CN116199913A - ABS (Acrylonitrile butadiene styrene) high-light-color master batch and preparation method thereof - Google Patents
ABS (Acrylonitrile butadiene styrene) high-light-color master batch and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
- C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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Abstract
The invention relates to the field of ABS color master batches, in particular to an ABS high-color master batch and a preparation method thereof. The invention adopts N-beta- (aminoethyl) -gamma-aminopropyl trimethoxy silane modified colorant, adopts TPU resin and vinyl acetate to modify ABS resin, and is assisted with dispersant and surface brightening agent to prepare the ABS high-light-color master batch with self-repairing capability. The dye is uniformly dispersed, the glossiness is high, physical damage can be repaired by microwaves, the color and the brightness are kept almost unchanged, and the ABS color master batch is extremely excellent in performance.
Description
Technical Field
The invention relates to the field of ABS color master batches, in particular to an ABS high-color master batch and a preparation method thereof.
Background
The conventional methods for coloring plastics include dry (float) coloring, paste-like coloring, liquid coloring, and color-grain coloring. These methods have various disadvantages such as poor pigment dispersibility, large fly, environmental pollution, harm to the health of workers, difficult control of pigment metering, poor coloring effect, high cost, etc. Particularly, in products with extremely small pigment addition, color difference is generated due to poor pigment dispersibility. For products with high pigment concentration, the product processability is poor and the physical and mechanical properties are reduced due to the poor affinity of the pigment with the resin.
The color master batch coloring well solves the problems existing in the traditional plastic coloring method, so the color master batch coloring has become a main means for obtaining high-quality plastic coloring products. The color master batch has the advantages of excellent coloring effect, convenient use, energy conservation and no pollution of dust, sewage and the like. In addition, the color master batch coloring process has the advantages of accurate color matching, stable color, excellent processing performance, good product performance and the like. The color master batch can be widely applied to various plastic molding methods such as injection molding, extrusion, hollow blow molding, calendaring and the like, and has more advantages for injection molding of ultrathin products and concentrated color products.
The color master batch is also called pigment concentrate, and is a novel special colorant for high polymer materials. The aggregate is prepared by uniformly loading an ultra-large amount of pigment into resin, and generally consists of three basic elements of pigment, carrier resin and additive. The basic pigment content of the high-concentration color master batch can reach 30-40wt percent, the carrier content can reach 60wt percent, and in addition, a lubricant can be respectively added according to the application and performance requirements of the product to increase the fluidity of the colored resin; the brightening agent enables the product to be easy to release the film and the surface to be bright; an antioxidant for improving the antioxidant properties of the product; the ultraviolet absorbent is used for increasing the ageing resistance of the product and the like, and also produces the multifunctional color master batch for endowing the product with special properties.
The ABS resin for short is one kind of high molecular material with great requirement and fast development between engineering plastic and common plastic. 3 components of styrene, acrylonitrile and butadiene which form the ABS resin have excellent comprehensive physical and mechanical properties. Acrylonitrile makes ABS have good chemical resistance and surface hardness, butadiene makes ABS tough, and styrene makes it have good processability and dyeability. Therefore, ABS resins are widely used in electronics, electric appliances, automobiles, textile equipment, construction, living goods, and the like.
The ABS resin is colored by three methods, namely a toner coloring method, a color paste coloring method and a masterbatch coloring method. However, with the development of plastic manufacturing industry, the toner coloring method and the color paste coloring method are gradually eliminated, and the color master batch coloring method has been adopted by more and more ABS plastic processing enterprises due to the advantages of the color master batch coloring method.
The existing various pigments for the ABS color master batch have different characteristics, different performances and different coloring mechanisms. Meanwhile, ABS is copolymerized by three monomers, and because of three different components, the melt fluidity is complex, the proportion of the three components is different, and the properties are different, so that the ABS has higher requirements on the dispersibility of the color master batch for coloring. The common carbon black or carbon black master batch has no requirements on glossiness and scratch resistance, but the inorganic pigment such as carbon black has poor dispersibility, low coloring strength and insufficient bright color. If the glossiness of the plastic is to be improved, only a solution of polishing the mold can be adopted, but in this way, the initial processing and the later maintenance cost of the mold are not small.
Compared with inorganic pigment, organic pigment has the advantages of high tinting strength, good dispersibility, bright color, complete color spectrum, small relative density, etc., but has poor light resistance, heat resistance and migration resistance. CN 102838828B discloses a bright black functional black master batch for ABS engineering plastics and a preparation method thereof, wherein the raw materials comprise the following components in parts by mass: 100 parts of matrix resin, 60-120 parts of aniline black, 0-30 parts of carbon black, 0.2-20 parts of nano inorganic matters, 0.3-2 parts of antioxidant and 1-10 parts of lubricant. The aniline black is adopted to replace carbon black, chromium element is contained in the aniline black, the aniline black is harmful to human bodies, and the aniline black has poor dispersibility and is insufficient for meeting the requirements of ABS color master batches. Therefore, further studies on the properties of ABS color master batches have been required to develop high-color master batches having good dispersibility, light resistance, heat resistance, migration resistance, and abrasion resistance.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides an ABS high-light-color master batch and a preparation method thereof. The ABS high-light color master batch comprises the following raw materials in parts by mass: 40-80 parts of modified ABS resin, 14-24 parts of modified colorant, 15-25 parts of dispersing agent and 5-10 parts of surface brightening agent.
Preferably, the ABS high-light color master batch comprises the following raw materials in parts by mass: 55-70 parts of modified ABS resin, 16-20 parts of modified colorant, 15-20 parts of dispersing agent and 5-10 parts of surface brightening agent.
The dispersing agent is one or a mixture of a plurality of Meng Dansuan esters, zinc stearate, barium laurate, glyceryl palmitate, turpentine and white oil.
The surface brightening agent is one or a mixture of a plurality of PE wax, GMS, silicone or silicone oil.
The preparation method of the modified colorant comprises the following steps: mixing 10-30 parts of colorant and 60-90 parts of absolute ethyl alcohol by mass, transferring into a planetary ball mill, ball milling for 4-8 hours at normal temperature at a rotating speed of 160-200r/min to obtain colorant slurry, adding 3-6 parts of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane into the colorant slurry, stirring for 1-3 minutes at a rotating speed of 800-1200r/min, refluxing for 20-30 hours at a temperature of 100-200 ℃, and drying to obtain the modified colorant.
The colorant is one or a mixture of more of inorganic pigment and organic pigment.
The preparation method of the modified ABS resin comprises the following steps:
s1, mixing 40-80 parts of ABS resin, 15-20 parts of TPU resin and 2-5 parts of vinyl acetate according to parts by mass, stirring for 5-10min at a rotating speed of 60-80r/min, adding 10-20 parts of silicone oil and 5-10 parts of vinyltrimethoxysilane, and stirring for 10-20min at a rotating speed of 60-80r/min to obtain a mixture;
s2, placing the mixture into an internal mixer for banburying to obtain the modified ABS resin, wherein the banburying temperature is 200-250 ℃.
The invention also provides a preparation method of the ABS high-light-color master batch.
A preparation method of ABS high-light color master batch comprises the following steps:
(1) Mixing 55-70 parts by mass of modified ABS resin, 16-20 parts by mass of modified colorant, 15-20 parts by mass of dispersing agent and 5-10 parts by mass of surface brightening agent, and putting into a high-speed mixer to be fully stirred for 5-10min;
(2) And adding the mixed materials into a double-screw extruder, and melting, extruding, granulating and drying to obtain the ABS high-gloss master batch.
Parameters of the screw extruder: host rotational speed: 100-150r/min, feeding speed: 20-30r/min, length-diameter ratio of the extruder: 25-40, four sections of reference temperatures of screw heating are respectively: the temperature of the first area is 120-125 ℃, the temperature of the second area is 140-145 ℃, the temperature of the third area is 160-165 ℃, the temperature of the fourth area is 175-180 ℃, the residence time is 1-2min, and the pressure is 10-15Mpa.
The existing various pigments for the ABS color master batch have different characteristics, different performances and different coloring mechanisms. Meanwhile, ABS is copolymerized by three monomers, and because of three different components, the melt fluidity is complex, the proportion of the three components is different, and the properties are different, so that the ABS has higher requirements on the dispersibility of the color master batch for coloring. The common pigment master batch is adopted, and the gloss and scratch resistance of the pigment master batch are not required.
The invention firstly adopts ABS resin, colorant, dispersant and surface brightening agent to mix and prepare ABS high-light color master batch, which is a common preparation method of ABS color master batch at present, and the dyed ABS resin is scratched and subjected to microwave treatment, so that the color difference value and the glossiness change are larger, which indicates that the prior common technology is insufficient to prepare ABS color master batch with longer service life.
Further, the invention treats the adopted colorant, reduces the particle size of the colorant through ball milling, and adopts the mixture of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane and the colorant, so that the N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane is grafted on the surface of the colorant, which is beneficial to improving the dispersibility of the colorant and promoting the compatibility of the colorant and ABS resin. This is advantageous to some extent in improving the gloss of the ABS color master batch after coloring (Table 2), while reducing the color degradation due to high temperature, ultraviolet and other factors, and extending the color retention time. However, the gloss of the resin is significantly reduced due to the scratch, and color difference is generated, which affects the beauty.
In order to solve the problem, the invention further adopts TPU resin and vinyl acetate to modify the ABS resin, utilizes the chemical interaction between the TPU and EVA to strengthen the viscoelasticity flow of the resin, and is assisted by a certain amount of microwaves, so that the ABS resin can be promoted to heal autonomously, and the surface scratches are repaired, thereby reducing the color and glossiness changes of the ABS resin product caused by physical damage and prolonging the service life of the ABS resin. The invention considers that the TPU resin and the vinyl acetate contain a large amount of amino groups, vinyl groups and ester groups, can be coupled and grafted with the N-beta- (aminoethyl) -gamma-aminopropyl trimethoxy silane on the surface of the modified colorant, and promote the flow and dispersion of the colorant in the process of microwave repair, so that the dispersibility of the colorant on the surface of the resin after the microwave repair is kept in relative balance, and the color difference and the brightness change of the resin after the microwave repair are extremely small. And the addition of TPU resin and vinyl acetate can also obviously improve the glossiness of the color master batch, thereby achieving the effect of highlighting.
The colorant is not modified, only TPU resin and vinyl acetate are used for modifying the ABS resin, and the ABS resin has self-repairing performance, but the colorant has poor dispersibility and no fluidity, so that the color difference change of the repaired resin surface is obvious, and the glossiness of the resin is obviously reduced. Therefore, only the N-beta- (aminoethyl) -gamma-aminopropyl trimethoxy silane is adopted to modify the colorant, and TPU resin and vinyl acetate are adopted to modify the ABS resin, so that the glossiness of the prepared ABS color master batch can be effectively improved, and the service life of the ABS color master batch can be prolonged.
Still further, the present invention has found that different dispersants have a greater impact on their gloss in this formulation, wherein the montanate is best effective, which not only improves the gloss of the master batch, but also reduces the change in gloss and color difference after repair.
The invention has the beneficial effects that
The invention adopts N-beta- (aminoethyl) -gamma-aminopropyl trimethoxy silane modified colorant, adopts TPU resin and vinyl acetate to modify ABS resin, and is assisted with dispersant and surface brightening agent to prepare the ABS high-light-color master batch with self-repairing capability. The dye is uniformly dispersed, the glossiness is high, physical damage can be repaired by microwaves, the color and the brightness are kept almost unchanged, and the ABS color master batch is extremely excellent in performance.
Detailed Description
Montanate, model: licowax KSL, a company of chemical industry, coryn, china.
PE wax, model: 200a, henan, a company of Chimonanthus, inc.
N- β - (aminoethyl) - γ -aminopropyl trimethoxysilane, CAS number: 1760-24-3.
TPU resin, model: EB85A, dongguan city, a city plasticization limited.
Vinyl acetate, cat No.: YS021, shandong chemical Co., ltd.
ABS resin, product number: JS3633, hubei Jusheng technology Co., ltd.
Silicone oil, cat No.: n025, shenyang Enalapeng chemical Co., ltd.
Example 1
The ABS high-light color master batch comprises the following raw materials in parts by mass: 60 parts of ABS resin, 18 parts of colorant, 16 parts of dispersing agent and 6 parts of surface brightening agent.
The dispersing agent is montanate.
The surface brightening agent is PE wax.
The colorant is phthalocyanine blue.
A preparation method of ABS high-light color master batch comprises the following steps:
(1) 60 parts of ABS resin, 18 parts of coloring agent, 16 parts of dispersing agent and 6 parts of surface brightening agent are mixed according to parts by mass, and the mixture is put into a high-speed mixer to be fully stirred for 10min;
(2) And adding the mixed materials into a double-screw extruder, and melting, extruding, granulating and drying to obtain the ABS high-gloss master batch.
Parameters of the screw extruder: host rotational speed: 120r/min, feeding speed: 24r/min, the length-diameter ratio of the extruder is 30, and four sections of reference temperatures for screw heating are respectively as follows: the temperature of the first area is 125 ℃, the temperature of the second area is 140 ℃, the temperature of the third area is 160 ℃, the temperature of the fourth area is 175 ℃, the residence time is 2min, and the pressure is 15Mpa.
Example 2
The ABS high-light color master batch comprises the following raw materials in parts by mass: 60 parts of ABS resin, 18 parts of modified colorant, 16 parts of dispersing agent and 6 parts of surface brightening agent.
The dispersing agent is montanate.
The surface brightening agent is PE wax.
The preparation method of the modified colorant comprises the following steps: and (3) mixing 20 parts of colorant and 80 parts of absolute ethyl alcohol by mass, transferring into a planetary ball mill, ball-milling for 6 hours at normal temperature at a rotating speed of 180r/min to obtain colorant slurry, adding 5 parts of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane into the colorant slurry, stirring for 2 minutes at a rotating speed of 1000r/min, refluxing for 24 hours at 160 ℃, and drying to obtain the modified colorant.
The colorant is phthalocyanine blue.
A preparation method of ABS high-light color master batch comprises the following steps:
(1) 60 parts of ABS resin, 18 parts of modified colorant, 16 parts of dispersing agent and 6 parts of surface brightening agent are mixed according to parts by mass and put into a high-speed mixer to be fully stirred for 10min;
(2) And adding the mixed materials into a double-screw extruder, and melting, extruding, granulating and drying to obtain the ABS high-gloss master batch.
Parameters of the screw extruder: host rotational speed: 120r/min, feeding speed: 24r/min, the length-diameter ratio of the extruder is 30, and four sections of reference temperatures for screw heating are respectively as follows: the temperature of the first area is 125 ℃, the temperature of the second area is 140 ℃, the temperature of the third area is 160 ℃, the temperature of the fourth area is 175 ℃, the residence time is 2min, and the pressure is 15Mpa.
Example 3
The ABS high-light color master batch comprises the following raw materials in parts by mass: 60 parts of modified ABS resin, 18 parts of modified colorant, 16 parts of dispersing agent and 6 parts of surface brightening agent.
The dispersing agent is montanate.
The surface brightening agent is PE wax.
The preparation method of the modified colorant comprises the following steps: and (3) mixing 20 parts of colorant and 80 parts of absolute ethyl alcohol by mass, transferring into a planetary ball mill, ball-milling for 6 hours at normal temperature at a rotating speed of 180r/min to obtain colorant slurry, adding 5 parts of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane into the colorant slurry, stirring for 2 minutes at a rotating speed of 1000r/min, refluxing for 24 hours at 160 ℃, and drying to obtain the modified colorant.
The colorant is phthalocyanine blue.
The preparation method of the modified ABS resin comprises the following steps:
s1, mixing 50 parts of ABS resin, 17 parts of TPU resin and 3 parts of vinyl acetate according to parts by mass, stirring for 10min at a rotation speed of 80r/min, adding 15 parts of silicone oil and 6 parts of vinyl trimethoxysilane, and stirring for 15min at a rotation speed of 80r/min to obtain a mixture;
s2, placing the mixture into an internal mixer for banburying to obtain the modified ABS resin, wherein the banburying temperature is 240 ℃.
A preparation method of ABS high-light color master batch comprises the following steps:
(1) 60 parts of modified ABS resin, 18 parts of modified colorant, 16 parts of dispersing agent and 6 parts of surface brightening agent are mixed according to parts by mass and put into a high-speed mixer to be fully stirred for 10min;
(2) And adding the mixed materials into a double-screw extruder, and melting, extruding, granulating and drying to obtain the ABS high-gloss master batch.
Parameters of the screw extruder: host rotational speed: 120r/min, feeding speed: 24r/min, the length-diameter ratio of the extruder is 30, and four sections of reference temperatures for screw heating are respectively as follows: the temperature of the first area is 125 ℃, the temperature of the second area is 140 ℃, the temperature of the third area is 160 ℃, the temperature of the fourth area is 175 ℃, the residence time is 2min, and the pressure is 15Mpa.
Example 4
The ABS high-light color master batch comprises the following raw materials in parts by mass: 60 parts of modified ABS resin, 18 parts of modified colorant, 16 parts of dispersing agent and 6 parts of surface brightening agent.
The dispersing agent is montanate.
The surface brightening agent is PE wax.
The preparation method of the modified colorant comprises the following steps: and (3) mixing 20 parts of colorant and 80 parts of absolute ethyl alcohol by mass, transferring into a planetary ball mill, ball-milling for 6 hours at normal temperature at a rotating speed of 180r/min to obtain colorant slurry, adding 5 parts of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane into the colorant slurry, stirring for 2 minutes at a rotating speed of 1000r/min, refluxing for 24 hours at 160 ℃, and drying to obtain the modified colorant.
The colorant is phthalocyanine blue.
The preparation method of the modified ABS resin comprises the following steps:
s1, mixing 50 parts of ABS resin and 3 parts of vinyl acetate according to parts by mass, stirring for 10min at a rotation speed of 80r/min, adding 15 parts of silicone oil and 6 parts of vinyl trimethoxy silane, and stirring for 15min at a rotation speed of 80r/min to obtain a mixture;
s2, placing the mixture into an internal mixer for banburying to obtain the modified ABS resin, wherein the banburying temperature is 240 ℃.
A preparation method of ABS high-light color master batch comprises the following steps:
(1) 60 parts of modified ABS resin, 18 parts of modified colorant, 16 parts of dispersing agent and 6 parts of surface brightening agent are mixed according to parts by mass and put into a high-speed mixer to be fully stirred for 10min;
(2) And adding the mixed materials into a double-screw extruder, and melting, extruding, granulating and drying to obtain the ABS high-gloss master batch.
Parameters of the screw extruder: host rotational speed: 120r/min, feeding speed: 24r/min, the length-diameter ratio of the extruder is 30, and four sections of reference temperatures for screw heating are respectively as follows: the temperature of the first area is 125 ℃, the temperature of the second area is 140 ℃, the temperature of the third area is 160 ℃, the temperature of the fourth area is 175 ℃, the residence time is 2min, and the pressure is 15Mpa.
Example 5
The ABS high-light color master batch comprises the following raw materials in parts by mass: 60 parts of modified ABS resin, 18 parts of modified colorant, 16 parts of dispersing agent and 6 parts of surface brightening agent.
The dispersing agent is montanate.
The surface brightening agent is PE wax.
The preparation method of the modified colorant comprises the following steps: and (3) mixing 20 parts of colorant and 80 parts of absolute ethyl alcohol by mass, transferring into a planetary ball mill, ball-milling for 6 hours at normal temperature at a rotating speed of 180r/min to obtain colorant slurry, adding 5 parts of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane into the colorant slurry, stirring for 2 minutes at a rotating speed of 1000r/min, refluxing for 24 hours at 160 ℃, and drying to obtain the modified colorant.
The colorant is phthalocyanine blue.
The preparation method of the modified ABS resin comprises the following steps:
s1, mixing 50 parts of ABS resin and 17 parts of TPU resin according to parts by mass, stirring for 10min at a rotating speed of 80r/min, adding 15 parts of silicone oil and 6 parts of vinyl trimethoxy silane, and stirring for 15min at a rotating speed of 80r/min to obtain a mixture;
s2, placing the mixture into an internal mixer for banburying to obtain the modified ABS resin, wherein the banburying temperature is 240 ℃.
A preparation method of ABS high-light color master batch comprises the following steps:
(1) 60 parts of modified ABS resin, 18 parts of modified colorant, 16 parts of dispersing agent and 6 parts of surface brightening agent are mixed according to parts by mass and put into a high-speed mixer to be fully stirred for 10min;
(2) And adding the mixed materials into a double-screw extruder, and melting, extruding, granulating and drying to obtain the ABS high-gloss master batch.
Parameters of the screw extruder: host rotational speed: 120r/min, feeding speed: 24r/min, the length-diameter ratio of the extruder is 30, and four sections of reference temperatures for screw heating are respectively as follows: the temperature of the first area is 125 ℃, the temperature of the second area is 140 ℃, the temperature of the third area is 160 ℃, the temperature of the fourth area is 175 ℃, the residence time is 2min, and the pressure is 15Mpa.
Comparative example 1
The ABS high-light color master batch comprises the following raw materials in parts by mass: 60 parts of modified ABS resin, 18 parts of colorant, 16 parts of dispersing agent and 6 parts of surface brightening agent.
The dispersing agent is montanate.
The surface brightening agent is PE wax.
The colorant is phthalocyanine blue.
The preparation method of the modified ABS resin comprises the following steps:
s1, mixing 50 parts of ABS resin, 17 parts of TPU resin and 3 parts of vinyl acetate according to parts by mass, stirring for 10min at a rotation speed of 80r/min, adding 15 parts of silicone oil and 6 parts of vinyl trimethoxysilane, and stirring for 15min at a rotation speed of 80r/min to obtain a mixture;
s2, placing the mixture into an internal mixer for banburying to obtain the modified ABS resin, wherein the banburying temperature is 240 ℃.
A preparation method of ABS high-light color master batch comprises the following steps:
(1) 60 parts of modified ABS resin, 18 parts of coloring agent, 16 parts of dispersing agent and 6 parts of surface brightening agent are mixed according to parts by mass, and the mixture is placed into a high-speed mixer to be fully stirred for 10min;
(2) And adding the mixed materials into a double-screw extruder, and melting, extruding, granulating and drying to obtain the ABS high-gloss master batch.
Parameters of the screw extruder: host rotational speed: 120r/min, feeding speed: 24r/min, the length-diameter ratio of the extruder is 30, and four sections of reference temperatures for screw heating are respectively as follows: the temperature of the first area is 125 ℃, the temperature of the second area is 140 ℃, the temperature of the third area is 160 ℃, the temperature of the fourth area is 175 ℃, the residence time is 2min, and the pressure is 15Mpa.
Comparative example 2
The ABS high-light color master batch comprises the following raw materials in parts by mass: 60 parts of modified ABS resin, 18 parts of modified colorant, 16 parts of dispersing agent and 6 parts of surface brightening agent.
The dispersing agent is magnesium stearate.
The surface brightening agent is PE wax.
The preparation method of the modified colorant comprises the following steps: and (3) mixing 20 parts of colorant and 80 parts of absolute ethyl alcohol by mass, transferring into a planetary ball mill, ball-milling for 6 hours at normal temperature at a rotating speed of 180r/min to obtain colorant slurry, adding 5 parts of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane into the colorant slurry, stirring for 2 minutes at a rotating speed of 1000r/min, refluxing for 24 hours at 160 ℃, and drying to obtain the modified colorant.
The colorant is phthalocyanine blue.
The preparation method of the modified ABS resin comprises the following steps:
s1, mixing 50 parts of ABS resin, 17 parts of TPU resin and 3 parts of vinyl acetate according to parts by mass, stirring for 10min at a rotation speed of 80r/min, adding 15 parts of silicone oil and 6 parts of vinyl trimethoxysilane, and stirring for 15min at a rotation speed of 80r/min to obtain a mixture;
s2, placing the mixture into an internal mixer for banburying to obtain the modified ABS resin, wherein the banburying temperature is 240 ℃.
A preparation method of ABS high-light color master batch comprises the following steps:
(1) 60 parts of modified ABS resin, 18 parts of modified colorant, 16 parts of dispersing agent and 6 parts of surface brightening agent are mixed according to parts by mass and put into a high-speed mixer to be fully stirred for 10min;
(2) And adding the mixed materials into a double-screw extruder, and melting, extruding, granulating and drying to obtain the ABS high-gloss master batch.
Parameters of the screw extruder: host rotational speed: 120r/min, feeding speed: 24r/min, the length-diameter ratio of the extruder is 30, and four sections of reference temperatures for screw heating are respectively as follows: the temperature of the first area is 125 ℃, the temperature of the second area is 140 ℃, the temperature of the third area is 160 ℃, the temperature of the fourth area is 175 ℃, the residence time is 2min, and the pressure is 15Mpa.
Test example 1
Sample preparation for testing: the ABS high-light color master batches prepared in the examples 1-5, the comparative example 1 and the comparative example 2 are respectively mixed with ABS resin according to the mass ratio of 1:20, and are put into a high-speed mixer to be fully stirred for 10min; and adding the mixed materials into a double-screw extruder, and carrying out melting, extrusion, shaping and drying to obtain a test sample, wherein the size of the test sample is 5 cm-10 cm-1 cm.
Parameters of the screw extruder: host rotational speed: 120r/min, feeding speed: 24r/min, the length-diameter ratio of the extruder is 30, and four sections of reference temperatures for screw heating are respectively as follows: the temperature of the first area is 125 ℃, the temperature of the second area is 140 ℃, the temperature of the third area is 160 ℃, the temperature of the fourth area is 175 ℃, the residence time is 2min, and the pressure is 15Mpa.
Self-repairing samples: after scraping, placing the test sample in a household microwave oven for 5min, wherein the output power of the microwave oven is 700W, and the working frequency is 2450MHz, and obtaining the self-repaired sample.
According to the general standard of GMW 14688-2012: scratch resistance test method the scratch resistance condition of the surface of the material is tested according to the standard, the scratch resistance is 10N, and the self-repairing performance of the material is marked by the color difference value and the glossiness difference value of the sample before scratch and after self-repairing.
Gloss level: an angle of 60 degrees was selected according to the standard test of GB/T8807-1988 method for specular gloss test of plastics.
Table 1: color difference value and gloss difference test result
| Color difference value | Gloss difference/60 angle | |
| Example 1 | 13.325 | 8 |
| Example 2 | 10.127 | 7 |
| Example 3 | 0.921 | 2 |
| Example 4 | 8.214 | 4 |
| Example 5 | 7.923 | 5 |
| Comparative example 1 | 9.814 | 5 |
| Comparative example 2 | 3.227 | 3 |
Test example 2
Sample: ABS color master batches prepared in examples 1-5, comparative example 1 and comparative example 2.
Gloss level: an angle of 60 degrees was selected according to the standard test of GB/T8807-1988 method for specular gloss test of plastics.
Table 2: results of gloss test
| Gloss/60 angle | |
| Example 1 | 86 |
| Example 2 | 90 |
| Example 3 | 94 |
| Example 4 | 92 |
| Example 5 | 92 |
| Comparative example 1 | 91 |
| Comparative example 2 | 91 |
The existing various pigments for the ABS color master batch have different characteristics, different performances and different coloring mechanisms. Meanwhile, ABS is copolymerized by three monomers, and because of three different components, the melt fluidity is complex, the proportion of the three components is different, and the properties are different, so that the ABS has higher requirements on the dispersibility of the color master batch for coloring. The common pigment master batch is adopted, and the gloss and scratch resistance of the pigment master batch are not required.
As can be seen from Table 1, the ABS high-gloss master batch prepared in the embodiment 1 of the invention is prepared by mixing ABS resin, colorant, dispersant and surface brightening agent, and is a common preparation method of ABS master batch at present, and the dyed ABS resin is subjected to scraping and microwave treatment, so that the color difference value and glossiness of the dyed ABS resin are greatly changed, which indicates that the adoption of the conventional common technology is insufficient for preparing the ABS master batch with longer service life.
The present invention in example 2 treats the colorant used, reduces the particle size of the colorant by ball milling, and mixes the N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane with the colorant, so that the N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane grafts the colorant surface, which is advantageous for improving the dispersibility of the colorant and promoting the compatibility of the colorant and the ABS resin. This is advantageous to some extent in improving the gloss of the ABS color master batch after coloring (Table 2), while reducing the color degradation due to high temperature, ultraviolet and other factors, and extending the color retention time. However, the gloss of the resin is significantly reduced due to the scratch, and color difference is generated, which affects the beauty.
In order to solve the problem, in the embodiment 3 of the invention, the TPU resin and the vinyl acetate are further adopted to modify the ABS resin, the chemical interaction between the TPU and the EVA is utilized to enhance the viscoelasticity flow of the resin, and a certain amount of microwaves are assisted to promote the ABS resin to heal autonomously, repair the surface scratches, thereby reducing the color and glossiness changes of the ABS resin product caused by physical damage and prolonging the service life of the ABS resin. It can be seen from examples 1 and 2 of table 1 that scratch abrasion has a large influence on the color and glossiness of ABS resin, whereas example 3 adopts TPU resin and vinyl acetate to modify ABS resin, and only microwave treatment is needed to repair and improve the phenomenon to a great extent. The invention considers that the TPU resin and the vinyl acetate contain a large amount of amino groups, vinyl groups and ester groups, can be coupled and grafted with the N-beta- (aminoethyl) -gamma-aminopropyl trimethoxy silane on the surface of the modified colorant, and promote the flow and dispersion of the colorant in the process of microwave repair, so that the dispersibility of the colorant on the surface of the resin after the microwave repair is kept in relative balance, and the color difference and the brightness change of the resin after the microwave repair are extremely small. In addition, as can be seen from table 2, the addition of the TPU resin and the vinyl acetate can also obviously improve the glossiness of the color master batch, thereby achieving the effect of highlighting. The effect of using a single TPU resin, vinyl acetate, for example 4 and example 5 is significantly poorer.
Comparative example 1, in which the colorant was not modified, only the TPU resin and vinyl acetate were used to modify the ABS resin, and the ABS resin had self-repairing properties, but the dispersibility of the colorant was poor, fluidity was not possessed, and the color difference change of the repaired resin surface was remarkable, which also resulted in a remarkable decrease in the glossiness thereof. Therefore, only the N-beta- (aminoethyl) -gamma-aminopropyl trimethoxy silane is adopted to modify the colorant, and TPU resin and vinyl acetate are adopted to modify the ABS resin, so that the glossiness of the prepared ABS color master batch can be effectively improved, and the service life of the ABS color master batch can be prolonged.
Still further, the present invention has found that different dispersants have a greater impact on their gloss in this formulation, wherein the montanate is best effective, which not only improves the gloss of the master batch, but also reduces the change in gloss and color difference after repair.
Claims (8)
1. The preparation method of the ABS high-light color master batch is characterized by comprising the following steps of:
(1) Mixing the modified ABS resin, the modified colorant, the dispersing agent and the surface brightening agent, and putting the mixture into a high-speed mixer for fully stirring;
(2) And adding the mixed materials into a double-screw extruder, and melting, extruding, granulating and drying to obtain the ABS high-gloss master batch.
2. The method for preparing the ABS high-gloss master batch according to claim 1, wherein the parameters of the double screw extruder are as follows: host rotational speed: 100-150r/min, feeding speed: 20-30r/min, length-diameter ratio of the extruder: 25-40, four sections of reference temperatures of screw heating are respectively: the temperature of the first area is 120-125 ℃, the temperature of the second area is 140-145 ℃, the temperature of the third area is 160-165 ℃, the temperature of the fourth area is 175-180 ℃, the residence time is 1-2min, and the pressure is 10-15Mpa.
3. The method for preparing the ABS high-gloss master batch according to claim 1, wherein the dispersing agent is one or a mixture of Meng Dansuan ester, zinc stearate, barium laurate, glyceryl palmitate, turpentine and white oil.
4. The method for preparing the ABS high-gloss master batch according to claim 1, wherein the surface brightening agent is one or a mixture of more of PE wax, GMS, silicone or silicone oil.
5. The method for preparing the ABS high-gloss master batch according to claim 1, wherein the method for preparing the modified colorant comprises the following steps: mixing 10-30 parts of colorant and 60-90 parts of absolute ethyl alcohol by mass, transferring into a planetary ball mill, ball milling for 4-8 hours at normal temperature at a rotating speed of 160-200r/min to obtain colorant slurry, adding 3-6 parts of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane into the colorant slurry, stirring for 1-3 minutes at a rotating speed of 800-1200r/min, refluxing for 20-30 hours at a temperature of 100-200 ℃, and drying to obtain the modified colorant.
6. The method for preparing ABS high-gloss master batch according to claim 5, wherein the colorant is one or a mixture of inorganic pigment and organic pigment.
7. The method for preparing the ABS high-gloss master batch according to claim 1, wherein the method for preparing the modified ABS resin comprises the following steps:
s1, mixing 40-80 parts of ABS resin, 15-20 parts of TPU resin and 2-5 parts of vinyl acetate according to parts by mass, stirring for 5-10min at a rotating speed of 60-80r/min, adding 10-20 parts of silicone oil and 5-10 parts of vinyltrimethoxysilane, and stirring for 10-20min at a rotating speed of 60-80r/min to obtain a mixture;
s2, placing the mixture into an internal mixer for banburying to obtain the modified ABS resin, wherein the banburying temperature is 200-250 ℃.
8. An ABS high photochromic masterbatch prepared by the method of any one of claims 1 to 7.
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