WO2023024912A1 - Abs resin material having flat spectral transmission characteristics, preparation method therefor and application thereof - Google Patents

Abstract

The present invention relates to an ABS resin material having flat spectral transmission characteristics, a preparation method therefor and an application thereof. The ABS resin material having flat spectral transmission characteristics provided in the present invention comprises an acrylonitrile-butadiene-styrene copolymer, an antioxidant, a dispersant and an additive. The present invention constructs a non-glass material having flat spectral transmission characteristics and a relatively good neutral filtering effect in a relatively wide wavelength range of 380-980 nm. In addition, it has a simple processing procedure, high processing efficiency, low costs, and can be widely used in the preparation of optical products such as optical filters, video cameras or digital cameras.

Description

A kind of ABS resin material with flat light splitting transmission characteristics and its preparation method and application technical field

The invention belongs to the technical field of plastic products, and in particular relates to an ABS resin material with flat light-splitting and transmission characteristics, a preparation method and application thereof.

Background technique

Neutral optical filter is a commonly used lens in camera equipment, which can filter light non-selectively, can filter light equally and evenly, and has the same or similar reduction effect on light within a certain wavelength range . The neutral optical filter only weakens the light without any other influence on the color of the photographed object, so it can truly reproduce the contrast of the scene.

At present, 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 filter made of optical glass can neutrally filter a narrow range of wavelengths, and the preparation process of the glass filter is complicated and the cost is high, which cannot meet the diversified needs of customers. CN111522087A obtains a neutral density filter by directly growing graphene film on a glass substrate. Although the wavelength range of the neutral filter is greatly widened, it is still based on glass material, and the preparation process is also complicated and the cost is high. , unable to meet the diverse needs of customers.

Therefore, it is of great research significance and application value to develop a new type of filter material that has more excellent flat spectral transmission characteristics in a wider wavelength band, and has simple processing procedures and low cost.

Contents of the invention

The object of the present invention is to overcome the defects or deficiencies in the prior art, such as poor flat spectral transmission characteristics of optical filters, narrow suitable wavelength bands, complex processing procedures, and high cost, and provide a flat optical filter with flat spectral transmission characteristics. ABS resin material. The ABS resin material with flat spectral transmission characteristics provided by the present invention has a flat transmittance curve in the spectral band of 380-980nm, has flat spectral transmission characteristics, can achieve a better neutral filter effect, and is easy to process, The advantage of low cost can be widely used in the preparation of optical products, such as optical filters, video cameras or digital cameras.

Another object of the present invention is to provide a method for preparing the above-mentioned ABS resin material with flat spectral transmission properties.

Another object of the present invention is to provide the application of the above-mentioned ABS resin material with flat spectral transmission characteristics in the preparation of optical products.

In order to realize the above-mentioned purpose of the invention, the present invention adopts following technical scheme:

An ABS resin material with flat light-splitting transmission properties, comprising the following components in parts by weight:

The additive is a mixture of CuCr ₂ O ₄ , CuO and Cr ₂ O ₃ , 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 CuCr The D50 particle size of ₂ O ₄ is 0.1-1.0 μm.

The present invention constructs a non-glass material, which has flat spectral transmission characteristics, and has a better neutral filter effect in the wide band range of 380-980nm, and the fluctuation of light transmittance is less than 10%. , and the processing procedure is simple, has the advantages of high efficiency and low cost, and can be widely used in the preparation of optical products, such as optical filters, video cameras or digital cameras.

Specifically, ABS material (acrylonitrile-butadiene-styrene copolymer) has excellent acid and alkali resistance and processing fluidity, is easy to process, and is cheap. Using ABS material as a matrix material has high efficiency and low cost. The advantage of easy processing. Based on this basic system, the present application found that specific additives satisfy Lambert-Beer's law in this basic system, which in turn can endow the ABS resin material with flat spectral transmission characteristics.

Lambert-Birdine describes the relationship between the strength of a substance absorbing a certain wavelength of light and the concentration of the light-absorbing substance and the thickness of its liquid layer. Its mathematical expression is as follows:

A=Kbc=lg(1/T)

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 optical filter. The present invention uses CuCr ₂ O ₄ , CuO and Cr ₂ O ₃ as additives, and changes the additives through the specific ratio of the three The concentration c of the key component CuCr ₂ O ₄ particle size control endows the PMMA system with an equal amount of absorption of incident light in the 380-980nm spectral band, has excellent neutral filtering effect, and can be widely used in the preparation of optical products, such as optical filter film, camcorder, or digital still camera.

Conventional acrylonitrile-butadiene-styrene copolymers, antioxidants and dispersants in the art can all be used in the present invention.

Preferably, the acrylonitrile-butadiene-styrene copolymer has a melt index of 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 standard, the permeability at a thickness of 3 mm The rate is 85-90%.

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

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

More preferably, the phosphite antioxidant is tris(2,4-di-tert-butylphenyl) phosphite (168) or bis(2,6-di-tert-butyl-4-methyl One or both of phenyl) pentaerythritol diphosphate (PEP-36).

Further preferably, the antioxidants are 1076 and 168, and the weight ratio of 1076 and 168 is 1:1.

Preferably, the dispersant is sodium lauryl sulfate, methyl amyl alcohol, triethylhexanophosphoric acid, polyacrylamide, cellulose derivatives, ethylene bis stearic acid amide, stearate, ancient One or more of gelatin or fatty acid polyethylene glycol ester.

Preferably, the weight part of the additive is 0.06-0.08.

Preferably, the D50 particle size of the Cr ₂ O ₃ is 0.1-0.5 μm, more preferably 0.45-0.55 μm.

Preferably, the D50 particle size of the CuO is 10-100 nm, more preferably 45-55 nm.

Preferably, the D50 particle size of CuCr ₂ O ₄ in the additive is 0.6-0.8 μm, more preferably 0.55-0.65 μm.

Preferably, the weight ratio of CuCr ₂ O ₄ to CuO and Cr ₂ O ₃ in the additive is 8˜9:1:1.

The preparation method of the above-mentioned flat light-splitting ABS resin material includes the following steps: mixing acrylonitrile-butadiene-styrene copolymer, antioxidant, dispersant and additives, melt extruding, and granulating to obtain the described ABS resin material with flat split light transmission.

Preferably, the preparation method of the flat light-splitting ABS resin material includes the following steps: acrylonitrile-butadiene-styrene copolymer, antioxidant, dispersant and additives are mixed in a high-speed mixer for 3 to 5 minutes , to obtain a mixed material; put the mixed material into a twin-screw extruder, extrude and granulate after mixing, melting, and homogenizing, and cool to obtain an ABS resin material; wherein, the extrusion of the twin-screw extruder The length-to-diameter ratio of the screw is 40-65:1, the barrel temperature of the extruder is 200-230°C, and the speed of the main engine is 300-600r/min.

The preparation method of the flat light-splitting and transparent ABS resin material provided by the invention has simple processing technology and low cost, and can meet the diversified needs of customers.

The application of the above-mentioned flat light-splitting and transmissive ABS resin material in the preparation of optical products is also within the protection scope of the present invention.

Specifically, the ABS resin material with flat light splitting and transmission can be widely used to prepare products such as optical filters, video cameras or digital cameras.

Compared with the prior art, the present invention has the following beneficial effects:

The flat light-splitting ABS resin material provided by the present invention has flat light-splitting and transmission characteristics, and has a better neutral filter effect in the wide band range of 380-980nm, and the light transmittance fluctuation (transmittance The difference between the maximum value and the minimum value) is less than 5%, and the processing procedure is simple, the efficiency is high, and the cost is low, so it can be widely used in the preparation of optical products, such as optical filters, video cameras or digital cameras.

Description of drawings

Fig. 1 is the transmittance of the ABS resin material provided by each embodiment and comparative example.

Detailed ways

The present invention is further set forth below in conjunction with embodiment. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental method that does not indicate specific conditions in the following example embodiment, usually according to the conventional conditions in this field or according to the conditions suggested by the manufacturer; used raw materials, reagents, etc., if no special instructions, are available from commercial channels such as conventional markets Raw materials and reagents obtained. Any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention fall within the scope of the present invention.

The partial reagents that each embodiment of the present invention and comparative examples select are described as follows:

Acrylonitrile-butadiene-styrene copolymer 1#: MABS TR557, at a temperature of 220°C and a load of 10kg, it is 21g/10min, the transmittance is in accordance with ISO 13468-1 standard, 3mm is 90%, Korean LG ;

Acrylonitrile-butadiene-styrene copolymer 2#: MABS 982-X02, at a temperature of 220°C and a load of 10kg, it is 22g/10min, and the transmittance is 84% for 3mm according to the ISO 13468-1 standard. Japan Toray;

Antioxidant: phosphite antioxidant, antioxidant 168, Tianjin Lianlong New Material Co., Ltd.; hindered phenolic antioxidant, antioxidant 1076, Tianjin Lianlong New Material Co., Ltd.;

Dispersant: stearate, GLYCOLUBE-P, Lonza;

CuCr ₂ O ₄ 1#, Guangzhou Changjin New Material Technology Co., Ltd., D50 particle size is 0.6μm;

CuCr ₂ O ₄ 2#, Guangzhou Changjin New Material Technology Co., Ltd., D50 particle size is 0.1μm;

CuCr ₂ O ₄ 3#, Guangzhou Changjin New Material Technology Co., Ltd., D50 particle size is 1.0μm;

CuCr ₂ O ₄ 4#, Guangzhou Changjin New Material Technology Co., Ltd., D50 particle size is 2.0μm;

Cr ₂ O ₃ 1#, Zhongshan Huashan High-tech Ceramic Material Co., Ltd., D50 particle size is 0.5μm;

Cr ₂ O ₃ 2#, Zhongshan Huashan High-tech Ceramic Material Co., Ltd., D50 particle size is 0.1μm;

Cr ₂ O ₃ 3#, Zhongshan Huashan High-tech Ceramic Material Co., Ltd., D50 particle size is 1.0μm;

CuO1#, Guangzhou Changjin New Material Technology Co., Ltd., D50 particle size is 50nm;

CuO2#, Guangzhou Changjin New Material Technology Co., Ltd., D50 particle size is 10nm;

CuO3#, Guangzhou Changjin New Material Technology Co., Ltd., D50 particle size is 120μm;

Additives: OP-1-1#～OP-1-10#, self-made, details are as follows:

OP-1-1#, CuCr ₂ O ₄ 1# and CuO1#, Cr ₂ O ₃ 1# are mixed according to 8:1:1 (weight ratio, the same below);

OP-1-2#, CuCr ₂ O ₄ 1# and CuO1#, Cr ₂ O ₃ 1# are mixed according to 9:1:1;

OP-1-3#, CuCr ₂ O ₄ 1# and CuO1#, Cr ₂ O ₃ 1# are mixed according to 5:5:1;

OP-1-4#, CuCr ₂ O ₄ 2# and CuO2#, Cr ₂ O ₃ 2# are mixed according to 8:1:1;

OP-1-5#, CuCr ₂ O ₄ 3# and CuO3#, Cr ₂ O ₃ 3# are mixed according to 8:1:1;

OP-1-6#, CuCr ₂ O ₄ 4# and CuO1#, Cr ₂ O ₃ 1# are mixed according to 8:1:1;

OP-1-7#, CuCr ₂ O ₄ 1# and CuO1#, Cr ₂ O ₃ 1# are mixed according to 5:8:1;

OP-1-8#, CuCr ₂ O ₄ 1# and CuO1#, Cr ₂ O ₃ 1# are mixed according to 5:1:8;

OP-1-9#, CuCr ₂ O ₄ 1# and CuO1#, Cr ₂ O ₃ 1# are mixed according to 12:1:1;

Nigrosine: TN-870, Japan Oriental, D50 particle size is 0.2μm;

Carbon black: M717, American Cabot, D50 particle size is 22nm;

Composite coloring agent: red powder, blue powder, green powder and yellow powder are mixed according to 2:20:20:1 (weight ratio), wherein:

Red powder: iron oxide red, Bayer, Germany, D50 particle size is 0.3μm;

Green powder: cobalt green, Guangzhou Changjin New Material Technology Co., Ltd., D50 particle size is 0.6μm;

Blue powder: cobalt blue, Guangzhou Changjin New Material Technology Co., Ltd., D50 particle size is 0.6μm;

Yellow powder: bismuth vanadate yellow, Canadian DCC, D50 particle size is 0.6 μ m;

The ABS resin material of each embodiment of the present invention and comparative example is prepared by following process:

Weigh each raw material as required, mix for 3 to 5 minutes to obtain a mixed material; put the mixed material into a twin-screw extruder, knead, melt, homogenize, extrude and granulate, and cool to obtain an ABS resin material; Wherein, the length-to-diameter ratio of the extrusion screw of the twin-screw extruder is 52:1, the temperature of the extruder barrel is 220° C., and the rotational speed of the main engine is 450 r/min.

The transmittance testing method of the ABS resin material of each embodiment of the present invention and comparative example is as follows:

The granulated resin was injection-molded into a sample with a thickness of 1mm, and the transmittance was tested with a HunterLab-UltraScan VIS dual-light path spectrophotometer from Q-lab Company of the United States.

The transmittance fluctuation is the difference between the maximum value and the minimum value of the transmittance at different wavelengths.

Examples 1-8

This embodiment provides a series of flat and light-splitting ABS resin materials, the formula of which is shown in Table 1.

The formula (part) of table 1 embodiment 1～8

Example	1	2	3	4	5	6	7	8
Acrylonitrile-butadiene-styrene copolymer 1#	100	100	100	100	100	/	100	100
Acrylonitrile-butadiene-styrene copolymer 2#	/	/	/	/	/	100	/	/
Antioxidant 168	0.1	0.1	0.1	0.1	0.1	0.1	0.05	0.5
Antioxidant 1076	0.1	0.1	0.1	0.1	0.1	0.1	0.05	0.5
Dispersant	0.2	0.2	0.2	0.2	0.2	0.2	1.0	0.05
OP-1-1#	0.07	/	/	/	/	0.07	0.04	0.12
OP-1-2#	/	0.07	/	/	/	/	/	/
OP-1-3#	/	/	0.07	/	/	/	/	/
OP-1-4#	/	/	/	0.07	/	/	/	/
OP-1-5#	/	/	/	/	0.07	/	/	/

Comparative example 1～9

This comparative example provides a series of ABS resin materials, the formulations of which are shown in Table 2.

The formula (part) of table 2 comparative examples 1～9

The performance of the ABS resin material provided by each embodiment and comparative example is tested by the aforementioned performance test method, the result is shown in Figure 1, and the transmittance value of the ABS resin material provided by Example 1 is as follows

The transmittance values and transmittance fluctuation values of the ABS resin materials provided in Table 3 Examples 1-8

The transmittance values and transmittance fluctuation values of the ABS resin materials provided in Table 4 Comparative Examples 1 to 9

From the above test results, it can be known that the ABS resin materials provided by the various embodiments of the present invention have a better neutral filtering effect, and the transmittance data in the spectral band of 380-980nm is very stable, and the transmittance fluctuation is less than 5%, and the transmittance curve Tend to be parallel; Among them, the neutral filtration effect of the ABS resin material provided by Example 1 is the most excellent, meeting the index of 1.0mm transmittance of 30±2.5%. In comparison example 1, although the transmittance curve tends to be parallel, but because no specific additives are added, it is a pure transparent resin effect, and the luminous flux is relatively strong, which will cause the risk of overexposure when shooting images, and does not have a neutral gray filter effect. ; The particle size of CuCr ₂ O ₄ in comparative example 2 is larger, the dispersibility is poor, _and the transmittance _fluctuation of 380-980nm band _exceeds 10% _; The ratio is inappropriate, among which the transmittance fluctuation of comparative example 3 is >20% in the 380-680nm band; the fluctuation range of comparative example 4 is more than 15% in the 380-560nm band; the transmittance of comparative example 5 is gradually higher after 680nm , does not have a neutral filter effect; conventional carbon black and aniline black are added in comparative examples 6 to 7, although the ABS resin material obtained by it is consistent with each embodiment and is also a black material, but its infrared band (760 ~ 980nm ) transmittance is gradually higher, resulting in large fluctuations in transmittance; in comparative example 8, red, yellow, blue, green inorganic metal pigment composite colorants are added to obtain black materials, although the transmittance curve is higher than that of comparative examples 6- The addition of carbon black and aniline black in 7 is flat but poor in stability, and the fluctuation range of the transmittance in the 380-980nm band exceeds 10%. %, the light absorption is too strong, it is pure black, and does not have a neutral filtering effect.

Those skilled in the art will appreciate that the embodiments herein are to help readers understand the principles of the present invention, and it should be understood that the protection scope of the present invention is not limited to such specific statements and embodiments. Those skilled in the art can make various other specific modifications and combinations based on the technical revelations disclosed in the present invention without departing from the essence of the present invention, and these modifications and combinations are still within the protection scope of the present invention.

Claims (10)

1. An ABS resin material with flat light-splitting transmission properties, characterized in that it comprises the following components in parts by weight:

   

   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 (5-9):(1-5):1 , the D50 particle size of the CuCr ₂ O ₄ is 0.1-1.0 μm.
2. The ABS resin material with flat spectral transmission characteristics according to claim 1, characterized in that the melt index of the acrylonitrile-butadiene-styrene copolymer under the conditions of a temperature of 220°C and a load of 10kg is 20-20. 30g/10min, according to the ISO 13468-1-2019 standard, the transmittance at a thickness of 3mm is 85-90%.
3. According to claim 1, the ABS resin material with flat light-splitting and transmission characteristics is characterized in that, the antioxidant is a phenolic antioxidant, a phosphite antioxidant, a sulfur-containing antioxidant or an amine One or more of antioxidants.
4. The ABS resin material with flat light-splitting transmission properties according to claim 1, wherein the dispersant is sodium lauryl sulfate, methyl amyl alcohol, triethylhexyl phosphoric acid, polyacrylamide, cellulose One or more of derivatives, ethylene bis stearic acid amide, stearate, gull gum or fatty acid polyethylene glycol ester.
5. The ABS resin material with flat spectral transmission characteristics according to claim 1, wherein the D50 particle size of Cr ₂ O ₃ in the additive is 0.1-0.5 μm.
6. The ABS resin material with flat spectral transmission characteristics according to claim 1, characterized in that the D50 particle size of CuO in the additive is 10-100 nm.
7. The ABS resin material with flat spectral transmission characteristics according to claim 1, wherein the D50 particle size of CuCr ₂ O ₄ in the additive is 0.6-0.8 μm.
8. The ABS resin material with flat spectral transmission characteristics according to claim 1, characterized in that the weight ratio of CuCr ₂ O ₄ to CuO and Cr ₂ O ₃ in the additive is 8-9:1:1.
9. The preparation method of the ABS resin material with flat spectral transmission characteristics according to any one of claims 1 to 8, characterized in that it comprises the following steps: acrylonitrile-butadiene-styrene copolymer, antioxidant, dispersant It is mixed with additives, melted and extruded, and granulated to obtain the flat and light-splitting ABS resin material.
10. The application of the ABS resin material with flat light-splitting and transmission properties described in any one of claims 1 to 8 in the preparation of optical products.

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