TW201229070A - Photochromic polymer composition - Google Patents

Abstract

A photochromic polymer composition includes: an MABS (methyl methacrylate-acrylonitril-butadiene-styrenen copolymer) resin and a black pigment, wherein the black pigment is a dye or pigment and is 0.03% to 0.1% relative to the weight ratio of the MABS resin.

Description

201229070 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a polymer composition, and more particularly to a photochromic polymer composition. [Prior Art] Generally, printing a font or a design graphic on a plastic surface can be realized by various methods such as a PadPriming method, an Imprgnagna Qnprinting method, and a Laser Marking method. Among them, the gravure pad printing method is the most widely used. The main technical principle is to use a set of pre-mother words as the original word model, after the ink is brushed on it by automatic machine, then a set of soft rubber blocks are pressed on it. When the rubber block is lifted, the writing ink is transferred to the rubber block. 'Weaving and then moving the rubber block to the white keyboard, pressing the rubber on the keyboard, the ink is printed on the keyboard; however, it has the following disadvantages : The processing speed is slow and the cost is high, the solvent used is likely to cause environmental pollution, and high equipment investment is required. The main principle of the dip printing method is to use a sublimation ink on a transfer film or paper and transmit it through the heating and pressing to make the ink penetrate into the plastic; however, the 'immersion printing method has high manufacturing cost and process Complex shortcomings. In another aspect, the main principle of the laser marking method is to use a laser beam to burn text marks on the surface of the object. The method is simple, and the method is low in cost and fast in speed, and can maintain the excellent durability and environmental protection of the printing material. Therefore, the laser marking method has a high industrial value (four); however, the photochromic material which is conventionally applied to the laser marking 201229070 method is often applied to components such as a keyboard or a button, and the surface is marked with text or graphics. And often need to press or rub, and the conventional laser marking method material is used to maintain the surface printing font or the contrast between the design pattern and the bottom substrate, but it cannot combine the resistance and the ductility of the material, and is easy to embrittle or Damage leads to a reduction in its life cycle, and the type of material used is limited. Currently, there are two colors, black and white. Among them, commonly used materials are polyacrylic acid acrylic acid, methyl vinegar (PMMA) or acrylonitrile-benzene. Ethylene-butadiene dilute copolymer (Nano resin). Please refer to Figure 1, which is a schematic diagram of the chemical formula of ABS tree. ABS resin consists of two incompatible phases, mainly by polybutylene. The dilute rubber and (following M) resin phase, due to the light scattering effect caused by the difference in refractive index between the two phases, the material loses transparency and is a material with poor transparency, and PMMA is brittle. Therefore, it is necessary to provide The photochromic polymer material having pressure resistance and good ductility while maintaining a constant color phase (contrast), and the color of the material can be formulated according to the demand # to solve the above problems. [Invention] The object of the present invention is to provide A photochromic polymer composition which can be discolored after being irradiated by a light beam. Embodiments of the present invention provide a photochromic polymer composition, including a MABS resin (Methyl methacrylate-Acrylonitril-Butadiene-Styrenen copolymer, methyl 201229070) A decyl acrylate-acrylonitrile-butadiene-styrene copolymer resin and a black colorant. Preferably, the black colorant is a dye or a pigment. Preferably, the weight ratio of the black color material to the MABS resin is Preferably, the black colorant is carbon black. Preferably, the photochromic polymer composition further comprises a first a resin, the second resin is a polymethyl methacrylate resin, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate or a Cuo alkyl (meth) acrylate. Preferably, the MABS resin is relative to The weight ratio of the second resin to the total amount of the MABS resin is 80% to 99%. Preferably, the weight ratio of the black colorant to the total resin content of the MABS resin and the second resin is 0.03% to 0.1%. Preferably, the light system is laser light, and the wavelength of the laser is between 355 nm and 10.6 um. Preferably, the photochromic polymer composition further comprises a second color material. Preferably, The photochromic polymer composition further comprises an auxiliary agent which is cerium. [Embodiment] 201229070 The present invention will be described in detail below with reference to the accompanying drawings and embodiments. MABS (Methyl methacrylate-Acrylonitril-Butadiene-Styrenen copolymer) resin is a kind of common ABS resin (acrylonitrile-butadiene-styrene) Copolymer, Acrylonitrile-Butadiene-Styrene copolymer) tree

The high-strength plastic with good mechanical quality and transparency has the same production cost as ordinary ABS resin, and its comprehensive quality is superior to ordinary plexiglass transparent material. among them,

AN is Acrylonitrile, SM is Styrene, BD is Butadiene, MMA is Methyl Methacrylate (Methyl Methacrylate)

Methacrylate ). Therefore, the difference between ABS resin and MABS resin is that ABS resin is a combination of AN-SM, and MABS resin is a combination of mMA-AN-SM, because it reduces the phase refraction of polybutadiene rubber and (MMA-AN-SM) resin. The rate difference 'and thus the light scattering effect' can achieve transparency in the visible light region; due to the difference in the chemical structure, the quality of the ABS resin and the MABS resin are greatly different, the MABS resin is a transparent material, and the MABS resin is transparent. The sex can reach 85%. Therefore, the present invention utilizes the formulation of the excellent characteristic mixed color material of the MABS resin material to provide a photochromic polymer composition suitable for a method of marking a character or a pattern of light of a specific wavelength, and the light of the specific wavelength is preferably a thunder. Shoot light. In the first embodiment of the photochromic polymer composition of the present invention, the photochromic polymer composition comprises a MABS resin and a black colorant (c〇1〇ring 201229070 agent), as described above, the MABS resin has a comparative Good mechanical quality and transparency, of which the transparency of MABS resin can reach 85%. The black coloring material may be a dye or a pigment, and the weight ratio of the black coloring material to the MABS resin is 0.03% to 0.1%. Preferably, the black coloring material may be carbon black; In a further refinement, an auxiliary agent may be continuously added to the photochromic polymer composition, for example, cerium (WAX) is added as an auxiliary agent, so that the distribution of the coloring material in the MABS resin is more uniform. When the photochromic polymer composition is irradiated with light, for example, when the photochromic polymer composition is irradiated with a laser beam for a suitable period of time, the photochromic polymer composition is composed of the original color (this The example is black) converted to white marking, and as time increases, white will turn yellowish and eventually turn yellow in a certain amount of time. Among them, the preferred wavelength of the laser beam is between 355 nm and 10.6 um. According to the experimental data, when the photochromic polymer composition is irradiated with C02 laser light having a wavelength of 10600 nm, a thermochemical reaction is generated, which marks a similar engraving effect; when a wavelength of 1064 nm is selected, Nd:YAG (yttrium aluminum) is selected. When the garnet crystal is irradiated with the photochromic polymer composition by laser light, a thermochemical reaction is generated, and the effect of the marking is better than the above; when the photochromic polymer composition is irradiated with UV laser light having a wavelength of 355 nm. Because it is a collimated laser beam, the effect of marking is better. In a second embodiment of the photochromic polymer composition of the present invention, the light 201229070 color-changing polymer composition includes another coloring material, that is, a second coloring material, in addition to the MABS resin and the black coloring material. Further, the color required for the photochromic polymer composition is further modified by the second colorant composition, in other words, the photochromic polymer composition of the present invention can be formulated by MABS resin and black colorant and second color material. Pre-set colors can be customized. In addition, in a further improvement, an auxiliary agent may be further added to the photochromic polymer composition, for example, cerium (WAX) is added as an auxiliary agent, so that the black coloring material and the second coloring material can be used in the MABS resin. The distribution in the film is more uniform; the embodiment when the photochromic polymer composition is irradiated with light is similar to the first embodiment, and the description thereof will not be repeated. In a third embodiment of the photochromic polymer composition of the present invention, the photochromic polymer composition further comprises a second resin in addition to the MABS resin and the black colorant; wherein the MABS resin is relative to the The weight ratio of the second resin to the total amount of the MABS resin is 80% to 99%, in other words, the weight ratio of the second resin to the total amount of the second resin and the MABS resin may be 1% to 20%, The ratio of the actual demand is adjusted; in addition, the weight ratio of the black colorant to the total amount of the resin of the MABS resin and the second resin is 0.03% to 0.1%. In this embodiment, the second resin may be one or a combination of the following materials: polymethyl methacrylate resin (PMMA), ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate or (曱基)C 201229070 Cenoic acid C1-10 alkyl ester. Of course, in the photochromic polymer composition of the present embodiment, another color material, that is, the second color material, may be added to further modify the photochromic polymer composition by the second color material blending. The desired color, in other words, the photochromic polymer composition of the present invention can be prepared by the MABS resin, the second resin, the black colorant and the second color to achieve the desired color. In addition, in a further improvement, an auxiliary agent may be continuously added to the photochromic polymer composition, for example, cerium (WAX) is added as an auxiliary agent, so that the black coloring material and the second coloring material can be used in the MABS resin. The distribution in the film is more uniform; the embodiment when the photochromic polymer composition is irradiated with light is similar to the first embodiment, and the description thereof will not be repeated. Referring to FIG. 2, FIG. 2 shows an experimental procedure of the photochromic polymer composition of the present invention. First, a formulation of a photochromic polymer composition, that is, a mixture of materials thereof; wherein a double axis can be used; The extruder is used as a processing machine, and the preferred processing temperature is 200 degrees Celsius to 220 degrees Celsius. Secondly, the formulation after the kneading process is granulated; wherein, the injection molding machine can be used as the processing machine, and the preferred processing temperature is 200 degrees Celsius to 220 degrees Celsius; then, tensile test pieces, impact test pieces, and color plate tests are performed on the granulated material; 9 201229070 wherein, in the tensile test piece, the universal tensile tester is used for granulation. The material is subjected to tensile strength test and elongation test. In the impact test piece, the impact strength test is performed on the granulated material by the impact tester; in the swatch test, the granulated material is used by the laser marking machine. A laser marking evaluation was performed, and then the white mark after the laser marking was subjected to hue evaluation using a spectrometer; the thickness of the tested swatch was 2 mm. Please refer to Figure 3, which is the weight ratio of the materials used in the experiment. The experiment is divided into five kinds of experimental materials. First, the dyes (Dye) and wax (Wax) are not necessary materials for the present invention. The experimental system is added in proportion to increase the color development characteristics. The materials are described in detail as follows: Material 1: The material 1 is made of PMMA resin and carbon black (CB), dye (Dye) and wax. (Wax), wherein the weight ratio of carbon black to the PMMA resin is 0.05%, the weight ratio of the dye to the PMMA resin is 0.0475%, and the weight ratio of the wax to the PMMA resin is 0.06%. Material 2: The material 2 is made by using MABS resin and adding carbon black (CB), dye (Dye) and wax (Wax), wherein the weight ratio of carbon black to the MABS resin is 0.05%, and the dye is relative to The weight ratio of the MABS resin was 201229070 0.0475%, and the weight ratio of the wax to the MABS resin was 〇.〇6〇/0. Material 3: The material 3 is made by using ABS resin and adding carbon black (CB), dye (Dye) and wax (Wax), wherein the weight ratio of carbon black to the ABS resin is 0.05%, and the dye is relative to The weight ratio of the ABS resin was 0.0475%, and the weight ratio of the wax to the ABS resin was 〇.〇6%. Material 4: The material 4 is made of PMMA resin (20%) and ABS resin (80%) and added with carbon black (CB), dye (Dye) and soil (Wax), wherein carbon black is relative to the PMMA resin. And the weight ratio of the total amount of the ABS resin is 0.05%, the weight ratio of the dye to the total amount of the PMMA resin and the ABS resin is 0.0475%, and the weight ratio of the wax to the total amount of the PMMA resin and the ABS resin is 0.06. %. Material 5: The material 5 is made of PMMA resin (20%) and MABS resin (80%) and added with carbon black (CB), dye (Dye) and wax (Wax), wherein carbon black is relative to the PMMA resin. The weight ratio of the total amount of the MABS resin was 0.05%, the weight ratio of the dye to the total amount of the PMMA resin and the MABS resin was 0.0475%, and the weight ratio of the wax to the total amount of the PMMA resin and the MABS resin was 0.06%. 201229070 Please refer to FIG. 3 to FIG. 6 , FIG. 4 is the result of the hue experiment corresponding to the material shown in FIG. 3 ' FIG. 5 is an example of the hue experiment result corresponding to the material shown in FIG. 3 , and FIG. 6 is the physical property experiment corresponding to the material shown in FIG. 3 . As a result, it can be known from FIG. 4 that when PMMA resin is used as the main raw material (material f... can obtain a better hue difference (dL*), the value can reach 52.93, please refer to the material shown in FIG. From the naked eye, there is a clear difference in hue between black and white; from Fig. 4, it can be seen that when #肖MABS resin is used as the main raw material (material f 2), sub-optimal hue difference (dL) can be obtained. *), up to 49.44, please refer to material 2 shown in Figure 6, the difference in hue between black and white is also obvious; from Figure 4, you can see that material 3 (ABS tree is Main) and material 4 (pMMA resin 2 defeat and aBS resin 80%)'s hue difference (dL*) is not good, its value is only 38 39 and 26 28, please refer to material 3 and material shown in Figure 6. 4 The difference in hue between black and white is less obvious, which is the result of the conventional materials; finally, it can be seen from Fig. 4 that the use of tender resin (8〇%) and Xinjiang A resin (20%) ) When it is the main raw material (Material 5), a better hue difference (dL*) can be obtained, and its value can reach 5〇25. Please refer to the material 5 shown in Figure 6, which is black and white. There is also a significant difference in the degree of hue difference between the two. Therefore, it can be seen from the above test that, in terms of the degree of hue difference, the present invention utilizes MABS resin or MABS resin and PMMA mixed material as main raw materials, which can be maintained and conventionally known. The hazard difference (dL*) exhibited by the PMMA resin after irradiation is equivalent to that of ABS or ABS and PMMA resin. [S] 12 201229070 The photochromic polymer composition of the main raw material is the color difference (Zhao* ) The effect is better.

Referring to Figure 6, the results obtained from the physical property test show that when PMMA resin is used as the main raw material (Material 1), although it has better tensile strength (up to 680 KgW), its elongation is not It is only 7%, and the strength of the impact resistance is measured in the conversion material 2, in other words, the m is too high but the extensibility is not ^, which is easy to produce embrittlement life cycle is easier to shorten due to external damage; however, using MABS « When it is the main raw material (material f & it has a considerable degree of rigidity (405 Kg / em) ' and its elongation is reachable, the ability of the righting hammer can be measured and converted up to 15 s <, it has both rigidity and The elongation can reach a certain level. In practical application, it is less susceptible to damage due to external force, and its tensile strength is still within the range of connection. 'Material 3 (ABS resin-based) and material 4 (PMMA resin) 20% and ABS resin 80%), the tensile strength (423 Kg/cm2 and 45〇Kg/cm2) and the elongation (20%, respectively) are significantly reduced, although more extensible than material 1, but The defects of some materials are still insufficient in elongation, and it is impossible to have a good balance of elongation and rigidity, and according to the foregoing, ABS The grease is a material with poor transparency, and its practical application has its limitations. However, in the preferred embodiment of the present invention (material 5), when MABS resin (80%) and PMMA resin (20%) are used as main raw materials, not only will it not be used. High rigidity (tensile strength 440 Kg/cm2), and it has a good elongation (extensibility), its value can reach 50%, its impact strength can be measured up to [S] 13 201229070 10, not only It is also resistant to pressure, and it is not easily damaged by the embrittlement problem. Further, according to the above, it is possible to have a better hue difference (dL: lc). Therefore, the present invention transmits transparency and machine α. Maple °. A good quality MABS resin and black colorant are properly matched as a light two-color polymer composition, which not only has good pressure resistance and ductility, but also maintains a certain color change effect, thereby facilitating The surface of the plastic part is formed with a better effect on the text, the pattern, etc., and by adding the second color material, the required color can be matched with the actual requirement, and it is not limited to the black or white substrate. The preferred embodiment of the invention is not limited The present invention has various modifications and changes to the present invention. Any modifications, equivalent substitutions, improvements, etc. within the spirit and scope of the present invention should be included in the protection of the present invention. Within the scope. [Simple description of the schema]

The drawings are provided to provide a further understanding of the present invention, and the drawings are incorporated in the specification and constitute a part of the specification. BRIEF DESCRIPTION OF THE DRAWINGS Exemplary embodiments of the present invention, in the accompanying circle: FIG. 1 is a schematic diagram of a chemical formula of an ABS resin; FIG. 2 is a photochromic polymer composition of the present invention (4) (four) (four) (four) FIG. 3 is a weight ratio of a material used in the experiment; 4 is a color phase experiment result corresponding to the material shown in FIG. 3. 201229070 FIG. 5 is a color phase experiment result corresponding to the material shown in FIG. 3; FIG. 6 is a physical property test result corresponding to the material shown in FIG.

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Claims (1)

201229070 VII. Patent application scope: 1. A photochromic polymer composition comprising: a MABS (Methyl methacrylate-Acrylonitril-Butadiene-Styrenen copolymer) methyl methacrylate-acrylonitrile-butadiene-styrene copolymer ) Resin and a black colorant. 2. The photochromic polymer composition according to claim 1, wherein the black colorant is a dye or a pigment. 3. The photochromic polymer composition according to claim 1, wherein the weight ratio of the black colorant to the MABS resin is from 0.03% to 0.1%. 4. The photochromic polymer composition of claim 1, wherein the black colorant is carbon black. 5. The photochromic polymer composition of claim 1, wherein the photochromic polymer composition further comprises a second resin, the second resin being a polymethyl methacrylate resin (PMMA), ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate or (meth)acrylic acid C o 烧 vinegar. 6. The photochromic polymer composition according to claim 5, wherein the weight ratio of the MABS resin to the total amount of the second resin and the MABS resin is from 80% to 99%. [S] 16 201229070 7. The photochromic polymer composition of claim 5, wherein the weight ratio of the black colorant to the total resin of the MABS resin and the second resin is 0.03. %~0.1%. 8. The photochromic polymer composition according to claim 1, wherein the light system is laser light, and the wavelength of the laser is between 355 nm and 1.06 um. The photochromic polymer composition of claim 1 or 5, further comprising a second colorant. 10. The photochromic polymer composition according to claim 1 or 5, further comprising an auxiliary agent. The auxiliary agent is a wax. The photochromic polymer composition according to claim 9, further comprising an auxiliary agent which is hydrazine. 12' The photochromic polymer composition of the invention of claim </ RTI> wherein the light changes the photochromic polymer composition from black to white. [S3 17