CN112980054A - Strip-shaped aluminum pigment for high white brightness of ABS (acrylonitrile butadiene styrene) and preparation method thereof - Google Patents
Strip-shaped aluminum pigment for high white brightness of ABS (acrylonitrile butadiene styrene) and preparation method thereof Download PDFInfo
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- CN112980054A CN112980054A CN202110223395.1A CN202110223395A CN112980054A CN 112980054 A CN112980054 A CN 112980054A CN 202110223395 A CN202110223395 A CN 202110223395A CN 112980054 A CN112980054 A CN 112980054A
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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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
- C08K7/00—Use of ingredients characterised by shape
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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Abstract
The invention discloses a strip-shaped aluminum pigment for high white brightness of ABS and a preparation method thereof, wherein the method comprises the following steps: the method comprises the following steps: selecting an aluminum pigment, and coating the aluminum pigment to obtain polymer-coated flaky aluminum particles; step two: and (3) mixing the polymer-coated flaky aluminum particles obtained in the step one with carrier resin, a promoting arrangement auxiliary agent and a dispersing agent, stirring for pre-dispersion, drying, and performing extrusion molding to obtain a finished product, wherein the carrier resin is modified PMMA resin or modified ASA resin. According to the invention, the surface of the flaky aluminum particle is coated, and the carrier resin is selected, so that the compatibility of the flaky aluminum particle and ABS is improved, and the orientation of the flaky aluminum particle is obviously improved by adding the auxiliary agent for promoting arrangement in the formula; the pigment is specifically applied to ABS products, the white brightness (L value) and the metal effect of the pigment in spraying-free ABS application are improved, the appearance of the product is improved, the differentiation advantage can be created for the product of a customer, and the added value of the product is improved.
Description
Technical Field
The invention relates to the technical field of aluminum pigment production, in particular to a strip-shaped aluminum pigment for high white brightness of ABS and a preparation method thereof.
Background
Spraying-free metal effect plastics (hereinafter referred to as spraying-free plastics) develop rapidly under the environment-friendly high-pressure condition in recent years, are mainly used in industries such as household appliances, automobiles, packaging and the like, improve the texture and appearance of plastics, mainly have the advantages of environmental protection, no VOC (volatile organic compounds) emission, cost reduction of more than 30 percent, no spraying transfer, assembly after molding and the like, and are gradually favored by host plants and household power plants.
However, the disadvantages of the spray-free plastic are also obvious, for example, the most common ABS (acrylonitrile-butadiene-styrene) plastic product, the strip aluminum pigment in the market uses PE wax as a carrier, when applied to ABS plastic, the orientation arrangement of the flake aluminum particles is poor, the included angle is large, the specific characterization is that the difference between the data measured along and against the injection direction by the pentagonal colorimeter is large, which results in the disadvantages of large difference in white brightness (poor metal texture), flow marks and weld lines, surface pits and pits, etc. compared with spray coating, and these disadvantages also limit the rapid development of spray-free.
In order to solve the bottleneck of no-spraying metal texture and poor white brightness, I have carried out special research, and aiming at improving the coating treatment and arrangement flatness of the flaky aluminum particles, the metal effect and the white brightness of the flaky aluminum particles are improved.
Disclosure of Invention
The invention aims to provide a strip-shaped aluminum pigment for high white brightness of ABS and a preparation method thereof, which solve the problem that the white brightness and metal effect are poor when the existing strip-shaped aluminum pigment is applied to spraying-free ABS.
The invention realizes the purpose through the following technical scheme:
a preparation method of a strip-shaped aluminum pigment for high white brightness of ABS comprises the following steps:
the method comprises the following steps: selecting an aluminum pigment, and coating the aluminum pigment to obtain polymer-coated flaky aluminum particles;
step two: and (3) mixing the polymer-coated flaky aluminum particles obtained in the step one with carrier resin, a promoting arrangement auxiliary agent and a dispersing agent, stirring for pre-dispersion, drying, and performing extrusion molding to obtain a finished product, wherein the carrier resin is modified PMMA resin or modified ASA resin.
The further improvement is that the aluminum pigment is selected from aluminum pigments with 60-70 percent of aluminum content, 0.2-0.5 mu m of flaky aluminum particles and 10-15 mu m of flaky aluminum particle diameter D50.
The further improvement is that the specific operation of the coating treatment is as follows: putting aluminum pigment into a reaction kettle, adding a solvent, adding a monomer, stirring at the rotating speed of 20-25rpm, heating the reaction kettle to 70-80 ℃ for constant temperature, dripping an azo initiator at the speed of 0.08-0.12ml per minute, keeping stirring for 3-4h, stopping heating and aging for 2-3h after stirring is finished, discharging, press-filtering and removing the solvent to obtain the polymer-coated flaky aluminum particles with the solid content of 65-75%.
The further improvement is that when 1 part of aluminum pigment is added, 4-6 parts of solvent are added, and 0.1-0.2 part of monomer is added.
The further improvement is that the solvent is one or a mixture of two of D60 solvent and D70 solvent, and the monomer is one or a mixture of two of methyl methacrylate and butyl methacrylate.
The further improvement is that the molecular weight of the modified PMMA resin is 40000-60000, the TG point is 100-120 ℃, the molecular weight of the modified ASA resin is 60000-100000, and the flow rate under the condition of ASTM D-12385 KG/200 ℃ is more than 2.
The further improvement is that the arrangement promoting assistant is one or more of CAB cellulose acetate butyrate, ethylene acrylic acid copolymer and ethylene maleic anhydride graft copolymer.
The further improvement is that the dispersing agent is one or more of magnesium stearate, silicone powder and EVA with molecular weight less than 5000 and melting point less than 100 ℃.
The further improvement is that the mixing weight ratio of the polymer-coated flaky aluminum particles to the carrier resin, the arrangement promoting assistant and the dispersing agent is 70-75:15-25:1-5: 1-5.
The further improvement is that the concrete operations of stirring pre-dispersion, drying and extrusion molding are as follows: putting the mixed raw materials into a stirrer according to the proportion, and stirring at 15-20rpm for 20-30min for pre-dispersion; then putting the pre-dispersed material into an oven for drying at the drying temperature of 130-150 ℃ for 10-12 h; and then the dried material is put into an extruder for extrusion molding, the extrusion temperature is 200 plus 230 ℃, and the rotating speed of a host is 400 plus 500rpm, so as to obtain a finished product.
The invention also provides a strip-shaped aluminum pigment for ABS high white brightness, which is prepared by the method.
The invention has the beneficial effects that: according to the invention, the surface of the flaky aluminum particle is coated, and the carrier resin is selected, so that the compatibility of the flaky aluminum particle and ABS is improved, and the orientation of the flaky aluminum particle is obviously improved by adding the auxiliary agent for promoting arrangement in the formula; the pigment is specifically applied to ABS products, the white brightness (L value) and the metal effect of the pigment in spraying-free ABS application are improved, the appearance of the product is improved, the differentiation advantage can be created for the product of a customer, and the added value of the product is improved.
Drawings
FIG. 1 is an external view of different ABS color plates.
Detailed Description
The present application is described in further detail below with reference to examples, and it should be noted that the following detailed description is provided for further explanation of the present application and should not be construed as limiting the scope of the present application, and that certain insubstantial modifications and adaptations of the present application may be made by those skilled in the art based on the above-mentioned disclosure.
Equipment selection, extrusion equipment: 35 twin-screw extruder, length-diameter ratio: 44-52; stirring equipment: 100L single blade mixer; drying equipment: 500L vacuum drying oven.
Example 1
A preparation method of a strip-shaped aluminum pigment for high white brightness of ABS comprises the following steps:
the method comprises the following steps: selecting an aluminum pigment with the aluminum content of 60%, the thickness of flaky aluminum particles of 0.2 mu m and the particle size D50 of the flaky aluminum particles of 10 mu m, adding 1 part of the aluminum pigment into a reaction kettle, adding 4 parts of a D60 solvent, adding 0.1 part of a methyl methacrylate monomer, stirring at a rotating speed of 20rpm, heating the reaction kettle to 70 ℃ for constant temperature, dropping an azo initiator at a speed of 0.08ml per minute, keeping stirring for 4 hours, closing heating and aging for 2 hours after stirring, discharging, press-filtering and desolventizing after aging, and preparing polymer-coated flaky aluminum particles with the solid content of 65%;
step two: mixing the polymer-coated flaky aluminum particles obtained in the step one with modified PMMA resin (molecular weight is 40000-; then putting the pre-dispersed material into an oven for drying at the drying temperature of 130 ℃ for 12 hours; and putting the dried material into an extruder for extrusion molding, wherein the extrusion temperature is 200 ℃, and the rotating speed of a main machine is 500rpm, so as to obtain a finished product.
Example 2
A preparation method of a strip-shaped aluminum pigment for high white brightness of ABS comprises the following steps:
the method comprises the following steps: selecting an aluminum pigment with the aluminum content of 65 percent, the thickness of flaky aluminum particles of 0.3 mu m and the particle size D50 of the flaky aluminum particles of 12 mu m, adding 1 part of the aluminum pigment into a reaction kettle, adding 5 parts of a D70 solvent, adding 0.15 part of a butyl methacrylate monomer, stirring at a rotating speed of 22rpm, heating the reaction kettle to 75 ℃ for constant temperature, dropping an azo initiator at a speed of 0.1ml per minute, keeping stirring for 3.5h, closing heating and aging for 2.5h after stirring, discharging, press-filtering and desolventizing after aging, and preparing 70 percent solid polymer-coated flaky aluminum particles;
step two: mixing the polymer-coated flaky aluminum particles obtained in the step one with modified ASA resin (with the molecular weight of 60000-100000 and the flow rate of more than 2 at the temperature of ASTM D-12385 KG/200 ℃), ethylene acrylic acid copolymer and silicone powder according to the weight ratio of 72:20:3:3, putting the mixed raw materials into a stirrer according to the ratio, and stirring at 18rpm for 25min for pre-dispersion; then putting the pre-dispersed material into an oven for drying, wherein the drying temperature is 140 ℃, and the drying time is 11 hours; and putting the dried material into an extruder for extrusion molding, wherein the extrusion temperature is 220 ℃, and the rotating speed of a main machine is 450rpm, so as to obtain a finished product.
Example 3
A preparation method of a strip-shaped aluminum pigment for high white brightness of ABS comprises the following steps:
the method comprises the following steps: selecting an aluminum pigment with the aluminum content of 70%, the thickness of flaky aluminum particles of 0.5 mu m and the particle size D50 of the flaky aluminum particles of 15 mu m, adding 1 part of the aluminum pigment into a reaction kettle, adding 6 parts of a D60 solvent, adding 0.2 part of a butyl methacrylate monomer, stirring at a rotating speed of 25rpm, heating the reaction kettle to 80 ℃ for constant temperature, dropping an azo initiator at a speed of 0.12ml per minute, keeping stirring for 3 hours, stopping heating and aging for 3 hours after stirring, discharging, press-filtering and desolventizing after aging to prepare a polymer-coated aluminum pigment with the solid content of 75%;
step two: mixing the polymer-coated aluminum pigment obtained in the step one with a modified PMMA resin (the molecular weight is 40000-60000, and the TG point is 100-120 ℃), an ethylene maleic anhydride graft copolymer and EVA (ethylene vinyl acetate) with the molecular weight of less than 5000 and the melting point of less than 100 ℃, wherein the mixing weight ratio is 75:25:5:5, putting the mixed raw materials into a stirrer according to the proportion, and stirring at 20rpm for 20min for pre-dispersion; then putting the pre-dispersed material into an oven for drying at 150 ℃ for 10 hours; and putting the dried material into an extruder for extrusion molding, wherein the extrusion temperature is 230 ℃, and the rotating speed of a main machine is 400rpm, so as to obtain a finished product.
The ABS color plate sample prepared in example 2 (after improvement) and the ABS color plate sample prepared by applying the common strip-shaped aluminum pigment to ABS (before improvement) are selected, as shown in FIG. 1, the ABS color plate before improvement is arranged on the left side of the figure, and the ABS color plate after improvement is arranged on the right side of the figure, so that the visual effects of white brightness and metal texture of the improved ABS color plate are improved.
In addition, the ABS sample before and after the modification were tested with a penta-colorimeter, which is 15 °, 25 °, 45 °, 75 ° and 110 °, respectively, and includes a forward test and a reverse test, which states: the light source is forward along the injection molding direction, and the light source is reverse against the injection molding direction.
(1) Test data before improvement (five angles):
(2) modified test data (five angles):
(3) test data before and after modification (integrating sphere):
to summarize: the difference of forward and reverse data of 15 degrees and 25 degrees before improvement is large, which shows that the arrangement of the flaky aluminum particles in the color plate has a certain included angle with the plane of the color plate, and the test results in different directions have differences; after improvement, the arrangement of the flaky aluminum particles is more parallel to the surface, the forward and reverse data are closer, and the visual effect is also greatly improved.
The test principle is as follows: the more parallel the flaky aluminum particles are arranged to the plane of the color plate, the flatter the reflecting surface formed by the aluminum sheet is, the higher the L values of the 15-degree and 25-degree tests are, and the less difference is found in the test results in different directions. Example (c): the sprayed color plate is tested by a penta-angle color difference meter, the test direction has little influence on L data, and because a process of solvent volatilization and aluminum sheet orientation is carried out after spraying, most of aluminum sheets are arranged in a direction parallel to the paint surface, and the formed reflecting surface is flat; the color plate made by the spraying-free process has the advantages that the arrangement of aluminum sheets is not smooth in spraying, a certain included angle is formed, when testing is carried out in different directions, the L value data have differences, the differences are the largest in the two directions of the injection molding direction and the injection molding direction, and the difference is the largest.
Comparative example 1
A preparation method of a strip-shaped aluminum pigment for high white brightness of ABS comprises the following steps of basically the same as example 2, and the only difference is that: the cleanup additive is replaced by CAB cellulose acetate butyrate with equivalent amount from ethylene acrylic acid copolymer.
Comparative example 2
A preparation method of a strip-shaped aluminum pigment for high white brightness of ABS comprises the following steps of basically the same as example 2, and the only difference is that: the drainage promoting assistant is replaced by CAB cellulose acetate butyrate with equivalent amount from ethylene acrylic acid copolymer, and then the carrier resin is replaced by modified ASA resin with equivalent amount from modified PMMA resin.
The strip-shaped aluminum pigments obtained in comparative example 1 and comparative example 2 were tested according to the same test method as described above, and the results were as follows:
comparative example 1 test data (five angles):
comparative example 2 test data (five angles):
from the detection results, compared with the comparative example 1, the CAB cellulose acetate butyrate is matched with the modified ASA resin, so that the difference of the forward and reverse data is very small, particularly 15 degrees and 25 degrees, which shows that the arrangement of the flaky aluminum particles in the color plate has almost no included angle with the plane of the color plate, and the overall effect is better than that of the scheme of the example 2 (the ethylene acrylic acid copolymer is matched with the modified ASA resin); in contrast, in comparative example 2, CAB cellulose acetate butyrate was used in combination with the modified PMMA resin, and the difference in the forward and reverse data was substantially the same as that in example 2, and was not significantly different. Therefore, the unexpected technical effect of combining CAB cellulose acetate butyrate and modified ASA resin is shown, the improvement of the arrangement of the aluminum pigment can be further promoted, and the effect of combining CAB cellulose acetate butyrate with other resins or combining modified ASA resin with other arrangement-promoting assistants is similar and is inferior to the scheme of combining CAB cellulose acetate butyrate and modified ASA resin.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (10)
1. A preparation method of strip aluminum pigment for ABS high white brightness is characterized in that: the steps include
The method comprises the following steps: selecting an aluminum pigment, and coating the aluminum pigment to obtain polymer-coated flaky aluminum particles;
step two: and (3) mixing the polymer-coated flaky aluminum particles obtained in the step one with carrier resin, a promoting arrangement auxiliary agent and a dispersing agent, stirring for pre-dispersion, drying, and performing extrusion molding to obtain a finished product, wherein the carrier resin is modified PMMA resin or modified ASA resin.
2. The method for preparing a striped aluminum pigment with high white brightness for ABS according to claim 1, wherein: the aluminum pigment is prepared from 60-70% of aluminum, 0.2-0.5 μm of flaky aluminum particles and 10-15um of flaky aluminum particles with the particle size D50.
3. The method for preparing a striped aluminum pigment with high white brightness for ABS according to claim 1, wherein: the coating treatment comprises the following specific operations: putting aluminum pigment into a reaction kettle, adding a solvent, adding a monomer, stirring at the rotating speed of 20-25rpm, heating the reaction kettle to 70-80 ℃ for constant temperature, dripping an azo initiator at the speed of 0.08-0.12ml per minute, keeping stirring for 3-4h, stopping heating and aging for 2-3h after stirring is finished, discharging, press-filtering and removing the solvent to obtain the polymer-coated flaky aluminum particles with the solid content of 65-75%.
4. The method for preparing a striped aluminum pigment with high white brightness for ABS according to claim 3, wherein: when 1 part of aluminum pigment is added, 4-6 parts of solvent and 0.1-0.2 part of monomer are added.
5. The method for preparing a striped aluminum pigment with high white brightness for ABS according to claim 3, wherein: the solvent is one or a mixture of two of D60 solvent and D70 solvent, and the monomer is one or a mixture of two of methyl methacrylate and butyl methacrylate.
6. The method for preparing a striped aluminum pigment with high white brightness for ABS according to claim 1, wherein: the molecular weight of the modified PMMA resin is 40000-60000, the TG point is 100-120 ℃, the molecular weight of the modified ASA resin is 60000-100000, and the flow rate under the condition of ASTM D-12385 KG/200 ℃ is more than 2.
7. The method for preparing a striped aluminum pigment with high white brightness for ABS according to claim 1, wherein: the arrangement promoting auxiliary agent is one or more of CAB cellulose acetate butyrate, ethylene acrylic acid copolymer and ethylene maleic anhydride graft copolymer, and the dispersing agent is one or more of magnesium stearate, silicone powder and EVA with the molecular weight lower than 5000 and the melting point lower than 100 ℃.
8. The method for preparing a striped aluminum pigment with high white brightness for ABS according to claim 1, wherein: the weight ratio of the polymer-coated flaky aluminum particles to the carrier resin, the arrangement promoting assistant and the dispersing agent is 70-75:15-25:1-5: 1-5.
9. The method for preparing a striped aluminum pigment with high white brightness for ABS according to claim 1, wherein: the concrete operations of stirring pre-dispersion, drying and extrusion molding are as follows: putting the mixed raw materials into a stirrer according to the proportion, and stirring at 15-20rpm for 20-30min for pre-dispersion; then putting the pre-dispersed material into an oven for drying at the drying temperature of 130-150 ℃ for 10-12 h; and then the dried material is put into an extruder for extrusion molding, the extrusion temperature is 200 plus 230 ℃, and the rotating speed of a host is 400 plus 500rpm, so as to obtain a finished product.
10. A strip-shaped aluminum pigment for high white brightness of ABS is characterized in that: prepared by the method of any one of claims 1 to 9.
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| CN202110223395.1A CN112980054A (en) | 2021-03-01 | 2021-03-01 | Strip-shaped aluminum pigment for high white brightness of ABS (acrylonitrile butadiene styrene) and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113480827A (en) * | 2021-08-16 | 2021-10-08 | 珠海格力新材料有限公司 | Preparation method of metal effect imitation plastic |
| CN115819997A (en) * | 2022-12-13 | 2023-03-21 | 汕头市龙骅材料技术有限公司 | Preparation method of aluminum-based pearlescent pigment |
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| JPH11302558A (en) * | 1998-04-17 | 1999-11-02 | Kansai Paint Co Ltd | Colored aluminum pigment and coating composition containing the same |
| CN106220891A (en) * | 2016-07-28 | 2016-12-14 | 上海明园新材料科技有限公司 | A kind of preparation method of the aluminum pigment with resin high-affinity |
| CN107674282A (en) * | 2017-10-18 | 2018-02-09 | 安徽天易金属新材料有限公司 | A kind of aluminium pigment for 3D printing high polymer material and preparation method thereof |
| CN107674302A (en) * | 2017-10-18 | 2018-02-09 | 安徽天易金属新材料有限公司 | A kind of pre-dispersed aluminium pigment for bumper and preparation method thereof |
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2021
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH11302558A (en) * | 1998-04-17 | 1999-11-02 | Kansai Paint Co Ltd | Colored aluminum pigment and coating composition containing the same |
| CN106220891A (en) * | 2016-07-28 | 2016-12-14 | 上海明园新材料科技有限公司 | A kind of preparation method of the aluminum pigment with resin high-affinity |
| CN107674282A (en) * | 2017-10-18 | 2018-02-09 | 安徽天易金属新材料有限公司 | A kind of aluminium pigment for 3D printing high polymer material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113480827A (en) * | 2021-08-16 | 2021-10-08 | 珠海格力新材料有限公司 | Preparation method of metal effect imitation plastic |
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| CN115819997A (en) * | 2022-12-13 | 2023-03-21 | 汕头市龙骅材料技术有限公司 | Preparation method of aluminum-based pearlescent pigment |
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