CN114806054B - Infrared-transmitting scratch-resistant master batch, preparation method and application thereof - Google Patents
Infrared-transmitting scratch-resistant master batch, preparation method and application thereof Download PDFInfo
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
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- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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- C08K5/3475—Five-membered rings condensed with carbocyclic rings
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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Abstract
The invention provides an infrared-transmitting scratch-resistant master batch, a preparation method and application thereof, and relates to the technical field of resin modification; the master batch is prepared by uniformly mixing 100 parts of polymethyl methacrylate resin, 1-3 parts of infrared transmitting toner, 1.5-3 parts of weather resistant agent and 1-3 parts of antioxidant according to parts by weight and then preparing the master batch by a double screw extruder. The infrared-transmitting scratch-resistant master batch prepared by the invention can be widely applied to the fields of polymethyl methacrylate or polycarbonate resin plates, films or injection molding parts and the like, and has extremely high infrared transmittance when blocking visible light, and obvious infrared transmitting effect; the surface pencil hardness of the material can be greatly improved by using the material in the polycarbonate resin, and the scratch resistance is improved.
Description
Technical Field
The invention relates to the technical field of resin modification, in particular to an infrared-transmitting scratch-resistant master batch, a preparation method and application thereof.
Background
Polymethyl methacrylate resin (PMMA) has excellent light transmittance and surface pencil hardness, the light transmittance can reach more than 90%, and the conventional PMMA has a refractive index of 1.49; furthermore, PMMA also has excellent weather resistance due to the presence of acrylic esters in its molecular structure. Polycarbonate (PC) is an almost colorless amorphous polymer in a glassy state, has good heat resistance and high impact strength, has a visible light transmittance of 88% and a refractive index of 1.58.PMMA and PC have the advantage of good light transmittance, so that the two materials are widely applied in the field of infrared transmitting materials; meanwhile, because PMMA and PC materials have beautiful pearl luster and metal luster when forming a blend, the blend is widely applied to liquid crystal displays, lamp tubes, communication equipment shells and electrical appliances and packaging materials with higher requirements on surface hardness and glossiness. However, the blend obtained by mixing PMMA and PC using the conventional method is mainly used for improving the wear resistance, the temperature resistance and the mechanical strength of the product, and the transparency of the product cannot be maintained, so that the advantages of the PMMA and the PC cannot be combined by the conventional method for ensuring the transparency.
For example, patent CN109721998A discloses an infrared-transmitting high-rigidity polycarbonate composition and a method for preparing the same, wherein zinc sulfide is used for improving the infrared-transmitting performance of glass fiber reinforced silicon-containing PC resin, the method is limited to light-colored materials, and the infrared transmittance of the materials per se is high; the infrared transmitting material disclosed in the patent CNCN105670265B proposes a solution for increasing the infrared transmittance of EVA toughened polycarbonate PC using KBr, which is also limited to light-colored or white materials.
It is known that heat is transmitted by infrared rays and if more infrared rays are absorbed, it is converted into vibrational energy and finally into thermal energy. For the black material, the black material can absorb visible light and infrared rays due to the color characteristics, so that heat is accumulated in the black material, and the surface temperature is increased; the core problem of researching the infrared transmitting performance of the black material is that the black material can absorb visible light and simultaneously transmit or reflect infrared rays, so that the material can not store heat and inhibit temperature rise.
Disclosure of Invention
The invention aims to provide an infrared-transmitting scratch-resistant master batch, a preparation method and application thereof, and the master batch ensures that the material has good infrared transmittance on the premise of preparing a black material, and realizes the infrared-transmitting effect under the condition that the surface temperature of the material cannot be increased.
In order to achieve the above purpose, the present invention proposes the following technical scheme: the infrared-transmitting scratch-resistant master batch comprises the following components in parts by weight: 100 parts of methyl methacrylate, 1-3 parts of infrared transmitting toner, 1.5-3 parts of weather-proof agent and 1-3 parts of antioxidant.
Further, the infrared transmitting toner consists of the following components in percentage by mass: 3:5:1, organic red powder, organic green powder, organic blue powder and organic yellow powder; the master batch exhibits the highest blackness value at this mass ratio.
Furthermore, the polymethyl methacrylate is ultralow molecular weight polymethyl methacrylate, the weather resistant agent is benzotriazole weather resistant agent, and the antioxidant is phosphite antioxidant.
The invention also discloses a preparation method of the infrared-transmitting scratch-resistant master batch, which comprises the following steps:
(1) According to the mass ratio of 7:3:5:1, weighing four kinds of toner of organic red, organic green, organic blue and organic yellow, and uniformly mixing to obtain infrared transmitting toner;
(2) According to the weight portions, respectively weighing 100 portions of methyl methacrylate, 1 to 3 portions of infrared transmitting toner, 1.5 to 3 portions of weather resistant agent and 1 to 3 portions of antioxidant, and uniformly mixing to obtain a mixed material; wherein the polymethyl methacrylate is ultralow molecular weight polymethyl methacrylate, the weather-proof agent is benzotriazole, and the antioxidant is phosphite antioxidant;
(3) And adding the mixed material into a double-screw extruder for melt extrusion, and obtaining the infrared-transmitting scratch-resistant master batch after water cooling, air cooling and granulating.
Further, the four toners in the step (1) and the components in the step (2) are uniformly mixed in a high-speed mixer, and the mixing time of the two times is 3-5min; the rotating speed of the double-screw extruder in the step (3) is 200-500r/min, and the extrusion temperature is 190-220 ℃.
The invention also discloses application of the infrared-transmitting scratch-resistant master batch, wherein the application comprises blending, modifying and granulating the infrared-transmitting scratch-resistant master batch and polycarbonate or polymethyl methacrylate, blending and extruding a plate, a film, a pipe, a bar and a profile, and directly injection-molding the blend by single-layer or multi-layer co-extrusion of the plate, the film, the pipe, the bar and the profile.
Further, the blending ratio of the infrared transmitting anti-scratch master batch and the polycarbonate or the polymethyl methacrylate is 10-40% of the mass ratio of the infrared transmitting anti-scratch master batch.
According to the technical scheme, the following beneficial effects are achieved:
the invention discloses an infrared-transmitting scratch-resistant master batch, a preparation method and application thereof, wherein the master batch comprises, by weight, 100 parts of methyl methacrylate, 1-3 parts of infrared-transmitting toner, 1.5-3 parts of weather-resistant agent and 1-3 parts of antioxidant, and is prepared by melt extrusion in a double-screw extruder, water cooling, air cooling and granulating; the prepared infrared-transmitting scratch-resistant master batch can be widely applied to the fields of polymethyl methacrylate or polycarbonate resin plates, films or injection molding parts and the like. Wherein, the infrared transmitting toner is 7:3:5:1, organic red powder, organic green powder, organic blue powder and organic yellow powder, and has good infrared transmittance on the premise of realizing that black master batch capable of blocking visible light is prepared, thereby ensuring that the surface temperature of a black material is not increased during application, and having remarkable infrared transmitting effect.
According to the master batch disclosed by the invention, the ultra-low molecular weight polymethyl methacrylate is used as a master batch substrate, on one hand, due to the low molecular weight, the refractive index is closer to that of polycarbonate, and good transparency can be ensured when the master batch is added into a large amount of polycarbonate resin, the polymethyl methacrylate can provide more excellent surface pencil hardness for the polycarbonate, a good scratch resistance function is realized, and the master batch can provide excellent weather resistance for the added resin when being matched with a weather-resistant agent.
It should be understood that all combinations of the foregoing concepts, as well as additional concepts described in more detail below, may be considered a part of the inventive subject matter of the present disclosure as long as such concepts are not mutually inconsistent.
The foregoing and other aspects, embodiments, and features of the present teachings will be more fully understood from the following description, taken together with the accompanying drawings. Other additional aspects of the invention, such as features and/or advantages of the exemplary embodiments, will be apparent from the description which follows, or may be learned by practice of the embodiments according to the teachings of the invention.
Drawings
The drawings are not intended to be drawn to scale. In the drawings, each identical or nearly identical component that is illustrated in various figures may be represented by a like numeral. For purposes of clarity, not every component may be labeled in every drawing. Embodiments of various aspects of the invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is an infrared absorption spectrum of each component of an infrared transmitting toner.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without creative efforts, based on the described embodiments of the present invention fall within the protection scope of the present invention. Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
The terms "first," "second," and the like in the description and in the claims, are not used for any order, quantity, or importance, but are used for distinguishing between different elements. Also, unless the context clearly indicates otherwise, singular forms "a," "an," or "the" and similar terms do not denote a limitation of quantity, but rather denote the presence of at least one. The terms "comprises," "comprising," or the like are intended to cover a feature, integer, step, operation, element, and/or component recited as being present in the element or article that "comprises" or "comprising" does not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
Research on the infrared transmitting performance of materials based on the prior art mainly focuses on light-colored or white materials, but the problem of the infrared transmitting performance of black materials is rarely concerned; the core of the problem of infrared transmitting performance of the black material is that the black material can absorb visible light and simultaneously transmit or reflect infrared rays, so that the material can not store heat, and thermal stress is not formed in the material during application to influence the service performance of the material. Aiming at the problems, the invention provides an infrared-transmitting scratch-resistant master batch, a preparation method and application thereof, and the master batch has extremely high infrared transmittance while blocking visible light and has obvious infrared transmitting effect.
The infrared transmitting scratch-resistant master batch disclosed by the invention comprises the following components in parts by weight: 100 parts of methyl methacrylate, 1-3 parts of infrared transmitting toner, 1.5-3 parts of weather resistant agent and 1-3 parts of antioxidant; wherein the polymethyl methacrylate is ultralow molecular weight polymethyl methacrylate, and the polymethyl methacrylate with the molecular weight of 5000-20000g/mol and the refractive index of 1.52 is generally selected; the weather-resistant agent is benzotriazole weather-resistant agent, such as UV360; the antioxidant is phosphite antioxidant, and can be selected from antioxidant 168; the infrared transmitting toner comprises the following components in percentage by mass: 3:5:1, organic red powder, organic green powder, organic blue powder and organic yellow powder, and enabling the master batch to present the highest blackness value under the mass ratio. In the examples, the organic red powder has a chemical composition of picene, the organic green and organic blue powder has a chemical composition of anthraquinone, the organic yellow powder has a chemical composition of quinophthalone, fig. 1 shows an infrared absorption spectrum of each component of the infrared-transmitting toner, and the results show that the above toner has no absorption peak in the near infrared band and shows good infrared transmittance.
The infrared-transmitting scratch-resistant master batch prepared by the invention can be applied to blending modification granulation with polycarbonate or polymethyl methacrylate, blending extrusion plates, films, pipes, bars and profiled bars, single-layer or multi-layer co-extrusion plates, films, pipes, bars and profiled bars, and blending direct injection molding to obtain modified black materials.
The method, effect and use of the infrared transmitting scratch resistant master batch of the present invention are further described below with reference to examples. Table 1 shows the raw materials used in each of the examples and comparative examples, all of which are commercially available.
Table 1 raw materials used in examples and comparative examples
The infrared transmitting scratch-resistant master batches are prepared according to the following preparation method, and are molded into standard test samples, namely: (1) Weighing four kinds of toner of organic red, organic green, organic blue and organic yellow according to the mass ratio, and uniformly mixing for 3-5min in a high-speed mixer to obtain infrared transmitting toner; (2) Respectively weighing methyl methacrylate, infrared transmitting toner, weather resistant agent and antioxidant according to the set parts by weight, and uniformly mixing in a high-speed mixer for 3-5min to obtain a mixed material; (3) Adding the mixed material into a double-screw extruder for melt extrusion, and preparing infrared-transmitting scratch-resistant master batch after water cooling, air cooling and granulating; the working parameters of the double-screw extruder are set to be the rotating speed of 200-500r/min and the extrusion temperature of 190-220 ℃.
The infrared-transmitting scratch-resistant master batch standard sample testing method comprises the following steps:
surface pencil hardness test standard is referenced to ISO 15184:2012;
the light transmittance test standard can be referred to GB/T2410-2008, the test wavelength range is 380-760nm, and the test thickness is 1mm;
the infrared transmittance test standard is referred to GB/T34603-2018, the test wavelength range is 780-940nm of the near infrared band, and the test thickness is 1mm;
the color difference L value is obtained by using a color plate under a spectrophotometer by using a transmission mode test, and the test thickness is 1mm; and (3) placing the test sample under solar noon for irradiation for 2 hours, and testing the surface temperature by using a remote sensing temperature gun.
Table 2 test results of examples 1-3 of ir-transmitting scratch resistant master batches
| Raw materials | Example 1 | Example 2 | Example 3 |
| Ultra low molecular weight PMMA | 100 | 100 | 100 |
| Infrared transmitting toner | 1 | 2 | 3 |
| Antioxidant | 2 | 1.5 | 2 |
| Weather-proof agent | 2 | 3 | 1 |
| Performance of | / | / | / |
| Surface pencil hardness | 3H | 3H | 3H |
| Visible light transmittance% | 1.5 | 0.8 | 0 |
| Infrared transmittance% | 34 | 25 | 21 |
| L value | 23.4 | 22.1 | 21.3 |
As shown in Table 2, the infrared transmitting scratch-resistant master batch prepared by the formula and the preparation method disclosed by the invention has the advantages of capability of fully blocking visible light, good infrared transmittance and excellent scratch resistance. The master batch prepared in example 2 was blended with PC or PMMA in the corresponding ratio, and then pelletized by twin screw extrusion, dried and injection molded into standard test samples, corresponding examples, comparative examples and test results are shown in Table 3 below.
Table 3 test results of examples 4-7 of ir-transmitting scratch resistant masterbatch applications
| Raw materials | Example 4 | Example 5 | Example 6 | Example 7 | Comparative example 1 | Comparative example 2 |
| PC | 90 | 70 | / | / | 98 | / |
| PMMA | / | / | 80 | 60 | / | 98 |
| Infrared-transmitting scratch-resistant master batch | 10 | 30 | 20 | 40 | / | / |
| Black matrix | / | / | / | / | 2 | 2 |
| Performance of | / | / | / | / | / | / |
| Surface pencil hardness | HB | H | H | H | 2B | H |
| Visible light transmittance% | 18.3 | 10.2 | 12.4 | 7.1 | 0 | 0 |
| Infrared transmittance% | 95 | 80 | 92 | 76 | 0 | 0 |
| L value | 27.4 | 27.2 | 26.5 | 26.1 | 26.8 | 23.6 |
| Surface temperature (DEG C) | 57.3 | 59.7 | 56.2 | 61.6 | 66.3 | 65.2 |
It can be seen from the combination of examples 4 to 7 that the infrared-transmitting scratch-resistant master batch has high infrared transmittance up to 95% on the premise of black material after 10-40% of the infrared-transmitting scratch-resistant master batch is added into PC or PMMA; meanwhile, the hardness of the surface pencil is improved from 2B to HB or H in PC after the master batch is added, a plurality of grades are improved, and the scratch resistance of the product modified material is greatly improved. By combining comparative example 1 and comparative example 2, the surface temperature data of the sample after direct irradiation of the sun for 2 hours can be obtained, and compared with the conventional black master batch (generally carbon black), the infrared-transmitting scratch-resistant master batch prepared by the invention can well reduce the surface temperature of the material after being blended with PC or PMMA, which shows that the polymethyl methacrylate can provide excellent weather resistance for the added PC or PMMA resin after being matched with the weather-resistant agent.
While the invention has been described with reference to preferred embodiments, it is not intended to be limiting. Those skilled in the art will appreciate that various modifications and adaptations can be made without departing from the spirit and scope of the present invention. Accordingly, the scope of the invention is defined by the appended claims.
Claims (7)
1. The application of the infrared-transmitting scratch-resistant master batch is characterized by comprising the steps of carrying out blending modification granulation on the infrared-transmitting scratch-resistant master batch and polycarbonate or polymethyl methacrylate, and carrying out blending extrusion on plates, films, pipes, bars and profiled bars, and carrying out single-layer or multilayer co-extrusion on plates, films, pipes, bars and profiled bars, wherein the blending is directly injection-molded; the blending ratio of the infrared transmitting anti-scratch master batch and the polycarbonate or the polymethyl methacrylate is 10-40% of the mass ratio of the infrared transmitting anti-scratch master batch, and the infrared transmission rate of the injection molding product after blending can reach 95%;
the infrared-transmitting scratch-resistant master batch comprises the following components in parts by weight: 100 parts of methyl methacrylate, 1-3 parts of infrared transmitting toner, 1.5-3 parts of weather resistant agent and 1-3 parts of antioxidant; wherein, the infrared transmitting toner consists of the following components in percentage by mass: 3:5:1, organic red powder, organic green powder, organic blue powder and organic yellow powder; the master batch exhibits the highest blackness value at this mass ratio.
2. The use of an infrared transmitting scratch resistant masterbatch according to claim 1 wherein the polymethyl methacrylate is an ultra low molecular weight polymethyl methacrylate.
3. The use of an infrared transmitting scratch resistant master batch according to claim 1, wherein the weathering agent is a benzotriazole weathering agent.
4. The use of an infrared transmitting scratch resistant masterbatch according to claim 1 wherein the antioxidant is a phosphite antioxidant.
5. The preparation method of the infrared-transmitting scratch-resistant master batch is characterized by comprising the following steps of:
(1) According to the mass ratio of 7:3:5:1, weighing four kinds of toner of organic red, organic green, organic blue and organic yellow, and uniformly mixing to obtain infrared transmitting toner;
(2) According to the weight portions, respectively weighing 100 portions of methyl methacrylate, 1 to 3 portions of infrared transmitting toner, 1.5 to 3 portions of weather resistant agent and 1 to 3 portions of antioxidant, and uniformly mixing to obtain a mixed material; wherein the polymethyl methacrylate is ultralow molecular weight polymethyl methacrylate, the weather-proof agent is benzotriazole, and the antioxidant is phosphite antioxidant;
(3) And adding the mixed material into a double-screw extruder for melt extrusion, and obtaining the infrared-transmitting scratch-resistant master batch after water cooling, air cooling and granulating.
6. The method for preparing infrared transmitting scratch-resistant master batch according to claim 5, wherein the four toners in step (1) and the components in step (2) are uniformly mixed in a high-speed mixer, and the mixing time is 3-5min.
7. The method for producing infrared transmitting scratch-resistant master batch according to claim 5, wherein the rotational speed of the twin screw extruder in the step (3) is 200-500r/min, and the extrusion temperature is 190-220 ℃.
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| CN109553910A (en) * | 2018-11-28 | 2019-04-02 | 宁波力达得为高分子科技有限公司 | A kind of infrared transmission black plastic and its preparation method and application |
| CN109721998A (en) * | 2018-12-29 | 2019-05-07 | 上海锦湖日丽塑料有限公司 | A kind of infrared high rigidity polycarbonate compositions and preparation method thereof |
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