN102585423A CN102585423A CN2011100054991A CN201110005499A CN102585423A CN 102585423 A CN102585423 A CN 102585423A CN 2011100054991 A CN2011100054991 A CN 2011100054991A CN 201110005499 A CN201110005499 A CN 201110005499A CN 102585423 A CN102585423 A CN 102585423A
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Abstract
The invention discloses a photochromic high-polymer composition. The photochromic high-polymer composition comprises methyl methacrylate-acrylonitril-butadiene-styrenencopolymer (MABS) resin and a coloring agent. The photochromic high-polymer composition disclosed by the invention not only has the advantages of better pressure resistance and high extensibility but also is capable of keeping a certain color-change effect, and thereby, characters and patterns with better effects can be conveniently formed on the surfaces of plastic parts.
Description
Technical field
The present invention relates to a kind of polymeric composition, particularly a kind of photochromic polymeric composition.
Background technology
Generally desire at frosting printing type face or design configuration, can see through accomplished in many ways, for example intaglio plate bat printing (Pad Printing) method, dipping printing (Impregnation Printing) method and laser labelling (Laser Marking) method etc.
Wherein, the application of intaglio plate pad printing method is the most extensive, and main technical principle is to utilize one group of character font as original type matrix;, again one group of soft rubber piece is pressed in above it, when lifting block rubber after brushing printing ink above it through automation; Writing printing ink will be transferred on the block rubber; And then block rubber moved on on the keyboard of space, block rubber is pressed on the keyboard, printing ink just has been printed on the keyboard; Yet it has drawback: the solvent that process velocity is slow and cost is high, used causes environmental pollution easily and needs higher facility investment etc.
And the cardinal principle of dipping printing process is on transcription film or paper, to use the ink with sublimability, and through heating and pressing mode ink bleed is advanced in the plastics; Yet the dipping printing process has the shortcoming of manufacturing cost height and complex process.
On the other hand; The cardinal principle of laser labeling method is to utilize laser beam to burn the literal vestige at body surface; Its method is simple; Relative preceding method cost is lower and speed is fast, can also keep the good persistence and the environmental protection of printing material, so laser labeling method has higher using value in industry; But the existing photochromic material that is applied to laser labeling method; Often be applied to assemblies such as keyboard or button, be characterized in that the surface needs mark or character or figure and often need push or rub, and the existing laser labeling method material of selecting for use be in order to keep the contrast gradient of surface printing font or design configuration and base material; But can't have the crushing resistance and the ductility of material concurrently; And be prone to embrittlement or damage causes reducing its life cycle, and the material color kind of using is restricted, and has only two kinds of colors of black and white at present; Wherein, material commonly used is polymethylmethacrylate (PMMA) or acrylonitrile-styrene-butadienecopolymer (ABS resin).
See also Fig. 1; This figure is the chemical formula synoptic diagram of ABS resin; ABS resin is by two incompatible phases, mainly mutually by polybutadiene rubber and (AN-SM) resin since two mutually between refractive index difference cause light scattering effect; Make material lose the transparency and be the relatively poor material of transparency, and that PMMA is prone to is crisp.
Therefore, be necessary to provide a kind of compressive resistance that has concurrently with good ductility and can keep certain variable color photochromic macromolecular material of (contrast gradient) mutually again, and can allocate material color, to address the above problem according to demand.
Summary of the invention
The technical problem that the present invention mainly solves provides a kind of photochromic polymeric composition, and it has compressive resistance concurrently with good ductility and can keep certain variable color (contrast gradient) mutually again, and can allocate material color according to demand.
The present invention provides a kind of photochromic polymeric composition; This photochromic polymeric composition comprises: a MABS resin (Methyl methacrylate-Acrylonitril-Butadiene-Styrenencopolymer, a MABS) resin and a black pigment.
Preferably, this black pigment is dyestuff or pigment.
Preferably, this black pigment is 0.03%～0.1% with respect to the part by weight of this MABS resin.
Preferably, this black pigment is a carbon black.
Preferably, this photochromic polymeric composition further comprises one second resin, and this second resin is plexiglass (PMMA), ethyl propenoate, Bing Xisuandingzhi, 2-EHA or (methyl) vinylformic acid C
1-10Alkyl ester.
Preferably, this MABS resin is 80%～99% with respect to the part by weight of this second resin and this MABS resin total amount.
Preferably, this black pigment is 0.03%～0.1% with respect to the part by weight of the resin total amount of this MABS resin and this second resin.
Preferably, this light is laser, and the wavelength of this laser is between between the 355nm to 1.06um.
Preferably, this photochromic polymeric composition further comprises one second colorant.
Preferably, this photochromic polymeric composition further comprises an auxiliary agent, and this auxiliary agent is a wax.
Preferably, this light makes this photochromic polymeric composition become white by black.
The invention has the beneficial effects as follows: the situation that is different from prior art; The present invention sees through that MABS resin and black pigment carry out suitable collocation as photochromic polymeric composition preferably with the transparency and mechanical quality; Not only have better crushing resistance and ductibility; Can also keep certain look and become effect, thereby be convenient to form the preferable literal of effect, pattern etc. on the plastic component surface, and through adding second colorant; Allocate required color voluntarily according to actual demand, do not need only to be confined to black or white substrate.
Description of drawings
Fig. 1 is the chemical formula synoptic diagram of ABS resin;
Fig. 2 is the experiment flow synoptic diagram of the photochromic polymeric composition of the present invention;
Fig. 3 is the part by weight of the employed material of experiment;
Fig. 4 is the corresponding form and aspect experimental result of material shown in Figure 3;
Fig. 5 is the corresponding physical property experiment result of material shown in Figure 3.
Embodiment
MABS (MABS; Methylmethacrylate-Acrylonitril-Butadiene-Styrenen copolymer) resin is a kind of common ABS resin (acrylonitrile-butadiene-styrene copolymer that has concurrently; Acrylonitrile-Butadiene-Styrene copolymer) highstrenghtpiston of the resin mechanical quality and the transparency; Its production cost is suitable with common ABS resin, and its overall quality is superior to common synthetic glass transparent material.Among Fig. 1, AN is vinyl cyanide (Acrylonitrile), and SM is vinylbenzene (Styrene), and BD is divinyl (Butadiene), and MMA is TEB 3K (methylmethacrylate).ABS resin and MABS resin difference are: ABS resin is the combination of AN-SM; And the MABS resin is the combination of MMA-AN-SM; Because be to reduce polybutadiene rubber and (MMA-AN-SM) resin refringence mutually, and then the attenuating light scattering effect, it is transparent to reach visible region; Because therefore the difference of said chemical formula structure make the quality of ABS resin and MABS resin have than big-difference, the MABS resin is a transparent material, and the light transmission of MABS resin can reach 85%.
Therefore, the photochromic polymeric composition of the method for the light that the present invention utilizes the prescription of the good characteristic mixing colorant of MABS resin material to provide to be applicable to specific wavelength and mark literal or figure, and the light of this specific wavelength is preferably laser.
In first embodiment of the photochromic polymeric composition of the present invention; This photochromic polymeric composition comprises MABS resin and black pigment (coloring agent); As stated; The MABS resin has mechanical quality and transparency preferably, and wherein, the transparency of MABS resin can reach 85%.This black pigment can be dyestuff (dye) or pigment (pigment), and this black pigment is 0.03%～0.1% with respect to the part by weight of this MABS resin, and preferably, this black pigment can be carbon black; In addition, in further evolutionary approach, can continue to add auxiliary agent, for example add wax (WAX), so, can make the distribution of this colorant in this MABS resin more even as auxiliary agent at this photochromic polymeric composition.
When using this photochromic polymeric composition of rayed; When for example in a reasonable time, using this photochromic polymeric composition of laser beam irradiation; This photochromic polymeric composition can be transformed into white (white marking) by native color (present embodiment is a black); When increasing along with the time, white can change inclined to one side Huang into thereupon, in specific time, can change yellow at last.Wherein, the preferred wavelength of laser beam is between the 355nm to 10.6um.According to testing data, be the CO of 10600nm when selecting wavelength for use
2During this photochromic polymeric composition of laser radiation, produce thermal chemical reaction, mark the effect of similar engraving; When selecting for use wavelength to be this photochromic polymeric composition of Nd:YAG (yag crystal) laser radiation of 1064nm, produce thermal chemical reaction, the effect of mark is more above-mentioned to be good; When selecting for use wavelength to be this photochromic polymeric composition of UV laser radiation of 355nm, because it is a collimated laser beam, the effect of mark is for better.
In second embodiment of the photochromic polymeric composition of the present invention; This photochromic polymeric composition has also added another kind of colorant except comprising MABS resin and black pigment, i.e. second colorant; Further to improve the required color of this photochromic polymeric composition through this second colorant allotment; In other words, the present invention's photochromic polymeric composition can mix the color that is presetted through MABS resin and black pigment and second colorant, can reach customized demand.In addition, in further evolutionary approach, can continue to add auxiliary agent, for example add wax, so, can make this black pigment and the distribution of this second colorant in this MABS resin more even as auxiliary agent at this photochromic polymeric composition; The embodiment and first embodiment when using this photochromic polymeric composition of rayed are similar, repeat no more at this.
In the 3rd embodiment of the photochromic polymeric composition of the present invention, this photochromic polymeric composition also further comprises second resin except comprising MABS resin and black pigment; Wherein, This MABS resin is 80%～99% with respect to the part by weight of this second resin and this MABS resin total amount; In other words, the part by weight of the total amount of relative this second resin of this second resin and this MABS resin can be 1%～20%, can allocate ratio according to actual demand; In addition, this black pigment is 0.03%～0.1% with respect to the part by weight of the resin total amount of this MABS resin and this second resin.In this embodiment, this second resin can be a kind of in the following material or several combination: plexiglass (PMMA), ethyl propenoate, Bing Xisuandingzhi, 2-EHA or (methyl) vinylformic acid C
1-10Alkyl ester.Certainly; In the photochromic polymeric composition of this embodiment, can add another colorant equally, i.e. second colorant; Further to improve the required color of this photochromic polymeric composition through this second colorant allotment; In other words, the present invention's photochromic polymeric composition can mix required color through MABS resin, second resin, black pigment and second colorant, can reach customized demand.In addition, in further evolutionary approach, can continue to add auxiliary agent, for example add wax, so, can make this black pigment and the distribution of this second colorant in this MABS resin more even as auxiliary agent at this photochromic polymeric composition; The embodiment and first embodiment when using this photochromic polymeric composition of rayed are similar, repeat no more at this.
See also Fig. 2, Fig. 2 representes the experiment flow of the photochromic polymeric composition of the present invention:
At first, with the prescription of photochromic polymeric composition, promptly wherein each material composition carries out mixing processing; Wherein, can use the twin shaft extruder as machine table, preferable processing temperature is 200 degrees centigrade～220 degrees centigrade;
Secondly, the prescription after the mixing processing is carried out granulation; Wherein, can use Jet forming machine as machine table, preferable processing temperature is 200 degrees centigrade～220 degrees centigrade;
Then, the material after the granulation is carried out tensile test specimen, impact test piece and colour table test etc.;
Wherein, in tensile test specimen, the material after using omnipotent tensile test machine to granulation carries out the tensile strength test to be tested with unit elongation;
In impact test piece, the material after using the impulse withstand test machine to granulation carries out the shock strength test;
In colour table test, the material after using laser marking machine to granulation carries out the laser labelling assessment, uses spectrometer to carry out the form and aspect assessment to the white marking behind the laser labelling then; The colour table thickness of test is 2mm.
See also Fig. 3, for testing the part by weight of employed material, this experiment is divided into 5 kinds of experiment materials; Be noted that at first dyestuff and wax are necessity interpolation material of non-the present invention, following experiment is to be added to scale to increase color feature; Close and chat brightly earlier, details are as follows in regular turn for its material:
Material 1:
Wherein material 1 forms for using the PMMA resin and adding carbon black (CB), dyestuff (Dye) and wax (Wax); Wherein carbon black is 0.05% with respect to the part by weight of this PMMA resin; This dyestuff is 0.0475% with respect to the part by weight of this PMMA resin, and this wax phase is 0.06% for the part by weight of this PMMA resin.
Material 2:
Wherein material 2 forms for using the MABS resin and adding carbon black (CB), dyestuff (Dye) and wax (Wax); Wherein carbon black is 0.05% with respect to the part by weight of this MABS resin; This dyestuff is 0.0475% with respect to the part by weight of this MABS resin, and this wax phase is 0.06% for the part by weight of this MABS resin.
Material 3:
Wherein material 3 forms for using ABS resin and adding carbon black (CB), dyestuff (Dye) and wax (Wax); Wherein carbon black is 0.05% with respect to the part by weight of this ABS resin; This dyestuff is 0.0475% with respect to the part by weight of this ABS resin, and this wax phase is 0.06% for the part by weight of this ABS resin.
Material 4:
Wherein material 4 forms for using PMMA resin (20%) and ABS resin (80%) and adding carbon black (CB), dyestuff (Dye) and wax (Wax); Wherein carbon black is 0.05% with respect to the part by weight ratio of this PMMA resin and ABS resin total amount; This dyestuff is 0.0475% with respect to the part by weight of this PMMA resin and ABS resin total amount, and this wax phase is 0.06% for the part by weight of the total amount of this PMMA resin and ABS resin.
Material 5:
Wherein material 5 forms for using PMMA resin (20%) and MABS resin (80%) and adding carbon black (CB), dyestuff (Dye) and wax (Wax); Wherein carbon black is 0.05% with respect to the part by weight of this PMMA resin and MABS resin total amount; This dyestuff is 0.0475% with respect to the part by weight of this PMMA resin and MABS resin total amount, and this wax phase is 0.06% for the part by weight of this PMMA resin and MABS resin total amount.
See also Fig. 3 to Fig. 5, Fig. 4 is the corresponding form and aspect experimental result of material shown in Figure 3, and Fig. 5 is the corresponding physical property experiment result of material shown in Figure 3; Can learn from Fig. 4 to have now when using the PMMA resin (material 1) that can obtain preferable form and aspect diversity factor (dL*), its value can reach 52.93 as main raw material; From Fig. 4, can learn (material 2) when using the MABS resin, can obtain time good form and aspect diversity factor (dL*), can reach 49.44 as main raw material; Can learn that from Fig. 4 its form and aspect diversity factor (dL*) is not good in material 3 (ABS resin is main) and material 4 (PMMA resin 20% and ABS resin 80%), its value only reaches 38.39 and 26.28, and this is the result of current material; At last; From Fig. 4, can learn when using MABS resin (80%) and PMMA resin (20%) (material 5) as main raw material; Can obtain preferable form and aspect diversity factor (dL*), its value can reach 50.25, therefore can know through above-mentioned test; With regard to its form and aspect diversity factor; When the present invention utilized MABS resin or MABS resin and PMMA mixing material for main raw material, it is suitable that it can keep the form and aspect diversity factor (dL*) that is appeared with current material PMMA resin irradiation back, even be that photochromic polymeric composition form and aspect diversity factor (dL*) effect of main raw material is better than ABS or ABS and PMMA resin mixed material.
See also Fig. 5, the result through the physical property experiment gained learns, and is existing when using the PMMA resin as main raw material (material 1), though it has preferable tensile strength (can reach 680Kg/cm
2), but its unit elongation is not good, only reaches 7%, and impact-resistant intensity is merely 2 through measuring to convert, and in other words, its rigidity is too high but extensibility not enough, and it very easily produces embrittlement, and life cycle is prone to damage because of external force and shortens; Yet when using the MABS resin as main raw material (material 2), it has the rigidity (405Kg/cm of certain degree
2), and its unit elongation can reach 40%, and impact-resistant ability can reach 15 through measuring to convert, and in brief, it has rigidity concurrently and extensibility all can reach certain level, and it difficultly damages because of external force in practical application, and its tensile strength is still in acceptable scope; In material 3 (ABS resin is main) and material 4 (PMMA resin 20% and ABS resin 80%), its tensile strength (423Kg/cm
2And 450Kg/cm
2) with unit elongation (being respectively 20%) obvious decline is arranged all, though more show extensibility than material 1, it is comparatively not enough that the defective of those materials is still extensibility; Can't have preferable extensibility and rigid balancing concurrently; And according to aforementioned, ABS resin is the relatively poor material of transparency, and practical application has its restriction; And the present invention's preferred embodiment (material 5) when using MABS resin (80%) and PMMA resin (20%) as main raw material, does not only have too high rigidity (tensile strength 440Kg/cm
2), and it has preferable unit elongation (extensibility), and its value can reach 50%, and its impact strength can reach 10 through measuring, and not only has crushing resistance concurrently, and it also is difficult for because of the embrittlement problem causes damage, moreover, according to aforementioned, can also have preferable form and aspect diversity factor (dL*) concurrently.
Therefore; The present invention see through with the transparency and mechanical quality preferably MABS resin and black pigment carry out suitable collocation as photochromic polymeric composition, not only have better crushing resistance and ductibility, can also keep certain look change effect; Thereby be convenient to form the preferable literal of effect, pattern etc. on the plastic component surface; And through adding second colorant, allocate required color voluntarily, do not need only to be confined to black or white substrate according to actual demand.
The above is merely embodiments of the invention; Be not so limit claim of the present invention; Every equivalent structure or equivalent flow process conversion that utilizes specification sheets of the present invention and accompanying drawing content to be done; Or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.
Claims (12)
1. photochromic polymeric composition; It is characterized in that; This photochromic polymeric composition comprises: a MABS (Methyl methacrylate-Acrylonitril-Butadiene-Styrenencopolymer, a MABS) resin and a black pigment.
2. photochromic polymeric composition according to claim 1 is characterized in that, this black pigment is dyestuff or pigment.
3. photochromic polymeric composition according to claim 1 is characterized in that, this black pigment is 0.03%～0.1% with respect to the part by weight of this MABS resin.
4. photochromic polymeric composition according to claim 1 is characterized in that, this black pigment is a carbon black.
5. photochromic polymeric composition according to claim 1; It is characterized in that; This photochromic polymeric composition further comprises one second resin, and this second resin is plexiglass (PMMA), ethyl propenoate, Bing Xisuandingzhi, 2-EHA or (methyl) vinylformic acid C
1-10Alkyl ester.
6. photochromic polymeric composition according to claim 5 is characterized in that, this MABS resin is 80%～99% with respect to the part by weight of this second resin and this MABS resin total amount.
7. photochromic polymeric composition according to claim 5 is characterized in that, this black pigment is 0.03%～0.1% with respect to the part by weight of the resin total amount of this MABS resin and this second resin.
8. photochromic polymeric composition according to claim 1 is characterized in that, this light is laser, and the wavelength of this laser is between between the 355nm to 1.06um.
9. according to claim 1 or 5 described photochromic polymeric compositions, it is characterized in that this photochromic polymeric composition further comprises one second colorant.
10. according to claim 1 or 5 described photochromic polymeric compositions, it is characterized in that this photochromic polymeric composition further comprises an auxiliary agent, this auxiliary agent is a wax.
11. photochromic polymeric composition according to claim 9 is characterized in that, this photochromic polymeric composition further comprises an auxiliary agent, and this auxiliary agent is a wax.
12. photochromic polymeric composition according to claim 1 is characterized in that, this light makes this photochromic polymeric composition become white by black.
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Cited By (2)
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| CN106928640A (en) * | 2015-12-29 | 2017-07-07 | 施乐公司 | Deformeter polymer comprising photo-chromic colorant |
| WO2019101037A1 (en) * | 2017-11-27 | 2019-05-31 | 合肥华凌股份有限公司 | Composite board, preparation method therefor, refrigeration device inner container and refrigeration device |
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| CN101531801A (en) * | 2009-04-20 | 2009-09-16 | 四川长虹模塑科技有限公司 | Preparation method of scratch-resistant lacquer-free ABS moulding composition with high glaze |
| CN101781438A (en) * | 2010-02-04 | 2010-07-21 | 青岛国恩科技发展有限公司 | High-transparency composite material and manufacturing method thereof |
| WO2010105735A1 (en) * | 2009-03-18 | 2010-09-23 | Merck Patent Gmbh | Pigment for laser marking |
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| WO2010105735A1 (en) * | 2009-03-18 | 2010-09-23 | Merck Patent Gmbh | Pigment for laser marking |
| CN101531801A (en) * | 2009-04-20 | 2009-09-16 | 四川长虹模塑科技有限公司 | Preparation method of scratch-resistant lacquer-free ABS moulding composition with high glaze |
| CN101781438A (en) * | 2010-02-04 | 2010-07-21 | 青岛国恩科技发展有限公司 | High-transparency composite material and manufacturing method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928640A (en) * | 2015-12-29 | 2017-07-07 | 施乐公司 | Deformeter polymer comprising photo-chromic colorant |
| US10381134B2 (en) * | 2015-12-29 | 2019-08-13 | Xerox Corporation | Strain gauge polymer comprising photochromic colorant |
| RU2720617C2 (en) * | 2015-12-29 | 2020-05-12 | Зирокс Корпорейшн | Strain-sensitive polymer containing photochromic dye |
| CN106928640B (en) * | 2015-12-29 | 2021-06-01 | 施乐公司 | Strain gauge polymers comprising photochromic colorants |
| WO2019101037A1 (en) * | 2017-11-27 | 2019-05-31 | 合肥华凌股份有限公司 | Composite board, preparation method therefor, refrigeration device inner container and refrigeration device |
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