CN111004428A - Special color master batch for polyethylene water supply pipe and preparation method and application thereof - Google Patents
Special color master batch for polyethylene water supply pipe and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a special color master batch for a polyethylene water supply pipe and a preparation method and application thereof. The composition is prepared from the following components in parts by weight: 40-80 parts of carrier resin, 2-25 parts of compatibilization resin, 28-55 parts of carbon black, 2-15 parts of dispersing agent, 1-3 parts of antioxidant, 0.05-0.2 part of carbon nanotube, 0.01-2 parts of titanium dioxide, 0.01-2 parts of zinc oxide and 0.2-1.5 parts of crosslinking inhibitor. According to the invention, the carbon black master batch is blended into black by using four toner systems, and the formula of the PE water supply pipe master batch is effectively improved, so that the definition of laser marking of the PE water supply pipe can be effectively improved, the edge definition is improved, the obtained product is more attractive, and the defect of laser marking of the carbon black master batch in the production application of the PE water supply pipe is effectively overcome. In addition, the color master batch has good matching property with the raw material of the pipe, can reduce the bad phenomena of scratches, hanging lines and the like, and has better surface finish.
Description
Technical Field
The invention belongs to the technical field of water supply plastic pipe coloring. More particularly, relates to a special color master batch for a polyethylene water supply pipe material, and a preparation method and application thereof.
Background
Polyethylene (PE) is a thermoplastic plastic, and has the characteristics of low density, good flexibility, strong corrosion resistance, excellent impact resistance, long service life, good insulating property, easiness in construction and installation and the like compared with steel pipes, cast iron pipes and UPVC pipes. The PE water supply pipe has the advantages of low density, low embrittlement temperature, good toughness, corrosion resistance, good insulating property, easy coloring, easy construction and installation and the like, and is widely applied to municipal water supply systems, building water supply systems, residential districts, plant area buried water supply systems, industry and water treatment pipeline systems.
Conventional methods for coloring plastics include dry (float) coloring, paste coloring, liquid coloring, and colored grain coloring. These methods have many disadvantages, such as poor dispersibility of the pigment, great flying, environmental pollution, harm to the health of workers, difficulty in controlling the amount of the pigment, poor coloring effect, high cost, and the like. Particularly, in a paper sheet containing a very small amount of pigment, the affinity between the pigment and the resin is poor, and the processability of the product is poor, and the physical and mechanical properties are deteriorated. The color master batch, also called pigment concentrate, is a special colorant for novel high polymer materials. The pigment is an aggregate prepared by uniformly supporting an excessive amount of pigment in a resin, and generally comprises three basic elements of the pigment, a carrier resin and an additive. The color master batch has the advantages of excellent coloring effect, convenient use, energy conservation and no pollution of dust, sewage and the like. However, with the wide application of color master batches, higher requirements are also put forward on the color master batches.
At present, the surface of a common PE water supply pipe adopts a surface ink code spraying technology to mark and trace factory and production information of the pipe, but the technology has the defects that marks are easy to abrade or fade off, the identification is difficult, the technical environment friendliness is poor, and the cost is high. In recent years, some manufacturers have utilized laser marking technology to improve the fastness and the environment-friendly defects of the surface mark of the PE water supply pipe, but because the PE water supply pipe is made of high-density polyethylene, the PE water supply pipe is polyethylene with a small amount of side groups or short branched chains, and the PE water supply pipe cannot be marked by laser without modification. While the color contrast can be improved after the carbon black is colored, white characters are not white enough after the marking, and the handwriting is fuzzy. In addition, the PE molecules have high flexibility and soft surfaces, and when sundries such as sand stones and burrs are attached to the sizing sleeve, the supporting plate or the sealing ring in the production process, poor appearance phenomena such as outer surface scratches and hanging wires can be generated, the interference on a laser marking production line is large, and the difficulty in popularization and application of the pipe laser marking is increased.
Chinese patent document CN 107353471A1 discloses a tube color master batch, which is prepared from the following raw materials in parts by weight: 58-62 parts of lithopone, 6-11 parts of pigment, 32-48 parts of polyethylene, 1-3 parts of bis (2-hydroxyethyl) methyltetradecyl chlorinated quaternary ammonium salt, 2-4 parts of heat stabilizer and 2-4 parts of ultraviolet absorbent. However, the addition of the color master batch of the pipe and other conventional color master batches into the PE water supply pipe cannot effectively improve the definition of laser marking, has adverse effects on the performance and appearance of a plastic matrix, and is a problem to be solved urgently in the production at present.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the special color master batch for the polyethylene water supply pipe, wherein the carbon black is blended into black by adopting four toner systems, and the color master batch formula of the PE water supply pipe is effectively improved, so that the definition of laser marking of the PE water supply pipe can be effectively improved, the product is more attractive, and the defect of laser marking of the carbon black in the production application of the PE water supply pipe is effectively overcome; the color stability of the color master batch special for the polyethylene water supply pipe is improved when the color master batch is colored, and the color difference is small.
The invention is realized by the following technical scheme:
the special color master batch for the polyethylene water supply pipe is prepared from the following components in parts by weight: 40-80 parts of carrier resin, 2-25 parts of compatibilization resin, 28-55 parts of carbon black, 2-15 parts of dispersing agent, 1-3 parts of antioxidant, 0.05-0.2 part of carbon nanotube, 0.01-2 parts of titanium dioxide, 0.01-2 parts of zinc oxide and 0.2-1.5 parts of crosslinking inhibitor.
By adopting the technical scheme, the carbon black color master batch is blended into black by utilizing four toner systems, and the color master batch formula of the PE water supply pipe is effectively improved, so that the definition of laser marking of the PE water supply pipe can be effectively improved, the heat conduction effect of the matrix is improved, the matrix is foamed more uniformly, the edge definition is improved, the obtained product is more attractive, and the defect of laser marking of the carbon black color master batch in the production application of the PE water supply pipe is effectively overcome. In addition, the color master batch has good matching property with the raw materials of the pipe, has the properties of high heat resistance, high hardness and high modulus, reduces the appearance defects of scratches, hanging wires and the like on the outer surface of a PE water supply pipe in production, and has better surface finish.
As a preferred scheme, the special color master batch for the polyethylene water supply pipe is prepared from the following components in parts by weight: 70 parts of carrier resin, 10 parts of compatibilization resin, 40 parts of carbon black, 2 parts of dispersant, 1.5 parts of antioxidant, 0.15 part of carbon nanotube, 0.5 part of titanium dioxide, 0.4 part of zinc oxide and 0.25 part of crosslinking inhibitor.
As a preferred embodiment, the carrier resin is PE100 grade resin; the compatibilized resin is a Cyclic Olefin Copolymer (COC); the carbon black is furnace carbon black with primary particle size of 20-25 nm.
Preferably, the dispersant is at least one selected from the group consisting of a fatty acid dispersant, an ester dispersant, a paraffin dispersant, a metal soap dispersant and a low molecular wax dispersant.
As a preferable scheme, the dispersing agent is selected from one or more of paraffin wax, polyethylene wax, oxidized polyethylene wax, fatty acid ester wax, barium stearate, zinc stearate, magnesium stearate or calcium stearate.
Preferably, the antioxidant is selected from hindered phenol antioxidants and/or phosphite antioxidants.
Preferably, the carbon nanotubes are selected from single-wall carbon nanotubes and/or double-wall carbon nanotubes.
Preferably, the crosslinking inhibitor is one or more of dimethyl sulfoxide, dimethylamine or dimethylformamide.
As a preferable scheme, the titanium dioxide is oily rutile type nano titanium dioxide dispersion liquid with the solid content of 20-40%.
As a preferable scheme, the zinc oxide is oily nano zinc oxide liquid with the solid content of 20-40%.
The invention also relates to a preparation method of the color master batch special for the polyethylene water supply pipe, which comprises the following steps:
s1, feeding the components into an internal mixer together according to a ratio, and internally mixing for 20-40 min at 130-160 ℃;
s2, pouring the black melt resin mass into a double-shaft tearing machine by using a tipping device, cooling the melt, synchronously tearing and crushing, conveying the crushed particles to a parallel co-rotating double-screw extruder for extrusion granulation, and obtaining the black color master batch special for the polyethylene water supply pipe.
The application of the color master batch or the color master batch prepared by the method in the preparation of the water supply pipe is also within the protection scope of the invention.
The invention also relates to a polyethylene water supply pipe suitable for laser marking, which is prepared by adopting the color master batch or the color master batch prepared by the method; the preparation method of the polyethylene water supply pipe suitable for laser marking comprises the following steps: adding the color master batch or the color master batch prepared by the method into PE 100-grade resin used for the water supply pipe according to the mass ratio of 4-10%, stirring for 2-6 min, uniformly mixing, and then extruding and shaping to obtain the water supply pipe.
Compared with the prior art, the invention has the following beneficial effects:
(1) the color master batch comprises four different inorganic powders of carbon black, carbon nano tube, titanium dioxide and zinc oxide, and is added into the PE water supply pipe in the form of the color master batch, so that the definition of laser marking of the PE water supply pipe can be effectively improved, and the performance and the appearance of a plastic matrix are not affected. The carbon nano tube is added into the carbon black color master, so that the heat conduction effect of the matrix is improved, the matrix is more uniformly foamed, the edge definition is improved, the energy absorption rate of the surface of the pipe is improved by adding the titanium dioxide and the zinc oxide, and the laser sensitivity of the surface of the pipe is improved. The obtained special color master batch for the polyethylene water supply pipe has the advantages of improved color stability, uniform dispersion and small color difference during coloring.
(2) The color master batch carrier in the invention selects PE100 resin and compatibilized resin Cyclic Olefin Copolymer (COC), the PE100 resin is special resin for the PE pipe for water supply, and the color master batch carrier is used as a carrier to keep the matching property of the color master batch and the raw material of the pipe. In addition, COC is PE high-compatibility resin, and the molecular side chain of the COC has polar groups and better fluidity, so that inorganic powder with a coloring effect can be better coated and dispersed; and the COC has the properties of high heat resistance, high hardness and high modulus, so that the poor appearance phenomena of outer surface scratches, hanging lines and the like generated in the production of the PE water supply pipe are reduced, and the surface smoothness is better.
(3) The invention improves the uniformity of pigment dispersion by three processes of mixing by an internal mixer, shredding by a mechanical tearing machine and granulating by a double screw, and reduces the influence of color master batches on the uneven marking effect of the matrix pipe and the mechanical property.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. The present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are intended to be included in the scope of the present invention.
Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Examples 1 to 3 and comparative examples 1 to 4
The invention provides the raw material ratios (in parts by weight) of examples 1-3 and comparative examples 1-4 shown in Table 1.
TABLE 1 raw material ratios (in parts by weight) of examples 1 to 3 and comparative examples 1 to 4
Wherein, the polyethylene is PE100 resin with a melt index of 0.2-0.35 g/10 min; the carbon black is furnace carbon black with the particle size of 20-25 nm; the compatibilization resin is a cycloolefin copolymer which is TOPAS 6013 of Thailand Corp, and the volume flow index (260 ℃/2.16kg) of the compatibilization resin is 12-15 mL/10 min; selecting the titanium dioxide as oily rutile type nano titanium dioxide dispersion liquid with the solid content of 30 percent; the zinc oxide is oily nano zinc oxide liquid with the solid content of 25 percent; polyethylene wax 617A is selected as the dispersant; the antioxidant is selected from hindered phenol antioxidant 1010 and phosphite ester antioxidant 168 according to the proportion of 1: 1 by mass ratio; the carbon nanotube is a single-walled carbon nanotube; dimethyl sulfoxide is selected as the crosslinking inhibitor.
Preparation d of the example and comparative example Components described aboven25X 2.3mm SDR11 polyethylene water supply pipe material, which comprises the following steps:
(1) preparing the color master batch special for the polyethylene water supply pipe: feeding the components into an internal mixer, mixing for 30min at 130-160 ℃, pouring black melt resin pellets into a double-shaft tearing machine by using a tipping device, cooling the melt, synchronously tearing and crushing, and conveying the crushed particles to a parallel co-rotating double-screw extruder for extrusion granulation to obtain black color master batches special for the polyethylene water supply pipe;
(2) preparing a polyethylene water supply pipe suitable for laser marking: the prepared special color master batch for the polyethylene water supply pipe is added into PE100 resin used for the water supply pipe according to the mass ratio of 5%, then the mixture is stirred for 4min by a stirrer to be uniformly mixed, and the obtained mixture is added into an extruder to be extruded and shaped, so that the finished product of the polyethylene water supply pipe is produced.
The polyethylene water supply pipes obtained in the above examples 1 to 3 and comparative examples 1 to 4 were tested according to the national standard GB/T13663.2-2018. The whiteness was tested according to the national standard GB 2913-1982. The definition after laser marking adopts the color difference appearance to beat the mark position and carry out the color difference measurement, divide into five grades, wherein:
first order represents the color difference change Δ L: 8-25;
second order represents the color difference change Δ L: 26-40;
three levels represent the color difference change Δ L: 41-55;
four levels represent color difference change Δ L: 56-70 parts of;
five levels indicate a color difference change Δ L > 70.
The laser machines in the examples and comparative examples used the same marking frequency parameters for the surfaces. The performance test results are shown in table 2:
TABLE 2 test results of examples 1 to 3 and comparative examples 1 to 4
According to the test results of table 2, it was found that: the definition of examples 1-3 is significantly higher than that of comparative examples 1-4, which proves that the black blended by the four toner systems is different from the conventional color master batch system only using carbon black, and the four toners are different. The invention obviously improves the sensitivity of the pipe to laser, improves the definition and realizes the synergistic effect by adding the carbon nano tube, the titanium dioxide and the zinc oxide, and the color stability of the obtained special color master batch for the polyethylene water supply pipe is improved, the dispersion is uniform and the color difference is small when the color master batch is colored. The marking definition of the embodiment 1, the embodiment 2 and the embodiment 3 is in four grades, the bad appearance phenomena such as scratch, thread hanging and the like do not exist, the surface smoothness is better, and the performance and the appearance of the plastic substrate are not affected. Example 1 has a higher dispersion grade and higher thermal stability than examples 2 and 3.
The results of comparative example 4 demonstrate that not only the dispersion uniformity of the colored powder is maintained but also the physical and mechanical properties of the pipe are more excellent by the addition of the cycloolefin copolymer.
Example 4
In an embodiment of the color master batch of the present invention, the proportioning and the preparation method of the color master batch are the same as those in embodiment 1. The polyethylene is PE100 grade resin, and the melt index of the polyethylene is 0.2-0.35 g/10 min; the carbon black is furnace carbon black with the particle size of 20-25 nm; the compatibilization resin is a cycloolefin copolymer which is TOPAS 6013 of Thailand Corp, and the volume flow index (260 ℃/2.16kg) of the compatibilization resin is 12-15 mL/10 min; selecting the titanium dioxide as oily rutile type nano titanium dioxide dispersion liquid with the solid content of 30 percent; the zinc oxide is oily nano zinc oxide liquid with the solid content of 25 percent. The difference lies in that:
fatty acid ester wax is selected as the dispersant in the embodiment; the antioxidant is selected from hindered phenol antioxidant 1010 and phosphite ester antioxidant 168 according to the proportion of 2: 1 by mass ratio; the carbon nano tube is a double-wall carbon nano tube; dimethylamine is selected as the crosslinking inhibitor.
Example 5
In an embodiment of the color master batch of the present invention, the proportioning and the preparation method of the color master batch are the same as those in embodiment 1. The polyethylene is PE100 grade resin, and the melt index of the polyethylene is 0.2-0.35 g/10 min; the carbon black is furnace carbon black with the particle size of 20-25 nm; the compatibilization resin is a cycloolefin copolymer which is TOPAS 6013 of Thailand Corp, and the volume flow index (260 ℃/2.16kg) of the compatibilization resin is 12-15 mL/10 min; selecting the titanium dioxide as oily rutile type nano titanium dioxide dispersion liquid with the solid content of 30 percent; the zinc oxide is oily nano zinc oxide liquid with the solid content of 25 percent. The difference lies in that:
the dispersant of this example was prepared from barium stearate, zinc stearate, magnesium stearate and calcium stearate in a ratio of 1: 1: 1: 1 by mass ratio; the antioxidant is selected from hindered phenol antioxidant 1010 and phosphite ester antioxidant 168 according to the proportion of 2: 1 by mass ratio; the carbon nano tube is a single-wall carbon nano tube and a double-wall carbon nano tube according to the proportion of 1: 1; the crosslinking inhibitor is dimethylformamide.
Example 6
In an embodiment of the color master batch of the present invention, the proportioning and the preparation method of the color master batch are the same as those in embodiment 1. The polyethylene is PE100 grade resin, and the melt index of the polyethylene is 0.2-0.35 g/10 min; the carbon black is furnace carbon black with the particle size of 20-25 nm; the compatibilization resin is a cycloolefin copolymer which is TOPAS 6013 of Thailand Corp, and the volume flow index (260 ℃/2.16kg) of the compatibilization resin is 12-15 mL/10 min; selecting the titanium dioxide as oily rutile type nano titanium dioxide dispersion liquid with the solid content of 30 percent; the zinc oxide is oily nano zinc oxide liquid with the solid content of 25 percent. The difference lies in that:
in the present example, the dispersant used paraffin, polyethylene wax, oxidized polyethylene wax was mixed according to a ratio of 1: 1: 1 by mass ratio; the antioxidant is hindered phenol antioxidant 1010; the carbon nano tube is a double-wall carbon nano tube; the crosslinking inhibitor adopts dimethyl sulfoxide, dimethylamine and dimethylformamide according to the weight ratio of 1: 1: 1, and the components are compounded according to the mass ratio of 1.
The color master batch prepared in the embodiment 4-6 is prepared into the polyethylene water supply pipe suitable for laser marking according to the method in the embodiment 1. The preparation method and the test method of the polyethylene water supply pipe material in the embodiments 4 to 6 are the same as those in the embodiment 1. In embodiments 4-6, the laser machine applies the same marking frequency parameter to the surface. Compared with the color master batches in the embodiments 1, 4, 5 and 6, the color master batches have no obvious difference in performance, have marking definition in four grades, do not have poor appearance phenomena such as scratches and hanging lines, have better surface finish and have no adverse effect on the performance and the appearance of the plastic matrix.
The applicant declares that the above detailed description is a preferred embodiment described for the convenience of understanding the present invention, but the present invention is not limited to the above embodiment, i.e. it does not mean that the present invention must be implemented by means of the above embodiment. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. The special color master batch for the polyethylene water supply pipe is characterized by being prepared from the following components in parts by weight: 40-80 parts of carrier resin, 2-25 parts of compatibilization resin, 28-55 parts of carbon black, 2-15 parts of dispersing agent, 1-3 parts of antioxidant, 0.05-0.2 part of carbon nanotube, 0.01-2 parts of titanium dioxide, 0.01-2 parts of zinc oxide and 0.2-1.5 parts of crosslinking inhibitor.
2. The special color master batch for the polyethylene water supply pipe material according to claim 1, which is characterized by being prepared from the following components in parts by weight: 70 parts of carrier resin, 10 parts of compatibilization resin, 40 parts of carbon black, 2 parts of dispersant, 1.5 parts of antioxidant, 0.15 part of carbon nanotube, 0.5 part of titanium dioxide, 0.4 part of zinc oxide and 0.25 part of crosslinking inhibitor.
3. The color master batch special for polyethylene water supply pipes according to claim 1, wherein the carrier resin is PE100 grade resin; the compatibilized resin is a Cyclic Olefin Copolymer (COC); the carbon black is furnace carbon black with primary particle size of 20-25 nm.
4. The color master batch special for polyethylene water supply pipes according to claim 1, wherein the dispersant is at least one selected from fatty acid dispersants, ester dispersants, paraffin dispersants, metal soap dispersants and low molecular wax dispersants;
the antioxidant is selected from hindered phenol antioxidant and/or phosphite antioxidant;
the carbon nanotubes are selected from single-wall carbon nanotubes and/or double-wall carbon nanotubes;
the crosslinking inhibitor is one or more of dimethyl sulfoxide, dimethylamine or dimethylformamide.
5. The color master batch special for polyethylene water supply pipes according to claim 4, wherein the dispersing agent is one or more selected from paraffin wax, polyethylene wax, oxidized polyethylene wax, fatty acid ester wax, barium stearate, zinc stearate, magnesium stearate or calcium stearate.
6. The color master batch special for polyethylene water supply pipes according to claim 1, wherein the titanium dioxide is oily rutile type nano titanium dioxide dispersion liquid with solid content of 20-40%.
7. The color master batch special for polyethylene water supply pipes according to claim 1, wherein the zinc oxide is oily nano zinc oxide liquid with a solid content of 20-40%.
8. The preparation method of the color master batch special for the polyethylene water supply pipe material as claimed in any one of claims 1 to 7, which is characterized by comprising the following steps:
s1, feeding the components into an internal mixer together according to a ratio, and internally mixing for 20-40 min at 130-160 ℃;
s2, pouring the black melt resin mass into a double-shaft tearing machine by using a tipping device, cooling the melt, synchronously tearing and crushing, conveying the crushed particles to a parallel co-rotating double-screw extruder for extrusion granulation, and obtaining the black color master batch special for the polyethylene water supply pipe.
9. Use of a masterbatch according to any one of claims 1 to 7 or prepared by the process of claim 8 in the preparation of a service pipe.
10. A polyethylene water supply pipe suitable for laser marking is characterized in that the polyethylene water supply pipe suitable for laser marking is prepared by using the color master batch of any one of claims 1 to 7 or the color master batch prepared by the method of claim 8;
the preparation method of the polyethylene water supply pipe suitable for laser marking comprises the following steps: adding 4-10% of the color master batch according to any one of claims 1-7 or the color master batch prepared by the method according to claim 8 into PE100 resin used for a water supply pipe, stirring for 2-6 min, uniformly mixing, and then extruding and shaping to obtain the color master batch.
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| CN112391003A (en) * | 2020-09-28 | 2021-02-23 | 中国石油化工股份有限公司 | Special resin with antibacterial property for polyethylene pipe and preparation method thereof |
| CN115260626A (en) * | 2022-06-30 | 2022-11-01 | 广东九彩新材料有限公司 | Blue-biased high-content pigment carbon black coloring polyethylene master batch and preparation method thereof |
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