ABS resin material having flat spectral transmission characteristics, method for producing the same, and use thereof

Abstract

The present invention relates to an ABS resin material having flat spectral transmission characteristics, its manufacturing method and use. The ABS resin material having flat spectral transmission characteristics provided by the present invention includes an acrylonitrile-butadiene-styrene copolymer, an antioxidant, a dispersant and an additive. The present invention constructs a non-glass material, which has flat spectral transmission characteristics and has excellent neutral filter effect in a wider wavelength range of 380-980 nm, and has a simple processing process, high efficiency, low cost, and can be widely used in the manufacture of optical products such as filters, video cameras, or digital cameras.

Description

Technical Field

[0001] The present invention belongs to the technical field of plastic products, and specifically relates to an ABS resin material having flat spectral transmission characteristics, a manufacturing method thereof, and uses thereof.

Background Art

[0002] A neutral optical filter is a lens commonly used in photographic equipment. It filters light non-selectively, filters light equally and uniformly, and brings an equal or similar reduction effect to light within a specific wavelength range. The neutral optical filter only weakens light and has no other influence on the color of the subject, so the contrast of the scene can be faithfully reproduced.

[0003] Currently, the research on neutral optical filters mainly focuses on optical glass filters. For example, CN105523713A constructs an optical glass filter based on a silicate glass composition. However, the optical glass filter has a narrow neutral filtration range, and the manufacturing process of the glass filter is complex and costly, so it cannot meet the diverse needs of customers. CN111522087A obtains a neutral filter by directly growing a graphene film on a glass substrate, and the bandwidth of the neutral filter is greatly expanded. However, it still uses a glass material as the substrate, and there are also problems such as a complicated manufacturing process, high cost, and inability to meet the diverse needs of customers.

[0004] Therefore, developing a new filter material with better flat spectral transmission characteristics in a wider wavelength band, a simple processing process, and low cost has great research significance and application value.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] The object of the present invention is to provide an ABS resin material having flat spectral transmission characteristics in order to overcome the defects or drawbacks of conventional optical filters in the prior art, such as poor flat spectral transmission characteristics, narrow appropriate wavelength bands, complex processing processes, and high costs. The ABS resin material having flat spectral transmission characteristics provided by the present invention has a flat transmittance curve in the spectral band of 380 to 980 nm, has flat spectral transmission characteristics, can achieve a better neutral filter effect, and has the advantages of easy processing and low cost, and can be widely used in the manufacture of optical products such as filters, video cameras, and digital cameras.

[0007] Another object of the present invention is to provide a method for manufacturing the ABS resin material having the above flat spectral transmission characteristics.

[0008] Another object of the present invention is to provide the use of the above ABS resin material having flat spectral transmission characteristics in the manufacture of optical products.

Means for Solving the Problems

[0009] In order to achieve the above object, the present invention uses the following technical solutions.

[0010] An ABS resin material having flat spectral transmission characteristics, comprising as components 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, 0.05 to 1.0 part by weight of antioxidant, 0.05 to 1.0 part by weight of dispersant, and 0.04 to 0.12 part by weight of additive,

[0011] The above additive is a mixture of CuCr2O4, and CuO and Cr2O3. The weight ratio of CuCr2O4, CuO, and Cr2O3 in the mixture is (5-9):(1-5):1, and the D50 particle size of CuCr2O4 is 0.1-1.0 μm.

[0012] The present invention has flat spectral transmittance characteristics, has an excellent neutral filter effect in a wider wavelength range of 380-980 nm, the variation in light transmittance is less than 10%, the processing process is simple and efficient, and the cost is low. It has the advantages of being widely used in the manufacture of optical products such as filters, video cameras, and digital cameras.

[0013] Specifically, the ABS material (acrylonitrile-butadiene-styrene copolymer) is excellent in acid resistance, alkali resistance, and processing fluidity, is easy to process and inexpensive, and has the advantages of high efficiency, low cost, and easy processing because it uses the ABS material as the base material. In the research of the present application, it has been found that based on this basic system, a specific additive can satisfy Lambert-Beer's law in this basic system and impart flat spectral transmittance characteristics to the ABS resin material.

[0014] Lambert-Beer's law describes the relationship between the intensity of light absorption of a specific wavelength by a substance, the concentration of the light-absorbing substance, and the thickness of the liquid layer, and its mathematical formula is as follows. [Equation 1] A = Kbc = lg(1 / T)

[0015] In the formula, A is the absorbance, K is the absorption coefficient, c is the concentration of the additive, b is the thickness of the filter, and T is the transmittance. Therefore, the absorbance A of the material is proportional to the concentration C of the colorant and the thickness b of the filter. In the present invention, compounds of CuCr2O4, CuO, and Cr2O3 are used as additives, and by changing these three specific ratios, the concentration c of the additive, and controlling the particle size of the main component CuCr2O4, the PMMA system absorbs an equal amount of incident light in the spectral band of 380-980 nm, resulting in an excellent neutral filter effect and being widely used in the manufacture of optical products such as filters, video cameras, and digital cameras.

[0016] Acrylonitrile-butadiene-styrene copolymer, antioxidant and dispersant commonly used in the art can be used in the present invention.

[0017] Preferably, the melt index of the acrylonitrile-butadiene-styrene copolymer is 20 - 30 g / 10 min at a temperature of 220 °C and a load of 10 kg, and according to the ISO 13468-1 standard, the transmittance at a thickness of 3 mm is 85 - 90%.

[0018] Preferably, the antioxidant is one or more of phenolic antioxidants, phosphite antioxidants, sulfur-containing antioxidants or amine antioxidants.

[0019] More preferably, the phenolic antioxidant is one or two of β-(3,5-di-tert-butyl-4-hydroxyphenyl) n-octadecanol propionate (1076) or tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester (1010).

[0020] More preferably, the phosphite antioxidant is one or two of tris(2,4-di-tert-butylphenyl) phosphite (168) or bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate (PEP-36).

[0021] Furthermore, preferably, the antioxidant is 1076 and 168, and the weight ratio of 1076 to 168 is 1:1.

[0022] Preferably, the dispersant is one or more of sodium lauryl sulfate, methyl pentanol, triethylhexyl phosphate, polyacrylamide, cellulose derivatives, ethylene bisstearamide, stearic acid, guar gum or fatty acid polyethylene glycol ester.

[0023] Preferably, the parts by weight of the above additive are 0.06 to 0.08.

[0024] Preferably, the D50 particle size of the above Cr2O3 is 0.1 to 0.5 μm, more preferably 0.45 to 0.55 μm.

[0025] Preferably, the D50 particle size of the above CuO is 10 to 100 nm, more preferably 45 to 55 nm.

[0026] Preferably, the D50 particle size of CuCr2O4 in the above additive is 0.6 to 0.8 μm, more preferably 0.55 to 0.65 μm.

[0027] Preferably, the weight ratio of CuCr2O4, CuO and Cr2O3 in the above additive is 8 to 9:1:1.

[0028] The method for producing the ABS resin material having the above flat spectral transmittance includes the steps of mixing an acrylonitrile-butadiene-styrene copolymer, an antioxidant, a dispersant, and an additive, melt-extruding and granulating to obtain a flat spectral transparent ABS resin material.

[0029] Preferably, the method for producing the ABS resin material having the above flat spectral transmittance includes the steps of mixing an acrylonitrile-butadiene-styrene copolymer, an antioxidant, a dispersant, and an additive in a high mixer for 3 to 5 minutes to obtain a mixed material, putting the mixed material into a twin-screw extruder, mixing, melting, and homogenizing, and then extruding and granulating and cooling to obtain an ABS resin material. The ratio of the length to the diameter of the extrusion screw of the twin-screw extruder is 40 to 65:1, the extruder barrel is 200 to 230 °C, and the main engine speed is 300 to 600 r / min.

[0030] The method for producing the ABS resin material having the above flat spectral transmittance provided by the present invention has a simple processing process, low cost, and can meet the diverse needs of customers.

[0031] The use of the ABS resin material having the above-mentioned flat spectral transmittance in the manufacture of optical products is also within the protection scope of the present invention.

[0032] Specifically, the ABS resin material having flat spectral transmittance can be widely used in the manufacture of products such as filters, video cameras, and digital cameras.

[0033] Compared with the prior art, the present invention has the following beneficial effects.

[0034] The ABS resin material having flat spectral transmittance provided by the present invention has flat spectral transmittance characteristics, has an excellent neutral filter effect in a wider wavelength range of 380-980 nm, the variation of the light transmittance (the difference between the maximum transmittance and the minimum transmittance) is less than 5%, and has the advantages of simple processing process, high efficiency, and low cost, and can be widely used in the manufacture of optical products such as filters, video cameras, and digital cameras.

Brief Description of the Drawings

[0035]

Figure 1

Modes for Carrying Out the Invention

[0036] Hereinafter, the present invention will be further described with reference to examples. These examples are only used to explain the present invention and do not limit the scope of the present invention. In the following examples, unless otherwise specified for the experimental methods of specific conditions, usually, according to the normal conditions in the field or the conditions proposed by the manufacturer, the raw materials and reagents used are all raw materials and reagents that can be obtained from conventional market routes such as the market unless otherwise specified. Any non-substantial changes and substitutions made by those skilled in the art based on the present invention are all included in the protection scope of the present invention.

[0037] Some of the reagents selected for each example and comparative example of the present invention are described below.

[0038] Acrylonitrile-butadiene-styrene copolymer 1#: MABS TR557, temperature 220 ℃、 At a load of 10 kg Melt Index 21 g / 10 min. According to ISO 13468-1, the transmittance at 3 mm is 90% (LG of South Korea). Acrylonitrile-butadiene-styrene copolymer 2#: MABS 982-X02, temperature 220 ℃、 At a load of 10 kg Melt Index 22 g / 10 min. According to ISO 13468-1, the transmittance at 3 mm is 84% (Toray of Japan). Antioxidant: Phosphite antioxidant, antioxidant 168, Tianjin Lier Chemical Co., Ltd., hindered phenolic antioxidant, antioxidant 1076, Tianjin Lier Chemical Co., Ltd. Dispersant: Stearic acid, GLYCOLUBE-P, Lonza of the United States CuCr2O4 1#, Guangzhou Changjin New Materials Technology Co., Ltd., D50 particle size is 0.6 μm CuCr2O4 2#, Guangzhou Changjin New Materials Technology Co., Ltd., D50 particle size is 0.1 μm CuCr2O4 3#, Guangzhou Changjin Materials Technology Co., Ltd., D50 particle size is 1.0 μm CuCr2O4 4#, Guangzhou Changjin Materials Technology Co., Ltd., D50 particle size is 2.0 μm Cr2O3 1#, Zhongshan Huashan High-Tech Ceramic Materials Co., Ltd., D50 particle size is 0.5 μm Cr2O3 2#, Zhongshan Huashan High-Tech Ceramic Materials Co., Ltd., D50 particle size is 0.1 μm Cr2O3 3#, Zhongshan Huashan High-Tech Ceramic Materials Co., Ltd., D50 particle size is 1.0 μm CuO 1#, Guangzhou Changjin Materials Technology Co., Ltd., D50 particle size is 50 nm CuO 2#, Guangzhou Changjin Materials Technology Co., Ltd., D50 particle size is 10 nm CuO 3#, Guangzhou Changjin Materials Technology Co., Ltd., D50 particle size is 120 μm Additives: OP-1-1# to OP-1-10#, self-made, details are as follows.

[0039] OP-1-1#, mix CuCr2O41#, CuO1#, and Cr2O31# at a ratio of 8:1:1 (by weight, the same below), OP-1-2#, mix CuCr2O41#, CuO1#, and Cr2O31# at a ratio of 9:1:1, OP-1-3#, mix CuCr2O41#, CuO1#, and Cr2O31# at a ratio of 5:5:1, OP-1-4#, mix CuCr2O42#, CuO2#, and Cr2O32# at a ratio of 8:1:1, OP-1-5#, mix CuCr2O43#, CuO3#, and Cr2O33# at a ratio of 8:1:1, OP-1-6#, mix CuCr2O44#, CuO1#, and Cr2O31# at a ratio of 8:1:1, OP-1-7#, mix CuCr2O41#, CuO1#, and Cr2O31# at a ratio of 5:8:1, OP-1-8#, mix CuCr2O41#, CuO1#, and Cr2O31# at a ratio of 5:1:8, OP-1-9#, mix CuCr2O41#, CuO1#, and Cr2O31# at a ratio of 12:1:1, Aniline black: TN-870, Orient Japan, D50 particle size is 0.2 μm, Carbon black: M717, Cabot USA, D50 particle size is 22 nm, Composite colorant: Mix red powder, blue powder, green powder, and yellow powder at a ratio of 2:20:20:1 (by weight), where Red powder: Iron oxide red, Bayer Germany, D50 particle size is 0.3 μm, Green powder: Cobalt green, Guangzhou Changjin New Materials Technology Co., Ltd., D50 particle size is 0.6 μm, Blue powder: Cobalt blue, Guangzhou Changjin New Materials Technology Co., Ltd., D50 particle size is 0.6 μm, Yellow powder: Bismuth vanadate yellow, DCC Canada, D50 particle size is 0.6 μm,

[0040] The ABS resin materials according to the examples and comparative examples of the present invention are obtained by the following manufacturing process.

[0041] Weigh the weight of each raw material as needed, mix for 3 to 5 minutes to obtain a mixed material, put the mixed material into a twin-screw extruder, after mixing, melting, and homogenizing, extrude and pelletize, and cool to obtain an ABS resin material. The ratio of the length to the diameter of the extrusion screw of the twin-screw extruder is 52:1, the barrel of the extruder is at 220 °C, and the main engine speed is 450 r / min.

[0042] The test method for the transmittance of the ABS resin materials according to each example and comparative example of the present invention is as follows.

[0043] The granulated resin was injection molded to produce a sample with a thickness of 1 mm, and the transmittance was tested using a HunterLab-UltraScan VIS dual-beam spectrophotometer from Q-lab, USA.

[0044] The transmittance variation refers to the difference between the maximum value and the minimum value of the transmittance at each wavelength.

[0045] Examples 1-8 This example provides an ABS resin material having a series of flat spectral transmittance characteristics, and its formulation method is shown in Table 1.

[0046]

Table 1

[0047] Comparative Examples 1-9 This example provides a series of ABS resin materials, and its formulation method is shown in Table 2.

[0048]

Table 2

[0049] Test the performance of the ABS resin materials provided by each example and comparative example according to the above performance test method. The results are shown in Figure 1. At the same time, the transmittance values of the ABS resin materials provided by Example 1 are as follows.

[0050]

Table 3

[0051]

Table 4

[0052] As can be seen from the above test results, the ABS resin materials provided by the respective examples of the present invention have a good neutral filter effect, and the transmittance data in the spectral band of 380 to 980 nm is very stable, with the variation in transmittance being less than 5%, and the transmittance curves tend to be parallel. The ABS resin material provided by Example 1 has the most excellent neutral filter effect and meets the index of a transmittance of 30 ± 2.5% at 1.0 mm. The transmittance curve of Comparative Example 1 tends to be parallel, but since no specific additive is added, it is the effect of a pure transparent resin. Because the light beam is strong, there is a risk of overexposure during image shooting, but there is no neutral gray filter effect. In Comparative Example 2, the particle size of CuCr2O4 is large and the dispersibility is low, and the transmittance in the 380 to 980 nm band fluctuates by more than 10%. In Comparative Examples 3 to 5, the ratio of CuCr2O4 to CuO and Cr2O3 is inappropriate, and the transmittance variation in the 380 to 680 nm band exceeds 20%. In Comparative Example 4, the variation range exceeds 15% in the 380 to 560 nm band. In Comparative Example 5, the transmittance in the band after 680 nm gradually increases and the neutral filter effect disappears. In Comparative Examples 6 to 7, conventional carbon black and aniline black are added, and the obtained ABS resin materials are black, consistent with the respective examples, but the transmittance in the infrared region (760 to 980 nm) gradually increases, resulting in a large variation in transmittance. In Comparative Example 8, a black material is obtained by adding a composite pigment of red, yellow, blue, and green inorganic metal pigments. Compared with Comparative Examples 6 to 7, the transmittance curve becomes flatter, but carbon black and aniline black are added, and the stability is not very good, with a transmittance variation of more than 10% in the 380 to 980 nm band. In Comparative Example 9, the amount of the additive is too large, the light transmittance in the 380 to 980 nm band is less than 10%, the light absorption is too strong, it is completely black, and the neutral filter effect disappears.

[0053] Those skilled in the art will understand that the examples provided here are to assist the reader in understanding the principles of the present invention, and it is desired that the scope of the present invention not be limited to such specific descriptions and examples. Those skilled in the art can make various other specific changes and combinations based on the technical teachings disclosed in the present invention without departing from the essence of the present invention, and these changes and combinations are still within the protection scope of the present invention. The aspects described in the claims of the present invention include the following. [1] An ABS resin material having flat spectral transmission characteristics, and as components, 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, 0.05 to 1.0 part by weight of antioxidant, 0.05 to 1.0 part by weight of dispersant, and 0.04 to 0.12 part by weight of additive are included, wherein the additive is a mixture of CuCr 2 O 4 , CuO, and Cr 2 O 3 , and the weight ratio of CuCr 2 O 4 , CuO, and Cr 2 O 3 in the mixture is (5 to 9):(1 to 5):1, and the D50 particle size of CuCr 2 O 4 is 0.1 to 1.0 μm, an ABS resin material having flat spectral transmission characteristics. [2] The melt index of the acrylonitrile-butadiene-styrene copolymer is 20 to 30 g / 10 min at a temperature of 220 °C and a load of 10 kg, and according to the ISO 13468-1-2019 standard, the transmittance at a thickness of 3 mm is 85 to 90%, the ABS resin material having flat spectral transmission characteristics according to [1]. [3] The antioxidant is one or more of a phenolic antioxidant, a phosphite antioxidant, a sulfur-containing antioxidant, or an amine antioxidant, the ABS resin material having flat spectral transmission characteristics according to [1]. [4] The dispersant is one or more of sodium lauryl sulfate, methylpentanol, triethylhexyl phosphate, polyacrylamide, cellulose derivative, ethylene bisstearamide, stearic acid, guar gum, or fatty acid polyethylene glycol ester, the ABS resin material having flat spectral transmission characteristics according to [1]. [5] The D50 particle size of Cr 2 O 3 in the additive is 0.1 to 0.5 μm, the ABS resin material having flat spectral transmission characteristics according to [1]. [6] The D50 particle size of CuO in the additive is 10 to 100 nm, the ABS resin material having flat spectral transmission characteristics according to [1]. [7] The D50 particle size of CuCr 2 O 4 in the additive is 0.6 to 0.8 μm, the ABS resin material having flat spectral transmission characteristics according to [1]. [8] The weight ratio of CuCr 2 O 4 , CuO, and Cr 2 O 3 in the additive is 8 to 9:1:1, the ABS resin material having flat spectral transmission characteristics according to [1]. A method for producing an ABS resin material having flat spectral transmission characteristics according to any one of [1] to [8], comprising the step of mixing an acrylonitrile-butadiene-styrene copolymer, an antioxidant, a dispersant, and an additive, followed by melt extrusion and granulation to obtain a flat and spectrally transparent ABS resin material. Use of an ABS resin material having flat spectral transmission characteristics according to any one of [1] to [8] in the production of optical products.

Claims

1. As components, 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, 0.05 to 1.0 part by weight of antioxidant, 0.05 to 1.0 part by weight of dispersant, and an ABS resin material containing 0.04 to 0.12 part by weight of additive, The additive is CuCr ２ O ４ , CuO, and Cr ２ O ３ a mixture of, and the weight ratio of CuCr ２ O ４ , CuO, and Cr ２ O ３ in the mixture is (5 - 9):(1 - 5):1, and the D50 particle size of CuCr ２ O ４ is 0.1 μm to 1.0 μm, and is characterized by an ABS resin material.

2. The melt index of the acrylonitrile-butadiene-styrene copolymer is 20 g to 30 g / 10 min at a temperature of 220 °C and a load of 10 kg, and according to ISO 13468-1-2019 standard, the transmittance at a thickness of 3 mm is 85 to 90%, which is characterized in that the ABS resin material according to Claim 1.

3. The antioxidant is one or more of phenolic antioxidants, phosphite antioxidants, sulfur-containing antioxidants or amine antioxidants, which is characterized in that the ABS resin material according to Claim 1.

4. The dispersant is one or more of sodium lauryl sulfate, methylpentanol, triethylhexyl phosphate, polyacrylamide, cellulose derivatives, ethylenebisstearamide, stearic acid, guar gum or fatty acid polyethylene glycol ester, which is characterized in that the ABS resin material according to Claim 1.

5. Cr in the additive ２ O ３ The ABS resin material according to claim 1, characterized in that the D50 particle size of is 0.1 μm to 0.5 μm.

6. The D50 particle size of CuO in the additive is 10 nm to 100 nm, which is characterized in that the ABS resin material according to Claim 1.

7. CuCr in the additive ２ O ４ The ABS resin material according to claim 1, characterized in that the D50 particle size of is 0.6 μm to 0.8 μm.

8. CuCr in the additive ２ O ４ , CuO and Cr ２ O ３ The ABS resin material according to claim 1, characterized in that the weight ratio of is 8 to 9:1:

1.

9. A method for producing an ABS resin material according to any one of Claims 1 to 8, characterized by including the steps of mixing an acrylonitrile-butadiene-styrene copolymer, an antioxidant, a dispersant, and an additive, melt-extruding and pelletizing to obtain the ABS resin material.

10. Use of the ABS resin material according to any one of Claims 1 to 8 in the manufacture of optical products.

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