Composite material as well as preparation method and application thereof

Abstract

The invention relates to a composite material as well as a preparation method and application thereof. The composite material comprises the following components: a resin matrix, rubber powder, a black dye and an auxiliary agent, the black dye comprises the following components: a perylene diimide derivative. The perylene diimide black dye is used for replacing the traditional black dye in the formula, so that the visible light absorption degree of the material is effectively improved on the premise that the glossiness is not reduced, and the blackness of the material is greatly improved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of spray-free materials, and particularly relates to a composite material and a preparation method and application thereof, in particular to a high-gloss high-blackness spray-free material and a preparation method thereof. BACKGROUND

[0002] The spray-free material is an aesthetic plastic with pigments added in resin, and the application of the material in the automobile field can reduce VOC by 99% and reduce the comprehensive cost by 20%-50%. For the spray-free plastic, the color and surface condition of the original spray material should be restored as much as possible. For the high-gloss black spray-free material, the parameters for measuring the color and surface condition are blackness and glossiness.

[0003] For the high-gloss black spray-free material, the improvement of blackness mainly depends on the selection of black dyes, and the commonly used black dyes mainly include carbon black, aniline black and oil-soluble black. The improvement of glossiness should use high-gloss molds for injection molding on the one hand, and use high-hardness base material plastics such as PC, ASA and ABS on the other hand.

[0004] Patent CN109486081A discloses a high-gloss high-blackness ASA material and a preparation method thereof. The ASA material uses oilized black as a black pigment, the L value is reduced to 24.8, and the glossiness is increased to 96.4%. Compared with conventional ASA materials, the blackness and glossiness are greatly improved. Patent CN103360670A discloses a general high-gloss black masterbatch. The masterbatch uses carbon black and oil-soluble black as black dyes. The L value of the ABS material using the masterbatch is reduced to 21.2, and the glossiness can reach 84%.

[0005] How to further improve the blackness of the material without reducing the glossiness is a problem to be solved at present. SUMMARY

[0006] To solve the above technical problems, the purpose of the present application is to provide a composite material and a preparation method and application thereof. By adding perylene diimide dyes in the ASA material, the absorption of visible light by the material can be effectively improved without reducing the glossiness, thereby greatly improving the blackness of the material and realizing the widening of the application range of commercial vehicle exterior.

[0007] To achieve this purpose, the present application adopts the following technical solutions:

[0008] In a first aspect, the present application provides a composite material, which comprises the following components: a resin matrix, a glue powder, a black dye and an additive; the component of the black dye comprises a perylene diimide derivative.

[0009] In the present application, the perylene diimide derivative has a specific conjugated structure, which can more efficiently absorb visible light. The perylene diimide derivative is a new type of high-performance organic dye, which is a class of fused ring ketone pigments. Compared with conventional carbon black, aniline black and other pigments, this type of pigment has the characteristics of high blackness and excellent dispersion performance.

[0010] Preferably, the resin matrix comprises acrylonitrile-styrene copolymer.

[0011] In the present application, the acrylonitrile-styrene copolymer (AS resin) has high gloss, good heat resistance and mechanical properties, and high chemical stability.

[0012] Preferably, the rubber powder comprises acrylonitrile-styrene-acrylate terpolymer rubber powder.

[0013] In the present application, the acrylonitrile-styrene-acrylate terpolymer rubber powder (ASA rubber powder) is a graft copolymer of styrene, acrylate and acrylonitrile, which is added to the AS resin to improve the impact strength of the material.

[0014] Preferably, the components of the acrylonitrile-styrene-acrylate terpolymer rubber powder comprise acrylonitrile-styrene-acrylate terpolymer and phthalic acid plasticizer.

[0015] Preferably, the mass percentage of acrylonitrile-styrene-acrylate terpolymer is 90%-98%, for example, it can be 91%, 93%, 95%, 96% or 97%, based on 100% of the mass percentage of the rubber powder.

[0016] Preferably, the weight fraction of the resin matrix is 40-60 parts, for example, it can be 43 parts, 45 parts, 50 parts, 52 parts or 55 parts, etc.

[0017] Preferably, the weight fraction of the rubber powder is 20-40 parts, for example, it can be 23 parts, 25 parts, 30 parts, 33 parts or 35 parts, etc.

[0018] Preferably, the auxiliary agent comprises an antioxidant and / or an anti-ultraviolet aging agent.

[0019] Preferably, the antioxidant comprises a primary antioxidant and a secondary antioxidant.

[0020] Preferably, the primary antioxidant comprises a hindered phenol and / or a hindered amine.

[0021] Preferably, the secondary antioxidant comprises any one or a combination of at least two of phosphite, organic sulfide or metal ion passivator.

[0022] In the present application, the primary antioxidant and the secondary antioxidant are used in combination, which has a synergistic protection effect.

[0023] Preferably, the anti-UV aging agent includes any one or a combination of at least two of the following: light shielding agent, UV absorber, quencher, or free radical scavenger.

[0024] Preferably, the light-shielding agent comprises any one or a combination of at least two of carbon black, zinc oxide, or titanium dioxide.

[0025] Preferably, the ultraviolet absorber includes any one or a combination of at least two of the following: salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, or triazines.

[0026] Preferably, the quenching agent comprises an organic complex of nickel.

[0027] Preferably, the free radical scavenger comprises a hindered amine derivative.

[0028] In this invention, light-shielding agents, ultraviolet light absorbers, quenchers, and free radical scavengers are used in combination to generate a multi-layered protective barrier, which plays a synergistic protective role.

[0029] Preferably, the antioxidant is present in 0.5-2 parts by weight, for example, 0.8 parts, 1 part, 1.2 parts, 1.5 parts or 1.8 parts, etc.

[0030] Preferably, the amount of the anti-UV aging agent is 0.3-2 parts by weight, for example, 0.5 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts or 1.8 parts, etc.

[0031] Preferably, the components of the black dye further include a masterbatch carrier and / or a dispersing agent.

[0032] Preferably, the color masterbatch carrier comprises an acrylonitrile-styrene-acrylate terpolymer carrier.

[0033] Preferably, the dispersing agent comprises an ethylene bis-stearamide dispersant.

[0034] Preferably, the black dye is present in 0.5-3 parts by weight, for example, 1 part, 1.5 parts, 2 parts, 2.5 parts or 2.8 parts, etc.

[0035] In this invention, the amount of black dye used needs to be controlled within a specific range. If too much black dye is used, it will partially agglomerate, reducing the surface uniformity of the material and decreasing its gloss. Furthermore, excessive black dye will increase the amount of dye decomposition after xenon lamp aging, thereby reducing xenon lamp aging resistance. If too little black dye is used, the blackness value will increase, and the blackness will decrease.

[0036] Preferably, based on the mass percentage content of the black dye being 100%, the mass percentage content of the perylene diimide derivative is 35%-45%, for example, it can be 37%, 39%, 40%, 41% or 43%, etc.

[0037] Preferably, the perylene diimide derivatives include compounds as shown in Formula I:

[0038] ;

[0039] R1 and R2 are each independently selected from unsubstituted C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18 or C19, etc.) saturated alkyl groups.

[0040] Preferably, the infrared absorption wavelength of the black dye is 750-1000 nm, for example, it can be 800 nm, 850 nm, 900 nm, 930 nm or 970 nm.

[0041] In this invention, for perylene diimide derivatives, the larger the molecular dipole moment, the greater the visible light absorption, and the higher the corresponding pigment blackness. The molecular dipole moment of perylene diimide derivatives can be measured by their near-infrared absorption wavelength; the longer the infrared absorption wavelength, the larger the molecular dipole moment and the higher the blackness. If the infrared absorption wavelength is too long, the resistance to xenon lamp aging deteriorates.

[0042] In this invention, the infrared absorption wavelength of the black dye refers to the maximum absorption wavelength of the black dye.

[0043] Preferably, the composite material comprises the following components in parts by weight: 40-60 parts resin matrix, 20-40 parts adhesive powder, 0.5-3 parts black dye, 0.5-2 parts antioxidant, and 0.3-2 parts UV aging agent.

[0044] In a second aspect, the present invention provides a method for preparing a composite material as described in the first aspect, the method comprising the following steps:

[0045] All components of the composite material are mixed to obtain a premix; the premix is ​​then compounded, extruded, and granulated to obtain the composite material.

[0046] Preferably, the mixing is carried out in a high-speed mixer.

[0047] Preferably, the mixing, extrusion, and granulation are carried out in a twin-screw extruder.

[0048] Preferably, the main motor speed of the twin-screw extruder is 350-450 rpm, for example, it can be 360 ​​rpm, 380 rpm, 400 rpm, 420 rpm or 440 rpm, etc.

[0049] Preferably, the barrel temperature of the twin-screw extruder is 210-240℃, for example, it can be 215℃, 220℃, 225℃, 230℃ or 235℃, etc.

[0050] Preferably, the die head temperature of the twin-screw extruder is 210-220℃, for example, it can be 212℃, 214℃, 215℃, 216℃ or 218℃, etc.

[0051] Thirdly, the present invention provides an application of the composite material as described in the first aspect in automotive exterior trim.

[0052] Compared with the prior art, the present invention has at least the following beneficial effects:

[0053] The composite material provided by this invention significantly improves the material's blackness by replacing traditional black dyes with perylene diimide-based black dyes in the ASA material formulation, while maintaining gloss. The dyes in this invention have simple structures, high photo-aging resistance, safe production processes, and moderate production costs, making them highly valuable and promising for market applications. Furthermore, by adjusting the formulation and selecting perylene diimide-based black dyes with different infrared absorption wavelengths and specific addition ratios, different blackness enhancement effects can be achieved, allowing for flexible matching of colors for commercial vehicle exterior metal paint parts. Detailed Implementation

[0054] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0055] The sources of some of the raw materials used in this invention are as follows:

[0056] AS resin was purchased from Chi Mei Corporation, and its grade is D-168.

[0057] ASA high-colloid powder was purchased from Mitsubishi Rayon Co., Ltd. of Japan, with the grade SX-006.

[0058] The oil-based black dyes were purchased from Dongguan Bosheng Plastics Technology Co., Ltd.

[0059] The AS carrier high-gloss black masterbatch (infrared absorption wavelengths of 750nm, 1000nm, and 1500nm) was purchased from BASF Chemical Company, with the grades Paliogen Black L 0086, Lumogen Black K 0087, and Lumogen Black K 0088.

[0060] Example 1

[0061] This embodiment provides a composite material and its preparation method. The composite material comprises the following components in parts by weight: 60 parts AS resin, 40 parts ASA high-gloss powder, 0.5 parts AS carrier high-gloss black masterbatch, 0.2 parts antioxidant 1010, 0.5 parts auxiliary antioxidant DLTP, and 0.3 parts anti-UV aging agent UV-327. The AS carrier high-gloss black masterbatch has an infrared absorption wavelength of 750 nm, and the perylene diimide derivative in the AS carrier high-gloss black masterbatch has the following structure:

[0062] .

[0063] The method for preparing the composite material includes the following steps:

[0064] (1) Weigh AS resin, ASA high-gloss powder, AS carrier high-gloss black masterbatch, antioxidant 1010, auxiliary antioxidant DLTP and anti-ultraviolet aging agent UV-327, mix them evenly with a high-speed mixer to obtain a premix.

[0065] (2) The obtained premixed material is placed in a twin-screw extruder for mixing. The main machine speed is 400 rpm, the barrel temperature is 210-240℃, the die head temperature is 210-220℃, and the material is melt-extruded. After being pulled, cooled in a water tank, and pelletized, the composite material is obtained.

[0066] Example 2

[0067] This embodiment provides a composite material and its preparation method. The composite material comprises the following components in parts by weight: 40 parts AS resin, 20 parts ASA high-gloss powder, 3 parts AS carrier high-gloss black masterbatch, 0.5 parts antioxidant 1010, 0.5 parts auxiliary antioxidant DLTP, and 2 parts UV-327 anti-ultraviolet aging agent. The AS carrier high-gloss black masterbatch has an infrared absorption wavelength of 750 nm.

[0068] The method for preparing the composite material includes the following steps:

[0069] (1) Weigh AS resin, ASA high-gloss powder, AS carrier high-gloss black masterbatch, antioxidant 1010, auxiliary antioxidant DLTP and anti-ultraviolet aging agent UV-327, mix them evenly with a high-speed mixer to obtain a premix.

[0070] (2) The obtained premixed material is placed in a twin-screw extruder for mixing. The main machine speed is 350 rpm, the barrel temperature is 210-240℃, the die head temperature is 210-220℃, and the material is melt-extruded. After being pulled, cooled in a water tank, and pelletized, the composite material is obtained.

[0071] Example 3

[0072] This embodiment provides a composite material and its preparation method. The composite material comprises the following components in parts by weight: 50 parts AS resin, 30 parts ASA high-gloss powder, 1 part AS carrier high-gloss black masterbatch, 0.5 parts antioxidant 1010, 1 part auxiliary antioxidant DLTP, and 1 part UV-327 anti-ultraviolet aging agent. The AS carrier high-gloss black masterbatch has an infrared absorption wavelength of 750 nm.

[0073] The method for preparing the composite material includes the following steps:

[0074] (1) Weigh AS resin, ASA high-gloss powder, AS carrier high-gloss black masterbatch, antioxidant 1010, auxiliary antioxidant DLTP and anti-ultraviolet aging agent UV-327, mix them evenly with a high-speed mixer to obtain a premix.

[0075] (2) The obtained premixed material is placed in a twin-screw extruder for mixing. The main machine speed is 450 rpm, the barrel temperature is 210-240℃, the die head temperature is 210-220℃, and the material is melt-extruded. After being pulled, cooled in a water tank, and pelletized, the composite material is obtained.

[0076] Example 4

[0077] This embodiment provides a composite material and its preparation method. The only difference from Example 1 is that the weight of the AS carrier high-gloss black masterbatch is 1.5 parts, and the other conditions are the same as in Example 1.

[0078] Example 5

[0079] This embodiment provides a composite material and its preparation method. The only difference from Example 1 is that the weight of the AS carrier high-gloss black masterbatch is 3 parts, and the other conditions are the same as in Example 1.

[0080] Example 6

[0081] This embodiment provides a composite material and its preparation method. The only difference from Example 4 is that the infrared absorption wavelength of the AS carrier high-gloss black masterbatch is 1000 nm, and the structure of the perylene diimide derivative in the AS carrier high-gloss black masterbatch is as follows:

[0082] .

[0083] Example 7

[0084] This embodiment provides a composite material and its preparation method. The only difference from Example 4 is that the infrared absorption wavelength of the AS carrier high-gloss black masterbatch is 1500 nm, and the structure of the perylene diimide derivative in the AS carrier high-gloss black masterbatch is as follows:

[0085] .

[0086] Comparative Example 1

[0087] This comparative example provides a composite material and its preparation method. The only difference from Example 4 is that the AS carrier high-gloss black masterbatch is replaced with the same weight parts of oil-based black dye.

[0088] Test methods

[0089] Gloss (60° angle) test: Refer to GB / T 8807-1988 for testing.

[0090] Color blackness L value test: Refer to GB / T 7921-2008 for testing.

[0091] Color difference test after xenon lamp aging (1000 h): Tested according to GB / T 16422-2022.

[0092] For gloss, a higher value indicates better gloss; for blackness, a lower value indicates better blackness; for color difference, a lower value indicates better resistance to xenon lamp aging.

[0093] The test results are shown in Table 1.

[0094] Table 1

[0095]

[0096] The test results show that:

[0097] (1) As can be seen from Examples 1-7, the present invention effectively improves the absorption of visible light by the material by replacing traditional black dyes with perylene diimide black dyes in the ASA material formulation without reducing the gloss, thereby significantly improving the blackness of the material.

[0098] (2) A comparison of Examples 1 and 4-5 shows that the present invention can achieve better technical effects by further limiting the amount of black dye used. When the infrared absorption wavelength is 750 nm, the more perylene diimide black dyes there are, the better the blackness of the material, but the gloss and resistance to xenon lamp aging gradually deteriorate.

[0099] A comparison of Examples 4 and 6-7 shows that the present invention achieves better technical results by further limiting the infrared absorption wavelength of the black dye. When the weight percentage of perylene diimide black dye is 1.5 parts, the longer the infrared absorption wavelength of the perylene diimide black dye, the better the blackness of the material, while the gloss does not change significantly. However, the resistance to xenon lamp aging gradually deteriorates. Considering that a color difference ≤1.5 is generally considered to be indistinguishable to the naked eye, when this material is used as an exterior component, the infrared absorption wavelength of the dye should not exceed 1000 nm.

[0100] (3) As can be seen from Example 1 and Comparative Example 1, if the black dye containing perylene diimide derivatives of the present invention is not used, the blackness and resistance to xenon lamp aging will deteriorate.

[0101] In summary, this invention significantly improves the blackness of ASA materials by replacing traditional black dyes with perylene diimide-based black dyes in the formulation, while maintaining gloss.

[0102] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A composite material, characterized in that, The composite material comprises the following components: resin matrix, adhesive powder, black dye, and additives; The black dye comprises perylene diimide derivatives.

2. The composite material according to claim 1, characterized in that, The resin matrix includes an acrylonitrile-styrene copolymer; Preferably, the adhesive powder comprises acrylonitrile-styrene-acrylate terpolymer adhesive powder; Preferably, the components of the acrylonitrile-styrene-acrylate terpolymer powder include: acrylonitrile-styrene-acrylate terpolymer and phthalic acid plasticizer; Preferably, based on the mass percentage of the adhesive powder being 100%, the mass percentage of the acrylonitrile-styrene-acrylate terpolymer is 90%-98%; Preferably, the resin matrix is ​​40-60 parts by weight; Preferably, the amount of adhesive powder is 20-40 parts by weight.

3. The composite material according to claim 1 or 2, characterized in that, The additives include antioxidants and / or anti-ultraviolet aging agents; Preferably, the antioxidant includes a primary antioxidant and a secondary antioxidant; Preferably, the primary antioxidant comprises hindered phenols and / or hindered amines; Preferably, the auxiliary antioxidant includes any one or a combination of at least two of phosphites, organic sulfides, or metal ion passivators; Preferably, the anti-UV aging agent includes any one or a combination of at least two of the following: light shielding agent, UV absorber, quencher, or free radical scavenger; Preferably, the light-shielding agent comprises any one or a combination of at least two of carbon black, zinc oxide, or titanium dioxide; Preferably, the ultraviolet light absorber includes any one or a combination of at least two of the following: salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, or triazines; Preferably, the quenching agent comprises an organic complex of nickel; Preferably, the free radical scavenger comprises a hindered amine derivative; Preferably, the antioxidant is present in 0.5-2 parts by weight; Preferably, the amount of the anti-UV aging agent is 0.3-2 parts by weight.

4. The composite material according to any one of claims 1-3, characterized in that, The components of the black dye also include a masterbatch carrier and / or dispersing agent; Preferably, the color masterbatch carrier comprises an acrylonitrile-styrene-acrylate terpolymer carrier; Preferably, the dispersing agent comprises an ethylene bis-stearamide dispersant; Preferably, the black dye is present in 0.5-3 parts by weight; Preferably, based on the black dye having a mass percentage content of 100%, the perylene diimide derivative has a mass percentage content of 35%-45%.

5. The composite material according to any one of claims 1-4, characterized in that, Perylene diimide derivatives include compounds as shown in Formula I: ； R1 and R2 are each independently selected from unsubstituted C1-C20 saturated alkyl groups; Preferably, the infrared absorption wavelength of the black dye is 750-1000 nm.

6. The composite material according to any one of claims 1-5, characterized in that, The composite material comprises the following components in parts by weight: 40-60 parts resin matrix, 20-40 parts adhesive powder, 0.5-3 parts black dye, 0.5-2 parts antioxidant, and 0.3-2 parts UV aging agent.

7. A method for preparing the composite material according to any one of claims 1-6, characterized in that, The preparation method includes the following steps: All components of the composite material are mixed to obtain a premix; the premix is ​​then compounded, extruded, and granulated to obtain the composite material.

8. The preparation method according to claim 7, characterized in that, The mixing is carried out in a high-speed mixer.

9. The preparation method according to claim 7 or 8, characterized in that, The mixing, extrusion, and granulation are carried out in a twin-screw extruder; Preferably, the main motor speed of the twin-screw extruder is 350-450 rpm; Preferably, the barrel temperature of the twin-screw extruder is 210-240℃; Preferably, the die head temperature of the twin-screw extruder is 210-220°C.

10. The application of a composite material as described in any one of claims 1-5 in automotive exterior trim.

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