Temperature-variable odor master batch, PC / ABS alloy, method and application

Abstract

The invention discloses a master batch capable of changing odor along with temperature, a PC / ABS alloy, a method and application, and belongs to the technical field of PC / ABS alloy materials. The master batch capable of changing odor along with temperature is prepared from the following components in parts by weight: 50-95 parts of carrier resin; 1 to 15 parts of compatilizer; 0.1 to 1 part of sodium copper chlorophyllin; 0.1 to 1 part of vanillin; and 0.1-1 part of zeolite powder. The invention also provides a low-emission PC / ABS alloy capable of changing odor along with temperature. The PC / ABS alloy is prepared from the following components in parts by weight: 50-90 parts of polycarbonate; 10 to 50 parts of ABS (acrylonitrile butadiene styrene); 1 to 10 parts of a toughening agent; 1-5 parts of a porous adsorbent; 0.5 to 3 parts of a deodorant; and 0.1-1 part of master batch capable of changing odor along with temperature. The PC / ABS alloy has the characteristic of low VOC (volatile organic compound), the technical indexes meet the mechanical property requirements of automotive interior materials, the PC / ABS alloy has bamboo fragrance at normal temperature and bean fragrance at high temperature, and the smell feels pleasant.

Description

Technical Field

[0001] This application belongs to the field of PC / ABS alloy material technology, and specifically relates to a temperature-dependent odor masterbatch, PC / ABS alloy, method, and application. Background Technology

[0002] The quality of the automotive interior environment has become a key indicator for measuring the overall quality and driving comfort of a vehicle. It is mainly divided into two indicators: VOCs (Volatile Organic Compounds) and odor. First, it must meet VOC limits, with benzene, toluene, ethylbenzene, xylene, styrene, formaldehyde, acetaldehyde, and acrolein being the main restricted substances. In addition, regarding odor indicators, it is necessary to meet both odor level requirements and odor perception requirements; that is, the odor should evoke a pleasant feeling in consumers, rather than a pungent or negative one. The following are some typical negative odor perceptions: Garbage smell: The smell of a garbage dump. It's a sulfurous, acidic, acetic acid-like odor.

[0003] Rotten fish smell: The smell of rotting fish, the smell of stale fish. This smell is caused by an amine.

[0004] Animal scent: The smell of animals, the smell of livestock hides and fur, the smell of livestock sheds. This is mainly the smell of phenols.

[0005] Irritating odor: An irritant odor that can be immediately felt in the nose or throat after inhalation or smelling.

[0006] During odor testing, material samples or component samples are typically heated to a specific temperature, commonly 80°C, and left for 2 hours. Under high-temperature conditions, the material releases small molecules, evoking different odor sensations.

[0007] Automotive interior materials, especially plastics, are susceptible to odor issues due to the heat resistance of their base resins and the presence of small molecule residues. To meet the performance requirements of these parts, numerous additives or masterbatches are often added. The more additives, the easier it is for small molecules to migrate to surfaces and release into the air at high temperatures, thus affecting the overall VOC levels and odor characteristics of the vehicle. Polycarbonate / acrylonitrile-butadiene-styrene copolymer (PC / ABS) alloys are widely used in automotive interior parts, such as dashboards and door panels, due to their excellent overall performance. However, the ABS component in PC / ABS materials has low heat resistance, and small molecules, especially thiols, remaining in ABS at high temperatures are difficult to remove through processing. Furthermore, these substances have an extremely low odor threshold, allowing them to be detected even at very low concentrations, resulting in a harsh, irritating odor.

[0008] To improve odor, existing technologies mainly employ three approaches: First, removing small molecules as much as possible to reduce VOCs and thus lower the odor level. However, this requires specific processing of the base material, and for surface-treated parts, without special odor-type treatment, it is very easy to develop a pungent, negative odor. For example, patent document CN101469122B discloses a low-odor, low-emission PC / ABS alloy material and its preparation method. It uses a hydrophobic odor inhibitor to create a hydrophobic odor masterbatch, and uses the hydrophobic odor adsorption masterbatch as a hydrophobic odor adsorption system to prepare low-odor, low-emission PC / ABS. The adsorption system adsorbs volatile small molecules and organic compounds that generate odors. Another example is patent document CN106751680B, which discloses an ultra-low-odor, ultra-low-emission PC / ABS alloy and its preparation method. It prepares a premix using the porous structure of silicate porous materials, adds silicate porous materials through a side feed port, and then pelletizes to obtain the PC / ABS composite material. Neither of these two approaches involves adding specific odor-causing substances to enhance the odor perception.

[0009] Secondly, to avoid negative odor perception, raw material manufacturers add specific fragrance substances to PC / ABS base materials, such as green tea and chrysanthemum scents. However, tests show that adding these substances easily causes VOC fluctuations, and the odor stability is insufficient at both room temperature and high temperatures, making it difficult to obtain a consistent evaluation. Especially at high temperatures, the amount and intensity of volatile odor substances increase, theoretically the odor perception should be more pronounced than at room temperature. However, due to the instability of odor tendencies, the reproducibility of odor perception is reduced. In actual vehicle use, the interior temperature is higher than the exterior temperature. For example, in summer, when the exterior temperature is about 30°C, the interior temperature often rises to around 40°C or even higher. Under these conditions, the odor tendencies of green tea and chrysanthemum scented PC / ABS modified materials are unstable and irregular during heating, making them unsuitable for mass production.

[0010] Third, odors can be masked by external conditions, such as using car air fresheners or perfumes, to transform them into a targeted pleasant experience. Currently, commonly used targeted odor scents are mainly green tea and chrysanthemum, but in actual testing and verification, due to the high temperature conditions, the odor type often changes, leading to negative feelings. At the same time, the odor effect is unstable and difficult to control and guide into a pleasant state for the tester.

[0011] Therefore, there is an urgent need in this field to develop an odor material that can stably and controllably impart a lasting odor sensation to the material and change positively with ambient temperature, as well as a PC / ABS alloy that can meet the basic requirements of low VOC and low odor level, meet the mechanical performance requirements of automotive interior materials, and satisfy the odor type requirements of pleasant odor from room temperature to high temperature. Summary of the Invention

[0012] To address the aforementioned issues, one of the main objectives of this application is to provide a temperature-dependent odor-changing masterbatch. This masterbatch itself possesses excellent stability and enables the modified polymer materials (especially PC / ABS alloys) to exhibit intelligent odor changes, emitting a bamboo-like aroma at room temperature and shifting to a bean-like aroma at high temperatures.

[0013] The second objective of this invention is to provide a PC / ABS alloy containing the above-mentioned masterbatch, which, while possessing intelligent odor function, also has excellent mechanical properties, heat resistance and low VOC characteristics.

[0014] A third objective of this invention is to provide a method for preparing a PC / ABS alloy comprising the above-mentioned masterbatch.

[0015] The fourth objective of this invention is to provide an application of a PC / ABS alloy containing the above-mentioned masterbatch in automotive interior materials.

[0016] To achieve the above objectives, the present invention adopts the following technical solution: In a first aspect, the present invention provides a temperature-dependent odor-variable masterbatch for PC / ABS alloys, comprising the following components in parts by weight: 82-95 parts of carrier resin; 1-15 parts compatibilizer; Sodium copper chlorophyllin 0.1-1 part; Vanillin 0.1-1 part; 0.1-1 part zeolite powder.

[0017] Furthermore, the carrier resin is polybutylene terephthalate.

[0018] Furthermore, the compatibilizer is an ethylene-methyl acrylate-glycidyl methacrylate terpolymer.

[0019] Furthermore, the purity of the sodium copper chlorophyllin is ≥98%.

[0020] Furthermore, the purity of the vanillin is ≥99.5%.

[0021] Furthermore, the zeolite powder has an ammonia absorption capacity of ≥160mmol / 100g and a particle size of 1000-5000 mesh.

[0022] Secondly, the present invention provides a PC / ABS alloy with low emission of temperature-dependent odor, made of components comprising the following parts by weight: Polycarbonate: 50-85 parts; ABS: 10-45 parts; Toughening agent: 1-10 parts; Porous adsorbent: 1-5 parts; Odor remover: 0.5-3 parts; Odor masterbatch: 0.1-1 part; The odor masterbatch used is the aforementioned temperature-dependent odor masterbatch.

[0023] Furthermore, the toughening agent includes one or more of the following: methyl methacrylate-styrene toughening agents, methyl methacrylate-acrylic toughening agents, acrylic toughening agents, and acrylic-silicone rubber toughening agents.

[0024] Furthermore, the toughening agent has a particle size of 50-700 nm; the mass ratio of the adhesive content in the toughening agent is 40%-90%.

[0025] Furthermore, the porous adsorbent includes one or more of zeolite powder or activated carbon.

[0026] Furthermore, the deodorizing agent includes one or more of active zinc oxide, phenolic antioxidant 1010, or phosphate ester antioxidant 168.

[0027] Furthermore, the number-average relative molecular weight of the ABS is 90,000-150,000, wherein the mass ratio of butadiene is 5-25 wt%, the mass ratio of acrylonitrile is 10-30 wt%, and the mass ratio of styrene is 40-70 wt%.

[0028] Furthermore, the polycarbonate has a number-average relative molecular weight of 18,000-30,000 and a glass transition temperature of 140-150°C.

[0029] Thirdly, the present invention provides a method for preparing the aforementioned low-emission, temperature-dependent odor-variable PC / ABS alloy, comprising the following steps: The carrier resin, compatibilizer, sodium copper chlorophyllin, vanillin and zeolite powder are mixed to obtain a mixture. The mixture is subjected to intensive kneading to obtain a temperature-dependent odor masterbatch. The temperature-dependent odor-variable masterbatch, polycarbonate, ABS, toughening agent, porous adsorbent, and deodorizing agent are premixed to obtain a premixed material; The premixed material is fed into a twin-screw extruder, nitrogen is injected from the first and second zones of the extruder, and supercritical carbon dioxide is injected into the third and fourth zones and the fifth and eighth zones of the extruder, respectively. After melt extrusion and granulation, the PC / ABS alloy is obtained.

[0030] Furthermore, the mixing temperature is 180-260℃, and the time is 8-15 minutes.

[0031] Fourthly, the present invention provides an application of the aforementioned low-emission, temperature-dependent odor-variable PC / ABS alloy in automotive interior materials.

[0032] Compared with the prior art, this application has the following beneficial effects: 1. This invention utilizes the high specific surface area of ​​zeolite powder to load two aroma compounds (sodium copper chlorophyllin and vanillin) onto the surface of the zeolite powder, thereby achieving the effect of fixing the aroma compounds, improving the migration performance of the aroma compounds, and allowing the aroma compounds to exhibit a bamboo aroma at room temperature and a bean aroma at high temperature at different temperatures. A carrier resin is added to the temperature-dependent aroma-variable masterbatch. This carrier resin can improve the dispersibility of the temperature-dependent aroma-variable masterbatch in the PC / ABS matrix, as well as the mechanical properties and temperature resistance of the PC / ABS matrix. The added compatibilizer enhances the binding force between the aroma compounds and the carrier resin.

[0033] 2. The low-emission, temperature-dependent variable odor PC / ABS alloy provided by this invention effectively solves the problem of unstable odor perception and the tendency for negative odors to occur when the odor masterbatch is added to the PC / ABS matrix from room temperature to high temperature. Furthermore, while imparting the temperature-dependent variable odor function to the material, it has no negative impact on its basic mechanical properties such as tensile strength, impact strength, and heat resistance, as well as its low VOC characteristics, thus solving the problem of performance degradation or VOC increase often caused by adding fragrance substances in existing methods.

[0034] Other features and effects of this application will be set forth in the following description and will be apparent in part from the description or may be learned by practicing this application. Attached Figure Description

[0035] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0036] Figure 1 A schematic flowchart of a method for preparing a low-emission, temperature-dependent odor PC / ABS alloy according to this application is shown. Detailed Implementation

[0037] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below in conjunction with the embodiments of this application. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0038] To achieve the above objectives, a first aspect of the present invention provides a temperature-dependent odor-variable masterbatch for PC / ABS alloys, comprising the following components in parts by weight: The carrier resin comprises 82-95 parts, preferably 85-90 parts; 1-15 parts of compatibilizer, preferably 6-9 parts; Sodium copper chlorophyllin, 0.1-1 part, preferably 0.2-0.5 parts; Vanillin 0.1-1 part, preferably 0.3-0.5 parts; 0.1-1 part of zeolite powder, preferably 0.1-0.5 parts.

[0039] Among current odor perception criteria, screening has revealed that bamboo (represented by bamboo mats and pillows) and bean (represented by soybean cake and Longjing green tea) are more readily accepted as positive odors and have a strong masking effect on negative odors. Further investigation revealed that vanillin, at high temperatures, leans towards a bean aroma and possesses antibacterial properties, while sodium copper chlorophyllin leans towards a bamboo aroma and has excellent deodorizing capabilities. When combined, the bamboo aroma at room temperature and the bean aroma at high temperatures are more likely to produce a pleasant odor experience. However, directly mixing these two substances into the matrix resin cannot guarantee the stability of the odor tendency. Therefore, this invention uses a carrier to carry these two substances, creating an odor masterbatch. The design concept is to first ensure that the addition of the odor masterbatch does not affect the basic physical properties of PC+ABS; secondly, to ensure that the VOC content of the material is not affected; and thirdly, to achieve an odor rating of ≤3, with an added odor pleasantness level, reaching 7 or higher for a positive odor experience.

[0040] This invention utilizes the high specific surface area of ​​zeolite powder to load two aroma compounds (sodium copper chlorophyllin and vanillin) onto the surface of the zeolite powder, thereby achieving the effect of fixing the aroma compounds, improving the migration performance of the aroma compounds, and allowing the aroma compounds to exhibit a bamboo-like aroma at room temperature and a bean-like aroma at high temperature at different temperatures. Furthermore, this invention adds a carrier resin to the temperature-dependent aroma-variable masterbatch. This carrier resin can improve the dispersibility of the temperature-dependent aroma-variable masterbatch in the PC / ABS matrix, as well as the mechanical properties and temperature resistance of the PC / ABS matrix. The added compatibilizer enhances the binding force between the aroma compounds and the carrier resin. In summary, the synergistic effect between the components of the temperature-dependent aroma-variable masterbatch effectively solves the problem of unstable aroma perception and the tendency to produce negative odor perception when the aroma masterbatch is added to the PC / ABS matrix from room temperature to high temperature. It also has a positive effect on improving the mechanical properties of the PC / ABS material.

[0041] In some preferred embodiments of the present invention, the carrier resin is polybutylene terephthalate (PBT). Further, the viscosity of polybutylene terephthalate is 0.6~1.2. The compatibilizer is ethylene-methyl acrylate-glycidyl methacrylate terpolymer (EMA-GMA). Further, the mass ratio of GMA (glycidyl methacrylate) is 5~10wt%. Controlling GMA within the above range can simultaneously provide compatibilizing and bonding properties, and control processing stability. The present invention utilizes EMA-GMA to effectively improve the binding force between PBT and aroma-enhancing substances. The resulting temperature-sensitive aroma-variable masterbatch has excellent flowability and, during post-processing, will be uniformly dispersed into the PC / ABS matrix, thereby effectively achieving the effect of temperature-sensitive aroma variation.

[0042] To further enhance the pleasantness of the temperature-dependent odor, in some preferred embodiments of the present invention, the sodium copper chlorophyllin has a purity of ≥98% or is extracted from bamboo fiber; and the vanillin has a purity of ≥99.5%.

[0043] To further efficiently load odor molecules, in some preferred embodiments of the present invention, the zeolite powder has an ammonia absorption capacity ≥160mmol / 100g and a particle size of 1000-5000 mesh.

[0044] A second aspect of the present invention provides a low-emission, temperature-dependent odor PC / ABS alloy, made of components comprising the following parts by weight: Polycarbonate: 50-85 parts, preferably 60-70 parts; ABS: 10-45 parts, preferably 30-40 parts; Toughening agent: 1-10 parts, preferably 2-7 parts; Porous adsorbent: 1-5 parts, preferably 2-3 parts; Odor remover: 0.5-3 parts, preferably 0.5-2 parts; Odor masterbatch: 0.1-1 parts, preferably 0.1-0.5 parts; wherein the odor masterbatch is the aforementioned temperature-dependent odor masterbatch.

[0045] This invention adds temperature-dependent odor masterbatch to PC and ABS matrices in extremely low amounts, and combines it with other additives. This results in a final material that not only retains the inherent excellent mechanical properties of PC / ABS, but also adds intelligent odor functions such as "bamboo fragrance at room temperature and bean fragrance at high temperature" to satisfy consumers' pleasant odor experience. At the same time, it does not contain harmful VOCs such as pentazocine and trialdehyde, halogenated hydrocarbons, etc., and maintains low VOC emission characteristics.

[0046] In some preferred embodiments of the present invention, the toughening agent includes one or more of the following: methyl methacrylate-styrene toughening agents (such as methyl methacrylate / butadiene / styrene copolymer MBS), methyl methacrylate-acrylic toughening agents (MABS resin), acrylic toughening agents (ACR resin), and acrylic-silicone rubber toughening agents (such as MPS resin). The particle size of the toughening agent is 50-700 nm. The mass ratio of the adhesive content in the toughening agent is 40%-90%. By adding the above-mentioned toughening agent to the alloy system, phase separation can be prevented, the phase interface between PC and ABS can be strengthened, and warpage deformation of the product during molding can be reduced by refining the phase morphology and reducing internal stress.

[0047] To further reduce VOC emissions from PC / ABS alloys, in some preferred embodiments of the present invention, the porous adsorbent comprises one or more of zeolite powder or activated carbon. The deodorizing agent comprises one or more of activated zinc oxide, phenolic antioxidant 1010, or phosphate ester antioxidant 168.

[0048] To further improve the overall performance of the PC / ABS alloy, in some preferred embodiments of the present invention, the ABS has a number-average relative molecular weight of 90,000-150,000, wherein the mass ratio of butadiene is 5-25 wt%, the mass ratio of acrylonitrile is 10-30 wt%, and the mass ratio of styrene is 40-70 wt%. The polycarbonate has a number-average relative molecular weight of 18,000-30,000 and a glass transition temperature of 140-150°C.

[0049] A third aspect of this invention also provides a method for preparing a PC / ABS alloy with low emission of temperature-dependent odor, such as... Figure 1 As shown, it includes the following steps: Step S1: Mix the carrier resin, compatibilizer, sodium copper chlorophyllin, vanillin and zeolite powder to obtain a mixture. Step S2: The mixture is kneaded to obtain a masterbatch with variable odor depending on temperature; Step S3: The temperature-dependent odor-variable masterbatch, polycarbonate, ABS, toughening agent, porous adsorbent, and deodorizing agent are premixed to obtain a premixed material; Step S4: The premixed material is fed into a twin-screw extruder, nitrogen is injected from the first and second zones of the extruder, and supercritical carbon dioxide is injected into the third and fourth zones and the fifth and eighth zones of the extruder, respectively. After melt extrusion, the PC / ABS alloy is obtained by granulation.

[0050] This invention pre-forms odor additives into odor masterbatches, which are then co-dispersed with the base resin to form a uniform, stable, and temperature-variable odor modified resin, ensuring batch-to-batch product quality stability and consistency. Furthermore, this invention incorporates the injection of nitrogen and supercritical carbon dioxide in separate zones during melt extrusion. Nitrogen isolates oxygen and moisture, preventing thermal oxidative degradation of the material under high-temperature processing. The introduction of supercritical carbon dioxide lowers the processing temperature, mitigating the risk of thermal oxidative degradation and hydrolysis of PC and ABS at high temperatures, regulating phase morphology, and achieving nanoscale dispersion and interface reinforcement.

[0051] In some preferred embodiments of the present invention, the mixing temperature is 180-260°C and the time is 8-15 minutes. The mixing time is 10-30 minutes.

[0052] In some preferred embodiments of the present invention, the temperature of the twin-screw extruder is 200-260°C, and the screw speed is 200-600 rpm. The premixing time is 5-30 min.

[0053] A fourth aspect of the present invention provides the application of the aforementioned low-emission temperature-dependent odor-variable PC / ABS alloy in automotive interior materials.

[0054] Based on the reasons mentioned above, the low-emission, temperature-dependent odor-variable PC / ABS alloy of the present invention can be applied to automotive interior trim panels or housings, effectively achieving the effect of temperature-dependent odor variation with a pleasant odor experience. It also possesses excellent mechanical and heat resistance properties, meeting the performance requirements of automotive interior components.

[0055] The present application will be further described in detail below with reference to specific embodiments, which should not be construed as limiting the scope of protection claimed in the present application.

[0056] A temperature-dependent odor-variable masterbatch is provided, wherein the composition of the temperature-dependent odor-variable masterbatch of Examples 1 to 6 is shown in Table 1.

[0057] Table 1

[0058] A method for preparing a low-emission, temperature-dependent odor PC / ABS alloy includes the following steps: Step S1: Prepare materials according to the weight proportions of each component of the temperature-dependent odor masterbatch; Step S2: Mix the prepared carrier resin, compatibilizer, sodium copper chlorophyllin, vanillin and zeolite powder for 15 minutes to obtain a mixture. Step S3: Place the above mixture in an internal mixer, set the temperature to 250°C, and shear and blend for 12 minutes to obtain a masterbatch with variable odor depending on temperature. Step S4: Prepare materials according to the weight ratio of the PC / ABS alloy with low emission and temperature-dependent odor. Step S5: The temperature-dependent odor-varying masterbatch, polycarbonate (relative molecular weight of 25,000, glass transition temperature of 145°C), ABS (relative molecular weight of 12,000, butadiene mass ratio of 15wt%, acrylonitrile mass ratio of 20wt%, styrene mass ratio of 65wt%), toughening agent (particle size of 100nm, adhesive content of 50%), porous adsorbent (zeolite powder, particle size of 4,000 mesh), and deodorizing agent (active zinc oxide, phenolic antioxidant 1010) are premixed for 20 minutes to obtain a premix. Step S6: Place the premixed material in a twin-screw extruder with a barrel temperature of 245°C and a screw speed of 450 rpm. Inject nitrogen gas through a gas pump from zones one and two of the extruder. Inject carbon dioxide into a delivery pump, controlling the carbon dioxide delivery pressure at a critical pressure of 7.4-50 MPa and the critical temperature above 31°C to convert it into supercritical carbon dioxide. Then, inject the supercritical carbon dioxide from zones three and four and zones five to eight of the extruder respectively. After melt extrusion, a PC / ABS alloy with low emission and temperature-dependent odor is obtained.

[0059] The only difference between the PC / ABS alloys of Comparative Examples 1 to 3 and the embodiments of the present invention is that no temperature-dependent odor masterbatch was added. The composition of the low-emission temperature-dependent odor PC / ABS alloys of Examples 1-6 and the composition ratio of the PC / ABS alloys of Comparative Examples 1-3 are shown in Table 2.

[0060] Table 2

[0061] The components of the temperature-dependent odor-variable masterbatch in Table 2 above are: 90 parts PBT resin, 9 parts compatibilizer EMA-GMA, 0.3 parts sodium copper chlorophyllin, 0.4 parts vanillin, and 0.3 parts zeolite powder.

[0062] Performance testing: 1. Comparison of mechanical properties: The addition of temperature-dependent odor masterbatch was verified to not affect the basic physical properties of the plastic. The core test items are as follows: Melt flow index: According to ISO 1133-1, test conditions: 260℃ * 5kg Tensile properties: Tested according to ISO 527, under the following conditions: tensile speed 50 mm / min, 23℃; Flexural modulus: Tested according to ISO 178, with a span of 64 mm and a test speed of 2 mm / min. Notched impact strength: According to ISO 179 / 1eA, test conditions: 4J pendulum, span of 62mm, impact velocity of 2.9m / s (notch is recommended to be machined). Vicat softening point: According to ISO 306, test conditions: 5kg, 50℃ / h.

[0063] The performance test results of the PC / ABS alloys of Examples 1 to 6 and Comparative Examples 1 to 3 are shown in Table 3.

[0064] Table 3

[0065] The test results in Table 3 above show that the effect of temperature-dependent odor masterbatch on the basic physical properties (tensile, bending, and impact properties) and thermal properties of the final PC / ABS alloy is negligible.

[0066] 2. VOC performance comparison: The addition of odor masterbatch must not affect the quantitative indicators of VOC and TVOC in the current plastic. The core test requirements are as follows: VOC: According to Chery New Energy standard Q / NEQ S1-125, the main controlled substances are "five benzenes and three aldehydes". The bag method is used for testing, with a heating temperature of 65℃ and a heating time of 2 hours.

[0067] TVOC, or Total Organic Carbon, refers to volatile organic compounds with retention times between n-hexane and n-hexadecane, as analyzed by gas chromatography. Testing was conducted according to Chery New Energy's standard Q / NEQ T1-7.

[0068] For PC / ABS materials, which are mainly used in instrument panels, sub-instrument panels and door panels, the content of each volatile substance must not exceed the content shown in Table 4 (VOC and TVOC requirements).

[0069] Table 4

[0070] The VOC performance of the low-emission, temperature-dependent odor PC / ABS alloys according to the component ratios of Examples 1 to 6 in Table 5 was compared with that of the PC / ABS alloys of Comparative Examples 3 and 4.

[0071] Table 5

[0072] The components of the temperature-dependent odor-variable masterbatch in Table 5 above are: 90 parts PBT resin, 9 parts compatibilizer EMA-GMA, 0.3 parts sodium copper chlorophyllin, 0.4 parts vanillin, and 0.3 parts zeolite powder.

[0073] The VOC performance test results of the PC / ABS alloy in Table 5 above are shown in Table 6. In the table, ND (Not Detected) indicates that the content of the target substance is lower than the detection limit of the detection equipment.

[0074] Table 6

[0075] Comparative Example 1 is a modified material of conventional PC / ABS, and Comparative Example 2 is a modified PC / ABS material with low emissions. As shown in Examples 1-5 and Comparative Example 1, the modified PC / ABS material of the present invention significantly reduces VOC and TOV compared to existing conventional modified PC / ABS materials. As shown in Examples 1-5 and Comparative Example 2, the PC / ABS material with temperature-dependent variable odor masterbatch added in the present invention has VOC and TOV levels comparable to existing low-emission modified PC / ABS materials, exhibiting low emissions and meeting the low VOC requirements for automotive interior materials.

[0076] 3. Comparison of odor performance: The addition of odor masterbatch must ensure that the odor evaluation meets specific level requirements and that the odor perception is free of negative effects; specific negative odor perceptions must be eliminated. Odor evaluators must provide not only the intensity of the odor evaluation but also the odor tendency, such as paint smell, solvent smell, acid smell, plastic smell, rubber smell, musty smell, rotten smell, fishy smell, etc.

[0077] Odor: According to Chery New Energy Q / NEQ T1-8 evaluation, the final odor rating result is the arithmetic mean of the scores given by three or five ratingrs. If the average is not an integer, it can be approximated to the level of the nearest multiple of the arithmetic mean. For example, if the average is 3.7, it should be approximated to level 3.5, and if the average is 3.8, it should be approximated to level 4.0.

[0078]

[0079] The odor performance of the low-emission, temperature-variable odor PC / ABS alloys according to the component ratios of Examples 1 to 6 in Table 7 was compared with that of the PC / ABS alloys of Comparative Examples 5 and 6.

[0080] Table 7

[0081] The components of the temperature-dependent odor-variable masterbatch in Table 7 above are: 90 parts PBT resin, 9 parts compatibilizer EMA-GMA, 0.3 parts sodium copper chlorophyllin, 0.4 parts vanillin, and 0.3 parts zeolite powder.

[0082] The odor performance test results of the PC / ABS alloy in Table 7 above are shown in Table 8. In Table 8, the high temperature odor perception and odor level evaluation refers to the odor smelling test conducted after being placed at a high temperature of 80℃ for 2 hours and then cooled to 60℃. The room temperature refers to the odor smelling test conducted at room temperature (25℃).

[0083] Table 8

[0084] Comparative Example 1 is a conventional PC+ABS modified material, and Comparative Example 2 is a low-emission PC / ABS modified material. The odor pleasantness evaluation is an additional test when customizing fragrances, applicable to perfumes, custom plastic odors, and custom fabric and leather odors. The rating is divided into 1-10 levels, with higher levels indicating higher pleasantness. A positive feeling of ≥7 indicates a pleasant psychological state.

[0085] Based on Examples 1-5 and Comparative Example 1, compared to conventional PC / ABS, the modified material with added odor masterbatch exhibited better odor performance at high temperatures. Examples 1-5 and Comparative Example 2 showed comparable odor performance compared to low-emission PC / ABS. In terms of odor perception, due to the presence of the odor masterbatch, Examples 1-5 all exhibited specific bamboo and bean aromas at both room and high temperatures. Since these two aromas have high olfactory acceptability, their odor pleasantness exceeded the pleasant state, with a rating of 8. The experimental results indicate that the addition of temperature-variable odor masterbatch achieved the same odor level for PC / ABS as low-emission PC / ABS, and showed significantly better performance in odor perception and odor pleasantness compared to low-emission PC / ABS.

[0086] Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of this application.

Claims

1. A temperature-dependent odor-variable masterbatch for PC / ABS alloys, characterized in that, It is made from the following components in parts by weight: 82-95 parts of carrier resin; 1-15 parts compatibilizer; Sodium copper chlorophyllin 0.1-1 part; Vanillin 0.1-1 part; 0.1-1 part zeolite powder.

2. The temperature-dependent odor-variable masterbatch according to claim 1, characterized in that, The carrier resin is polybutylene terephthalate.

3. The temperature-dependent odor-variable masterbatch according to claim 1, characterized in that, The compatibilizer is an ethylene-methyl acrylate-glycidyl methacrylate terpolymer.

4. The temperature-dependent odor-variable masterbatch according to claim 1, characterized in that, The purity of the sodium copper chlorophyllin is ≥98%; the purity of the vanillin is ≥99.5%; the ammonia absorption capacity of the zeolite powder is ≥160mmol / 100g, and the particle size is 1000-5000 mesh.

5. A PC / ABS alloy with low emission and temperature-dependent odor, characterized in that, It is made from the following components in parts by weight: Polycarbonate: 50-85 parts; ABS: 10-45 parts; Toughening agent: 1-10 parts; Porous adsorbent: 1-5 parts; Odor remover: 0.5-3 parts; Odor masterbatch: 0.1-1 part; Wherein, the odor masterbatch adopts the temperature-variable odor masterbatch according to any one of claims 1 to 4.

6. The low-emission, temperature-dependent odor PC / ABS alloy according to claim 5, characterized in that, The toughening agent includes one or more of the following: methyl methacrylate-styrene toughening agents, methyl methacrylate-acrylic toughening agents, acrylic toughening agents, and acrylic-silicone rubber toughening agents.

7. The low-emission, temperature-dependent odor PC / ABS alloy according to claim 5, characterized in that, The porous adsorbent includes one or more of zeolite powder or activated carbon; The deodorizing agent includes one or more of active zinc oxide, phenolic antioxidant 1010, or phosphate ester antioxidant 168; The ABS has a number-average relative molecular weight of 90,000-150,000, wherein the mass ratio of butadiene is 5-25 wt%, the mass ratio of acrylonitrile is 10-30 wt%, and the mass ratio of styrene is 40-70 wt%. The polycarbonate has a number-average relative molecular weight of 18,000-30,000 and a glass transition temperature of 140-150℃.

8. A method for preparing a low-emission, temperature-dependent odor PC / ABS alloy as described in any one of claims 5 to 7, characterized in that, Includes the following steps: The carrier resin, compatibilizer, sodium copper chlorophyllin, vanillin and zeolite powder are mixed to obtain a mixture. The mixture is subjected to intensive kneading to obtain a temperature-dependent odor masterbatch. The temperature-dependent odor-variable masterbatch, polycarbonate, ABS, toughening agent, porous adsorbent, and deodorizing agent are premixed to obtain a premixed material; The premixed material is fed into a twin-screw extruder, nitrogen is injected from the first and second zones of the extruder, and supercritical carbon dioxide is injected into the third and fourth zones and the fifth and eighth zones of the extruder, respectively. After melt extrusion and granulation, the PC / ABS alloy is obtained.

9. The method for preparing a low-emission, temperature-dependent odor-variable PC / ABS alloy according to claim 8, characterized in that, The mixing temperature is 180-260℃, and the time is 8-15 minutes.

10. The application of a low-emission, temperature-dependent odor PC / ABS alloy as described in any one of claims 5 to 7 in automotive interior materials.

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