CN113861613B - ABS resin material with flat light splitting transmission characteristic and preparation method and application thereof - Google Patents
ABS resin material with flat light splitting transmission characteristic and preparation method and application thereof Download PDFInfo
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- CN113861613B CN113861613B CN202110971015.2A CN202110971015A CN113861613B CN 113861613 B CN113861613 B CN 113861613B CN 202110971015 A CN202110971015 A CN 202110971015A CN 113861613 B CN113861613 B CN 113861613B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2248—Oxides; Hydroxides of metals of copper
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2251—Oxides; Hydroxides of metals of chromium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
Abstract
The invention relates to an ABS resin material with flat light splitting and transmitting characteristics, and a preparation method and application thereof. The ABS resin material with the flat spectral transmission characteristic provided by the invention comprises an acrylonitrile-butadiene-styrene copolymer, an antioxidant, a dispersing agent and an additive. The invention constructs a non-glass material which has the characteristics of flat light splitting and transmission, has better neutral filtering effect in a wider wave band range of 380-980nm, has simple processing procedure, high efficiency and low cost, and can be widely applied to the preparation of optical products, such as optical filters, video cameras or digital cameras.
Description
Technical Field
The invention belongs to the technical field of plastic products, and particularly relates to an ABS resin material with a flat light splitting and transmitting characteristic, and a preparation method and application thereof.
Background
The neutral optical filter is a lens commonly used for the image pickup device, can play a role of filtering light rays in a non-selective manner, can equally and uniformly filter the light rays, and has the same or similar reduction effect on the light rays in a certain wavelength range. The neutral optical filter only weakens the light and does not have other influences on the color of a photographic object, so that the contrast of the scenery can be truly reproduced.
Currently, research on neutral optical filters is mainly focused on optical glass filters; for example, CN105523713A, an optical glass filter based on a silicate glass composition was constructed. However, the optical filter made of the optical glass material has a narrow neutral filtering waveband range, and the preparation process of the glass optical filter is complex and has high cost, so that diversified requirements of customers cannot be met. CN111522087A obtains the neutral density filter by directly growing a graphene film on a glass substrate, and although the neutral density filter greatly widens the wave band range of neutral filtering, the neutral density filter still uses a glass material as a base, and the problems of complex preparation process, high cost and incapability of meeting diversified requirements of customers also exist.
Therefore, the development of a novel filter material which has more excellent flat spectral transmission characteristics in a wider waveband, simple processing procedure and low cost has important research significance and application value.
Disclosure of Invention
The invention aims to overcome the defects or shortcomings of poor flat spectral transmission characteristic, narrow suitable waveband, complex processing procedure and high cost of an optical filter in the prior art, and provides an ABS resin material with flat spectral transmission characteristic. The ABS resin material with the flat spectral transmission characteristic has a flat transmittance curve in a spectral band of 380-980nm, has the flat spectral transmission characteristic, can realize a better neutral filtering effect, has the advantages of easiness in processing and low cost, and can be widely applied to the preparation of optical products such as optical filters, video cameras or digital cameras.
The invention also aims to provide a preparation method of the ABS resin material with the flat spectral transmission characteristic.
The invention also aims to provide application of the ABS resin material with the flat spectral transmission characteristic in preparing optical products.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
an ABS resin material with flat spectral transmission characteristic comprises the following components in parts by weight:
the additive is CuCr 2 O 4 CuO and Cr 2 O 3 The mixture of (1), the mixture comprising CuCr 2 O 4 CuO and Cr 2 O 3 The weight ratio of (A) to (B) is 5-9 2 O 4 The D50 particle diameter of (B) is 0.1 to 1.0. Mu.m.
The invention constructs a non-glass material, which has the characteristics of flat light splitting and transmission, has better neutral filtering effect in a wider wave band range of 380-980nm, the fluctuation of the light transmission rate is less than 10%, and the invention has the advantages of simple processing procedure, high efficiency and low cost, and can be widely applied to the preparation of optical products, such as optical filters, video cameras or digital cameras.
Specifically, the ABS material (acrylonitrile-butadiene-styrene copolymer) has excellent acid and alkali resistance and processing fluidity, is easy to process and low in price, and has the advantages of high efficiency, low cost and easiness in processing by taking the ABS material as a base material. On the basis of the basic system, the research of the application finds that the specific additive meets the Lambert beer law in the basic system, and further can endow the ABS resin material with flat spectral transmission characteristics.
Lambertian beer's definition describes the relationship between the intensity of a substance absorbing light with a certain wavelength and the concentration of the light absorbing substance and the thickness of a liquid layer thereof, and the mathematical expression is as follows:
A＝Kbc＝lg(1/T)
in the formula, A is absorbance, K is absorption coefficient, c is concentration of additive, b is thickness of filter, and T is transmittance. Therefore, the absorbance A of the material is proportional to the concentration C of the colorant and the thickness b of the filter, and the invention uses CuCr 2 O 4 CuO and Cr 2 O 3 Compounding as an additive, and changing the concentration c of the additive and the key component CuCr according to the specific proportion of the three 2 O 4 The particle size is regulated, the PMMA system absorbs incident light in the 380-980nm spectral band in equal quantity, has excellent neutral filtering effect, and can be widely applied to light preparationOptical products such as filters, video cameras or digital cameras.
Acrylonitrile-butadiene-styrene copolymer, antioxidant and dispersant, which are conventional in the art, can be used in the present invention.
Preferably, the acrylonitrile-butadiene-styrene copolymer has a melt index of 20 to 30g/10min under a temperature of 220 ℃ and a load of 10kg, and a transmittance of 85 to 90% at a thickness of 3mm according to ISO 13468-1.
Preferably, the antioxidant is one or more of a phenol antioxidant, a phosphite antioxidant, a sulfur-containing antioxidant or an amine antioxidant.
More preferably, the phenolic antioxidant is one or two of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester (1076) or tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (1010).
More preferably, the phosphite antioxidant is one or two of tris (2, 4-di-tert-butylphenyl) phosphite (168) and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate (PEP-36).
Further preferably, the antioxidants 1076 and 168, and the weight ratio of 1076 to 168 is 1.
Preferably, the dispersant is one or more of sodium dodecyl sulfate, methyl amyl alcohol, triethyl hexanephosphoric acid, polyacrylamide, cellulose derivatives, ethylene bis stearamide, stearate, guar gum or fatty acid polyglycol ester.
Preferably, the weight portion of the additive is 0.06-0.08.
Preferably, the Cr is 2 O 3 The D50 particle diameter of (B) is 0.1 to 0.5. Mu.m, preferably 0.45 to 0.55. Mu.m.
Preferably, the particle size of the CuO D50 is 10 to 100nm, and more preferably 45 to 55nm.
Preferably, the additive is CuCr 2 O 4 The D50 particle diameter of (B) is 0.6 to 0.8. Mu.m, more preferably 0.55 to 0.65. Mu.m.
Preferably, the additive comprises CuCr 2 O 4 And CuO, cr 2 O 3 The weight ratio of (A) to (B) is 8-9.
The preparation method of the ABS resin material with flat spectral transmission comprises the following steps: mixing the acrylonitrile-butadiene-styrene copolymer, the antioxidant, the dispersant and the additive, melting, extruding and granulating to obtain the flat light-splitting transparent ABS resin material.
Preferably, the preparation method of the flat light-splitting transmitting ABS resin material includes the following steps: mixing the acrylonitrile-butadiene-styrene copolymer, the antioxidant, the dispersant and the additive in a high-speed mixer for 3-5 min to obtain a uniformly mixed material; putting the uniformly mixed material into a double-screw extruder, performing mixing, melting and homogenizing, then extruding, granulating and cooling to obtain an ABS resin material; wherein, the length-diameter ratio of an extrusion screw of the double-screw extruder is 40-65, the charging barrel of the extruder is 200-230 ℃, and the rotating speed of a main machine is 300-600 r/min.
The preparation method of the ABS resin material with flat spectral transmission provided by the invention has the advantages of simple processing technology and low cost, and can meet diversified requirements of customers.
The application of the ABS resin material with flat spectral transmission in the preparation of optical products is also within the protection scope of the invention.
Specifically, the ABS resin material with flat spectral transmission can be widely used for preparing products such as optical filters, video cameras or digital cameras.
Compared with the prior art, the invention has the following beneficial effects:
the ABS resin material with flat spectral transmission provided by the invention has flat spectral transmission characteristics, has a better neutral filtering effect in a wider waveband range of 380-980nm, has light transmission fluctuation (difference value between the maximum value and the minimum value of the transmittance) less than 5%, is simple in processing procedure, high in efficiency and low in cost, and can be widely applied to preparation of optical products such as optical filters, video cameras or digital cameras.
Drawings
Fig. 1 is a transmittance of ABS resin materials provided in each example and comparative example. Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Some of the reagents selected in the examples and comparative examples of the present invention are described below:
acrylonitrile-butadiene-styrene copolymer # 1: MABS TR557, 21g/10min at 220 ℃ under a load of 10kg, a transmittance according to ISO 13468-1 standard, 90% at 3mm, korean LG;
acrylonitrile-butadiene-styrene copolymer # 2: MABS 982-X02 with a transmittance of 84% according to ISO 13468-1 at a temperature of 220 ℃ under a load of 10kg at a rate of 22g/10min, and a transmittance of 84% at 3mm, east Li Japan;
antioxidant: phosphite antioxidants, antioxidant 168, tianjin Lianlong New materials GmbH; hindered phenol antioxidants, antioxidant 1076, new Tianjin Lianlong Material Co., ltd;
dispersing agent: stearate, glycoolube-P, usa lode;
CuCr 2 O 4 1#, guangzhou Changjin New Material science and technology, inc., with D50 particle size of 0.6 μm;
CuCr 2 O 4 2#, guangzhou Changjin New Material science and technology, inc., D50 particle size is 0.1 μm;
CuCr 2 O 4 3#, guangzhou Changjin New Material science and technology Limited, D50 particle size is 1.0 μm;
CuCr 2 O 4 4#, guangzhou Changjin New Material science and technology Limited, D50 particle size is 2.0 μm;
Cr 2 O 3 1# of Huashan high-new ceramic materials, inc. of Zhongshan city, D50 particle size is 0.5 μm;
Cr 2 O 3 2# high ceramic material of Huashan of Zhongshan city, ltd, D50 particle size 0.1 μm;
Cr 2 O 3 3# of Huashan high-new ceramic materials, inc. of Zhongshan city, D50 particle size is 1.0 μm;
CuO1#, guangzhou Changjin New Material science and technology, with a D50 particle size of 50nm;
CuO2#, guangzhou Changjin New Material science and technology Co., ltd, D50 particle size is 10nm;
CuO3#, guangzhou Changjin New Material science and technology Limited, D50 particle size is 120 μm;
additive: OP-1-1# -OP-1-10 #, which is made by self and specifically comprises the following steps:
OP-1-1#，CuCr 2 O 4 1#, cuO1#, cr 2 O 3 1# was mixed as 8;
OP-1-2#，CuCr 2 O 4 1#, cuO1#, cr 2 O 3 1# is mixed according to the following ratio of 9;
OP-1-3#，CuCr 2 O 4 1# and CuO1#, cr 2 O 3 1# is mixed according to 5;
OP-1-4#，CuCr 2 O 4 2# and CuO2#, cr 2 O 3 2# is mixed according to the following steps of 8;
OP-1-5#，CuCr 2 O 4 3# and CuO3#, cr 2 O 3 3# is mixed according to the following steps of 8;
OP-1-6#，CuCr 2 O 4 4# and CuO1#, cr 2 O 3 1# is mixed according to the following ratio of 8;
OP-1-7#，CuCr 2 O 4 1#, cuO1#, cr 2 O 3 1# is mixed according to 5;
OP-1-8#，CuCr 2 O 4 1# and CuO1#, cr 2 O 3 1# is mixed according to the following ratio of 5;
OP-1-9#，CuCr 2 O 4 1# and CuO1#, cr 2 O 3 1# is mixed according to 12;
nigrosine: TN-870, oriental Japan, having a D50 particle diameter of 0.2 μm;
carbon black: m717, kabot, U.S. with a D50 particle size of 22nm;
composite colorant: the red toner, the blue toner, the green toner and the yellow toner were mixed in a ratio of 2:
red toner: red iron oxide, bayer, germany, with a D50 particle size of 0.3 μm;
green powder: cobalt green, guangzhou Changjin New Material science and technology Limited, D50 particle size 0.6 μm;
blue toner: cobalt blue, guangzhou Changjin New Material science and technology Limited, with a D50 particle size of 0.6 μm;
yellow powder including yellow bismuth vanadate, DCC of Canada, and D50 particle size of 0.6 μm;
the ABS resin materials of the examples and comparative examples of the present invention were prepared by the following processes:
weighing the raw materials according to the requirement, and mixing for 3-5 min to obtain a uniformly mixed material; putting the uniformly mixed material into a double-screw extruder, performing mixing, melting and homogenizing, then extruding, granulating and cooling to obtain an ABS resin material; wherein the length-diameter ratio of an extrusion screw of the double-screw extruder is 52, the charging barrel of the extruder is 220 ℃, and the rotating speed of a main machine is 450r/min.
The transmittance test method of the ABS resin materials of the examples and comparative examples of the present invention is as follows:
the pelletized resin was injection-molded into a sample having a thickness of 1mm, and the transmittance was measured by a HunterLab-UltraScan VIS two-light-path spectrophotometer, manufactured by Q-lab of USA.
The transmittance fluctuation is the difference between the maximum value and the minimum value of the transmittance at different wavelengths.
Examples 1 to 8
This example provides a series of flat spectral transmission ABS resin materials, whose formulations are shown in Table 1.
TABLE 1 formulations (parts) of examples 1 to 8
Comparative examples 1 to 9
This comparative example provides a series of ABS resin materials having the formulation shown in Table 2.
TABLE 2 formulations of comparative examples 1 to 9 (parts)
The properties of the ABS resin materials provided in examples and comparative examples were measured according to the aforementioned property test method, and the results are shown in FIG. 1, while the transmittance of the ABS resin material provided in example 1 is shown in FIG. 1
TABLE 3 transmittance values and transmittance fluctuation values of ABS resin materials provided in examples 1 to 8
TABLE 4 transmittance values and transmittance fluctuation values of ABS resin materials provided in comparative examples 1 to 9
According to the test results, the ABS resin material provided by the embodiments of the invention has a good neutral filtering effect, the transmittance data of the spectrum band of 380-980nm is very stable, the transmittance fluctuation is less than 5%, and the transmittance curves tend to be parallel; among them, the ABS resin material provided in example 1 is the most excellent in neutral filtration effect, and satisfies the index of 30 ± 2.5% transmittance at 1.0 mm. In contrast, in comparative example 1, although the transmittance curves tend to be parallel, the transmittance curves are pure transparent resin effects due to the fact that no specific additive is added, and the light flux is strong, so that the risk of overexposure exists when an image is shot, and the neutral gray filtering effect is not achieved; cuCr in comparative example 2 2 O 4 The particle size is large, the dispersibility is poor, and the wave band transmittance fluctuation of 380-980nm is over 10 percent; comparative example3-5 of CuCr 2 O 4 And CuO, cr 2 O 3 The ratio of (A) is not appropriate, wherein in the comparative example 3, the transmission fluctuation is more than 20% in the wave band of 380-680 nm; comparative example 4 has a fluctuation range of over 15% in the 380-560nm band; the transmittance of the comparative example 5 is gradually higher in the waveband after 680nm, and a neutral filtering effect is not achieved; in comparative examples 6 to 7, conventional carbon black and aniline black were added, and although the obtained ABS resin material was the same as that of each example and was a black material, the transmittance in the infrared band (760 to 980 nm) was gradually increased, resulting in large transmittance fluctuation; in comparative example 8, red, yellow, blue and green inorganic metal pigment composite colorants are added to obtain a black material, the transmittance curve is flatter than that of comparative examples 6 to 7 in the case of adding carbon black and aniline black, but the stability is not good enough, and the fluctuation range of the transmittance in the wave band of 380 to 980nm exceeds 10%; the additive in the comparative example 9 is too large in dosage, the light transmittance of a 380-980nm wave band is lower than 10%, the light absorption is too strong, the color is pure black, and the neutral light filtering effect is not achieved.
It will be appreciated by those of ordinary skill in the art that the examples provided herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited examples and embodiments. Those skilled in the art, having the benefit of this disclosure, may effect numerous modifications thereto and changes may be made without departing from the scope of the invention in its aspects.
Claims (10)
1. An ABS resin material with flat spectral transmission characteristic is characterized by comprising the following components in parts by weight:
100 parts of acrylonitrile-butadiene-styrene copolymer;
0.05 to 1.0 portion of antioxidant;
0.05 to 1.0 portion of dispersant;
0.04 to 0.12 portion of additive;
the additive is CuCr 2 O 4 CuO and Cr 2 O 3 Mixture of (1) andCuCr in the mixture 2 O 4 CuO and Cr 2 O 3 The weight ratio of (5-9) to (1-5) to 1, the CuCr 2 O 4 The D50 particle diameter of (B) is 0.1 to 1.0. Mu.m.
2. The ABS resin material having a flat spectral transmission characteristic of claim 1, wherein the acrylonitrile-butadiene-styrene copolymer has a melt index of 20 to 30g/10min at a temperature of 220 ℃ and a load of 10kg, and has a transmittance of 85 to 90% at a thickness of 3mm in accordance with ISO 13468-1-2019.
3. The ABS resin material with flat spectral transmission characteristic of claim 1, wherein the antioxidant is one or more of phenolic antioxidant, phosphite antioxidant, sulfur-containing antioxidant or amine antioxidant.
4. The ABS resin material with flat spectral transmission characteristic of claim 1, wherein the dispersant is one or more of sodium dodecyl sulfate, methyl amyl alcohol, polyacrylamide, cellulose derivatives, ethylene bis stearamide, stearate, guar gum or fatty acid polyglycol ester.
5. The ABS resin material having a flat spectral transmission characteristic according to claim 1, wherein the additive contains Cr 2 O 3 The D50 particle diameter of (B) is 0.1 to 0.5. Mu.m.
6. The ABS resin material having a flat spectral transmittance characteristic according to claim 1, wherein the D50 particle size of CuO in the additive is 10 to 100nm.
7. The ABS resin material with flat spectral transmission characteristics according to claim 1, wherein the additive comprises CuCr 2 O 4 The D50 particle diameter of (B) is 0.6 to 0.8. Mu.m.
8. The ABS resin material with flat spectral transmission characteristics according to claim 1, wherein the additive comprises CuCr 2 O 4 CuO and Cr 2 O 3 The weight ratio of (A) to (B) is 8-9.
9. The method for preparing an ABS resin material having a flat spectral transmission characteristic according to any of claims 1 to 8, comprising the steps of: mixing the acrylonitrile-butadiene-styrene copolymer, the antioxidant, the dispersant and the additive, melting, extruding and granulating to obtain the flat light-splitting transparent ABS resin material.
10. Use of the ABS resin material having flat spectral transmittance characteristics according to any one of claims 1 to 8 for the production of optical products.
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| CN202110971015.2A CN113861613B (en) | 2021-08-23 | 2021-08-23 | ABS resin material with flat light splitting transmission characteristic and preparation method and application thereof |
| PCT/CN2022/111603 WO2023024912A1 (en) | 2021-08-23 | 2022-08-11 | Abs resin material having flat spectral transmission characteristics, preparation method therefor and application thereof |
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| CN102702672B (en) * | 2012-06-29 | 2014-07-16 | 广东银禧科技股份有限公司 | High-light-transmission high-light-shading ABS (acrylonitrile butadiene styrene) material and preparation method thereof |
| CN105348723A (en) * | 2015-11-23 | 2016-02-24 | 陈桂兴 | Modified ABS material lampshade and preparation method thereof |
| CN106398104A (en) * | 2016-12-12 | 2017-02-15 | 广东威林工程塑料股份有限公司 | Weather-resistant, bending-resistant, high-gloss and low-light-transmittance ABS material and preparation method thereof |
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| CN113683852B (en) * | 2021-08-23 | 2022-08-19 | 金发科技股份有限公司 | PMMA resin material, optical product, preparation method of optical product and application of optical product |
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