CN115418111A - Flow pattern master batch, flow pattern material and preparation method - Google Patents
Flow pattern master batch, flow pattern material and preparation method 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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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
- C08J2400/00—Characterised by the use of unspecified polymers
- C08J2400/12—Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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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
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Abstract
The invention discloses a flow pattern master batch, a flow pattern material and a preparation method thereof, and relates to the field of high polymer materials. The fluid pattern master batch comprises the following components in parts by weight: LCP resin: 70-85 parts; PET resin: 3-8 parts; a compatilizer: 3-7 parts; colorant: 9-15 parts; the melt flow rate of the compatibilizer is 0.5-8g/10min measured at 190 ℃ under 2.16 kg. The melting point that this application utilized LCP master batch and PA66 material is different, mixes the flow line master batch and PA66 resin and moulds plastics, lets the flow line master batch of high temperature soften the dispersion in microthermal PA66 material, selects different colorants, reaches the flow line special effect of different colours, realizes the flow line effect after moulding plastics, and processes such as fungible traditional spraying and silk screen printing, the lower processing technology of cost is more environmental protection.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a flow pattern master batch, a flow pattern material and a preparation method thereof.
Background
The PA66 is also called nylon 66, polyamide 66 or chinlon 66, is formed by mutual alternate polycondensation of hexamethylene diamine molecules and adipic acid molecules, has excellent heat resistance and mechanical properties, has the characteristics of high strength and high impact resistance, and can be widely applied to the related fields of aerospace, automobiles, electronics and electrics, buildings, fitness equipment, electric tools, industrial parts, agricultural machinery and the like.
Due to the ultrahigh heat-resistant characteristic of the PA66, the processing temperature of the PA66 is required to be 260 ℃ or above, and the high temperature enables the flow pattern master batch to be completely melted in the PA66 material, so that the flow pattern effect cannot occur, and at present, few flow pattern master batches applied to the PA66 material are available in the market, so that the application of the PA66 material to a flow pattern material product is limited.
Disclosure of Invention
The invention provides a flow pattern master batch, a flow pattern material and a preparation method thereof, and aims to solve the technical problem that the conventional PA66 material is difficult to produce due to overhigh processing temperature.
In order to solve the technical problems, the invention provides a flow line master batch which comprises the following components in parts by weight:
LCP resin: 70-85 parts;
PET resin: 3-8 parts;
a compatilizer: 3-7 parts of a stabilizer;
colorant: 9-15 parts;
the melt flow rate of the maleic anhydride grafted ethylene-octene copolymer elastomer is 0.5-8g/10min measured at 190 ℃, 2.16kg and ASTM D-1238. .
By adopting the scheme, the flow line master batch has a high melting point, can adapt to high-temperature processing conditions of PA66, selects different colorants to achieve flow line special effects with different colors, enables the high-temperature flow line master batch to be softened and dispersed in a low-temperature PA66 material, and enables a molded part to be in a flow line shape after injection molding; the melting point of LCP resin in the flow line master batch is obviously higher than that of PA66, insoluble plaques can appear in a PA66 system at the temperature of more than 280 ℃, and the PET resin is utilized to modify the LCP resin, so that the melting point of the flow line master batch is reduced to the temperature capable of softening and forming flow lines in the PA66 system, and the flow line master batch is prevented from being completely dissolved or generating insoluble blocks in the PA66 system to generate a flow line effect.
Preferably, the colorant is one or more of white pigment, black pigment, red pigment, yellow pigment, blue pigment and cyan pigment.
Preferably, the colorant is one or more of a colorant a, a colorant b and a colorant c; the colorant a is prepared from a white pigment, a yellow pigment, a blue pigment and a cyan pigment in a mass ratio of (3-8): (5-12): (12-18) and (0-2) compounding; the colorant b is prepared by compounding a white pigment and a yellow pigment according to the mass ratio of (3-8) to (13-21); the colorant c is compounded by white pigment, black pigment, yellow pigment and red pigment according to the mass ratio of (8-12) to (0-2) to (3-8) to (2-5).
As a preferable scheme, the colorant a is prepared by compounding vulcanized HD-S, 2GTI, 4702PG and K7104LW according to the mass ratio of 5; the colorant b is prepared from zinc sulfide HD-S, 2GTI and Yellow K1310 according to the mass ratio of 5:15:2, compounding; the colorant c is composed of zinc sulfide HD-S, M717, YELLOW K1310 and
the mass ratio of Red 350FA is 10:1:5:3, compounding.
Preferably, the compatilizer is maleic anhydride grafted ethylene-octene copolymer elastomer.
As a preferred scheme, the melting point of the flow line master batch is 260-280 ℃.
Preferably, the intrinsic viscosity of the PET resin is 0.50-1.20dl/g, and the PET resin is detected by GB/T14190-2008 & lt & gt test method for polyester chips (PET).
As a preferable scheme, the antioxidant also comprises 0.3 to 5 weight parts of antioxidant, wherein the antioxidant is one or more of phenols, phosphites, sulfur-containing antioxidants and amine antioxidants.
In order to solve the above technical problems, the second object of the present invention is to provide a method for preparing a flow-line masterbatch, comprising the following steps:
(1) LCP resin, PET resin, compatilizer, colorant and other components are mixed in a mixer for 3min-5min;
(2) And (2) putting the uniformly mixed material into a double-screw extrusion device, and extruding and granulating after mixing, melting and homogenizing, wherein the length-diameter ratio of an extrusion screw of the extrusion device is 48-65, the charging barrel temperature of the extrusion device is 270-290 ℃, the rotating speed of a main machine is 500r/min-700r/min, and cooling is carried out to obtain the flow pattern master batch.
In order to solve the above technical problems, the present invention provides a flow pattern material, comprising the flow pattern master batch as claimed in any one of claims 1 to 5 and PA66 in a mass ratio of (8 to 15): (85-92) compounding; the melt flow rate of the PA66 is 70-270g/10min measured at 275 ℃, 2.16kg and GB/T3682 standard.
Through adopting above-mentioned scheme, the melting point that LCP master batch and PA66 material were utilized to this application is different, lets the flow line master batch of high temperature soften the dispersion in microthermal PA66 material, and the colorant in the flow line master batch makes the finished piece outward appearance of moulding plastics into the flow line form, and processes such as fungible traditional spraying and silk screen printing are more environmental protection, and the lower processing technology of cost.
In order to solve the above technical problems, the fourth object of the present invention is to provide a method for preparing a flow pattern material, comprising the following steps: and adding the flow pattern master batch into PA66 resin, uniformly mixing, and then performing injection molding, wherein the injection molding temperature is 250-270 ℃, the injection molding backpressure is 0-0.5MPa, and the injection molding pressure is 40-60MPa, so as to obtain the flow pattern material.
In order to solve the above technical problems, a fifth object of the present invention is to provide an application of a flow pattern material in a housing of a home appliance and an electronic and electrical product, such as a housing of an electric cooker, a panel of an air conditioner, a housing of a charger, a housing of an absorber, etc.
Compared with the prior art, the embodiment of the invention has the following beneficial effects:
the application utilizes the different melting points of the flow line master batch and the PA66 material, and the high-temperature flow line master batch is softened and dispersed in the low-temperature PA66 material, different colorants are selected, the flow line special effects of different colors are achieved, the flow line effect is realized after injection molding, the traditional processes such as spraying and silk printing can be replaced, and the cost is lower, and the processing process is more environment-friendly.
Drawings
FIG. 1: the surface photographing result of the flow line material in the first embodiment of the invention is shown;
FIG. 2 is a schematic diagram: the surface photographing result of the flow pattern material in the fourth embodiment of the invention is shown;
FIG. 3: the surface photographing result of the flow line material in the fifth embodiment of the invention is shown;
FIG. 4: the surface photographing result of the flow pattern material in the fourth comparative example is shown in the invention;
FIG. 5 is a schematic view of: the surface photographing result of the flow pattern material in the fifth comparative example is shown in the invention;
FIG. 6: the surface photograph result of one of the flow-line materials in comparative example one of the present invention was obtained.
Detailed Description
The technical solutions in the embodiments of the present invention will be described below clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
Table 1 below shows the sources of the raw materials in the examples and comparative examples of the present application, and hindered phenolic antioxidants were commercially available and used in parallel experiments, unless otherwise specified.
TABLE 1-Source and Properties of the raw materials in the examples of the present application and comparative examples
Preparation examples 1 to 6
The specific contents of the components of the flow pattern master batch are shown in table 2, and the flow pattern master batch comprises LCP resin, PET resin, a compatilizer, a hindered phenol antioxidant and a colorant; the compatilizer is maleic anhydride grafted ethylene-octene copolymer elastomer; the antioxidant is 1098; the colorant comprises one or more of colorant a, colorant b and colorant c; colorant a comprises zinc sulfide HD-S, 2GTI, 4702PG and K7104LW in a mass ratio of 5; the colorant b comprises 5:15:2 zinc sulfide HD-S, 2GTI and Yellow K1310; the coloring agent c comprises the following components in a mass ratio of 10:1:5:3 zinc sulfide HD-S, M717, YELLOW K1310 and
red 350FA; the hindered phenol antioxidant is 1098.
The preparation method of the fluid-textured master batch comprises the following steps:
(1) Fully drying the LCP resin and the PET resin by a hot air drying oven at the drying temperature of 120 ℃ for 1 hour;
(2) Weighing the raw materials according to the proportion, and mixing the LCP resin, the PET resin, the compatilizer, the antioxidant and the colorant in a mixer for 5min;
(3) And (2) putting the uniformly mixed material into a double-screw extruder, mixing, melting, homogenizing, extruding and granulating, wherein the length-diameter ratio of an extrusion screw of the double-screw extruder is 52, the charging barrel of the extruder is 280 ℃, the rotating speed of a main engine is 600r/min, cooling is carried out to obtain the flow texture master batch, and the melting point is measured according to ISO 11357-1/-3 standard and is shown in Table 2.
TABLE 2 contents of components and melting points of the flow grain master batches in preparation examples 1 to 6 and comparative preparation examples 1 to 6
Examples 1 to 6 and comparative examples 1 to 10
The flow line material comprises the following components in percentage by mass (85-92): (8-15) the PA66 and the flow line master batch, which comprises the following preparation steps: and adding the flow pattern master grains obtained in the preparation example or the comparative preparation example into PA66 resin, uniformly mixing, and then performing injection molding at the injection molding temperature of 260 ℃, the injection molding backpressure of 0.3MPa and the injection molding pressure of 50MPa to obtain the flow pattern material with the flow pattern effect on the surface.
TABLE 3 Components and amounts in examples 1 to 6 and comparative examples 1 to 10
Performance test
1. Flow line effect: according to the combination of the flow pattern effect on the surface of the injection molding product and the sensory evaluation, the evaluation result is shown in table 4, and the evaluation criteria are as follows:
A. the flow lines are clear and rich in layering sense, and the evaluation grade is good, as shown in figures 1-3;
B. the flow line is slightly fuzzy, the layering sense is not strong, and the evaluation grade is general, as shown in fig. 6;
C. no flow mark effect and poor evaluation rating, as shown in fig. 4-5.
2. Evaluation standard of infusible particulate matter: infusible particles are particles having surface specks, as shown in fig. 4-5.
TABLE 4 Performance test results of examples 1 to 6 and comparative examples 1 to 10
The performance test results of example 1 and comparative example 1 in table 4 show that the melting point of LCP is reduced by the PET resin added to the flow-line master batch, and the melting point of the master batch is close to or lower than PA66 due to too high content, so that the master batch is compatible in PA66 and cannot have the flow-line effect, and the melting point of LCP is too high due to too low content, so that the master batch generates insoluble substances in PA66, and therefore, the melting point of the flow-line master batch is improved by the PET resin, the melting point of the flow-line master batch is higher than PA66, the temperature of the flow-line master batch is softened in a PA66 system to generate the flow-line effect, and no insoluble substances are generated.
The performance test results of embodiment 1 and comparative examples 2-3 in table 4 show that, the melting points of LCP master batch and PA66 material are different, so that the high-temperature flow pattern master batch is softened and dispersed in the low-temperature PA66 material, and the appearance of the molded part after injection molding has a flow pattern effect, and the melting point of the resin in the master batch is too low or the addition amount of LCP resin is too small, which leads to the reduction of the melting point of the final flow pattern master batch, so that the material is completely dissolved in the PA66 injection molding process, and the flow pattern effect cannot be generated.
Combining the performance test results of example 1 and comparative example 4 in table 4, it can be seen that the content of LCP resin is critical, and because the melting point of LCP resin is too high, it needs to be modified by PET resin to reduce the melting point, and too high content of LCP resin can result in insoluble plaque in PA66 system, while too low content can result in poor flow pattern retention and flow pattern disappearance.
The performance test results of example 1 and comparative examples 5-6 in table 4 show that the melt index of the compatibilizer affects the flow pattern effect of the product, the material compatibility is better when the melt index is too high, and the flow pattern effect is similar when the flow pattern easily disappears.
The performance test results of example 1 and comparative examples 7 to 8 in table 4 show that the addition proportion of the flow line master batch in the PA66 material system is too high or too low, which affects the flow line effect of the product, and that when the content is too high, insoluble patches appear, and when the content is too low, the flow line is poor to maintain, and the flow lines disappear.
According to the performance test results of the example 1 and the comparative examples 9-10 in the table 4, the flow line effect of the product is affected by the excessively low melt index of the PA66 material, and the flow line is poor to maintain and disappear due to the excessively low melt index of the PA66 material.
The above-mentioned embodiments are provided to further explain the objects, technical solutions and advantages of the present invention in detail, and it should be understood that the above-mentioned embodiments are only examples of the present invention and are not intended to limit the scope of the present invention. It should be understood that any modifications, equivalents, improvements and the like, which come within the spirit and principle of the invention, may occur to those skilled in the art and are intended to be included within the scope of the invention.
Claims (9)
1. The flow pattern master batch is characterized by comprising the following components in parts by weight:
LCP resin: 70-85 parts;
PET resin: 3-8 parts;
a compatilizer: 3-7 parts;
colorant: 9-15 parts;
the melt flow rate of the compatilizer is 0.5-8g/10min at 190 ℃ under the measurement of 2.16 kg.
2. The flow-textured masterbatch according to claim 1, wherein the colorant is one or more of a colorant a, a colorant b and a colorant c; the colorant a is prepared from a white pigment, a yellow pigment, a blue pigment and a cyan pigment according to the mass ratio of (3-8): (5-12): (12-18) and (0-2) compounding; the colorant b is prepared by compounding a white pigment and a yellow pigment according to a mass ratio of (3-8) to (13-21); the colorant c is compounded by zinc sulfide white pigment, black pigment, yellow pigment and red pigment according to the mass ratio of (8-12) to (0-2) to (3-8) to (2-5).
3. The flow-textured masterbatch of claim 1, wherein the compatibilizer is a maleic anhydride grafted ethylene-octene copolymer elastomer.
4. The rheo-chromatic master batch of claim 1, wherein the rheo-chromatic master batch has a melting point of 260 ℃ to 280 ℃.
5. The flow line masterbatch of claim 1, further comprising 0.3-5 parts by weight of an antioxidant, wherein the antioxidant is one or more of a phenol antioxidant, a phosphite antioxidant, a sulfur antioxidant, and an amine antioxidant.
6. A method for preparing a flow-textured masterbatch according to any one of claims 1 to 5, comprising the steps of:
(1) Mixing LCP resin, PET resin, a compatilizer, a colorant and other components in a mixer for 3-5 min;
(2) And (2) putting the uniformly mixed material into a double-screw extrusion device, and extruding and granulating after mixing, melting and homogenizing, wherein the length-diameter ratio of an extrusion screw of the extrusion device is 48-65, the charging barrel temperature of the extrusion device is 270-290 ℃, the rotating speed of a main machine is 500r/min-700r/min, and cooling is carried out to obtain the flow pattern master batch.
7. A flow-textured material, characterized by comprising the flow-textured masterbatch according to any one of claims 1 to 5 and PA66 in a mass ratio (8 to 15): (85-92) compounding, wherein the melt flow rate of the PA66 is 70-270g/10min at 275 ℃ and 2.16 kg.
8. A method of producing a flow-textured material, for producing a flow-textured material as claimed in claim 7, comprising the steps of: and adding the flow pattern master batch into PA66 resin, uniformly mixing, and then performing injection molding, wherein the injection molding temperature is 250-270 ℃, the injection molding backpressure is 0-0.5MPa, and the injection molding pressure is 40-60MPa, so as to obtain the flow pattern material.
9. Use of the flow-line material according to claim 7 in housings for household appliances, electronic and electrical products.
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| CN114634636A (en) * | 2022-02-22 | 2022-06-17 | 金发科技股份有限公司 | Color master batch with fluorescent flow pattern effect and preparation method and application thereof |
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