CN110294889A - A kind of Masterbatch is preparing the application in plastic products - Google Patents

A kind of Masterbatch is preparing the application in plastic products Download PDF

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Publication number
CN110294889A
CN110294889A CN201910659952.7A CN201910659952A CN110294889A CN 110294889 A CN110294889 A CN 110294889A CN 201910659952 A CN201910659952 A CN 201910659952A CN 110294889 A CN110294889 A CN 110294889A
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China
Prior art keywords
weight
pigment
parts
masterbatch
application according
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CN201910659952.7A
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Chinese (zh)
Inventor
常江
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Beijing Yiside Logistics Technology Co Ltd
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Beijing Yiside Logistics Technology Co Ltd
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Priority to CN201910659952.7A priority Critical patent/CN110294889A/en
Publication of CN110294889A publication Critical patent/CN110294889A/en
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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
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • 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
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2427/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon

Abstract

The present invention relates to color master-batch field, discloses a kind of Masterbatch and preparing the application in plastic products.The Masterbatch in starch master batch system have good compatibility and dispersibility.Masterbatch provided by the invention has good coloring and good toughness, can have good dispersibility in system, is suitable for blow-molded article, injection-molded item, extruded product etc..

Description

A kind of Masterbatch is preparing the application in plastic products
Technical field
The present invention relates to technical field of polymer materials, and in particular to a kind of Masterbatch is preparing answering in plastic products With.
Background technique
The full name of color masterbatch (Color Master Batch) is also color kind, is a kind of novel high polymer material Masterbatch Special coloring agent, also known as pigment preparation matter (PigmentPreparation).
Masterbatch is one kind by a high proportion of pigment or additive and thermoplastic resin, through plastics made of fine dispersion Toner, selected by resin to colorant have good wet and peptizaiton, and with by coloured material have it is good Compatibility.
Masterbatch has in extensive purposes, especially plastics, but is widely applied with color master-batch, to Masterbatch It proposes preferably to require.Such as it is more demanding for the stability and processing performance of Masterbatch during using color masterbatch, therefore, The auxiliary agent for needing to add various auxiliary agents in Masterbatch preparation process, and adding can dispersion performance and effect to color masterbatch pigment Have an adverse effect, and easily cause pigment in Masterbatch and be lost or change colour at high temperature, and subsequent product table obtained Face again can be uneven due to the discoloration or dispersion of Masterbatch, causes product white point occur, seriously affects the exterior quality of product；And show Some Masterbatch preparation methods and material respectively have its shortcoming again, for example, that there is raw material varieties is single, manufacturing method is thick It is rough, the problems such as properties of product are bad.
Summary of the invention
The purpose of the invention is to overcome drawbacks described above existing in the prior art, a kind of Masterbatch is provided and is moulded in preparation Application in material products, color masterbatch provided by the invention be used for plastic products when, show good mechanical property, dispersion performance with And color developing effect.
To achieve the goals above, the present invention provides a kind of Masterbatch to prepare the application in plastic products, the color Master batch contains pigment and carrier, and on the basis of the carrier of 100 parts by weight, the content of the pigment is 20-80 parts by weight.
Preferably, the carrier is polyethylene, polypropylene, polyvinyl chloride, polycarbonate, one in POE, ABS and EVA Kind is a variety of.
Preferably, the Masterbatch also contains processing aid.
Preferably, on the basis of the carrier of 100 parts by weight, the content of the processing aid is 20 parts by weight of 3-.
Preferably, the processing aid is selected from one of dispersing agent or additive or a variety of.
Preferably, the dispersing agent is selected from one of polyethylene low-molecular-weight wax, stearate and phosphate or a variety of.
Preferably, the additive is selected from one of fire retardant, brightener, antibacterial agent, antistatic agent and antioxidant Or it is a variety of.
Preferably, the partial size of the pigment is 1-30 μm.
Preferably, the pigment is organic pigment and/or inorganic pigment.
Preferably, the organic pigment is selected from that phthalocyanine is red, phthalocyanine blue, phthalocyanine green, everbright fast red, macromolecular are red, macromolecular One of Huang, permanent yellow, permanent violet, pigment yellow, pigment blue and azophloxine are a variety of.
Preferably, the inorganic pigment in cadmium red, cadmium yellow, titanium dioxide, carbon black, iron oxide red and iron oxide yellow one Kind is a variety of.
Preferably, the polyethylene is low density polyethylene (LDPE).
Preferably, the density of the POE is 0.85-1.20g/cm3And/or there is 20% crystallinity below.
Preferably, the carrier be one of polyethylene, polypropylene, polyvinyl chloride, polycarbonate, ABS and EVA or A variety of mixtures with POE.
Preferably, the content of POE is 30-70 weight % in the mixture.
Preferably, the partial size of the Masterbatch is 10-30 μm.
Masterbatch provided by the invention is preparing the application in plastic products, is particularly suitable for starch master batch, in starch mother There is good dispersibility in grain.
The present invention has the advantage that relative to existing product
1, cost of the invention is low, in addition to raw material documented in this patent, without adding other any raw materials, Neng Gouyou Effect ground reduces the economic cost of technique, and cooperates between used raw material, and the properties of product of acquisition are excellent；
2, POE elastomer of the invention, EVA elastomer, TPE elastomer be as main base elastomer body, with pigment plus Work auxiliary agent realizes extraordinary interaction, guarantees the uniformity of its product；
3, Masterbatch matter of the invention is soft, extension at break function admirable.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention will be described in detail by way of examples below.It is unless otherwise instructed, used in following embodiment Each material can be commercially available, and unless otherwise instructed, method used is the conventional method of this field.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
Contain in a first aspect, the present invention provides a kind of Masterbatch preparing the application in plastic products, the Masterbatch Pigment and carrier, on the basis of the carrier of 100 parts by weight, the content of the pigment is 20-80 parts by weight.
In order to guarantee the dispersion performance and color developing effect of color masterbatch, in the present invention, it is preferable that the carrier is polyethylene, poly- One of propylene, polyvinyl chloride, polycarbonate, POE, ABS and EVA are a variety of.
In order to guarantee the processability, stability and mechanical property of color masterbatch, in the present invention, it is preferable that the Masterbatch also contains There is processing aid.
Preferably, on the basis of the carrier of 100 parts by weight, the content of the processing aid is 20 parts by weight of 3-.
Preferably, the processing aid is selected from one of dispersing agent or additive or a variety of.
Preferably, the dispersing agent is selected from one of polyethylene low-molecular-weight wax, stearate, phosphate or a variety of.
Preferably, the additive is selected from one of fire retardant, brightener, antibacterial agent, antistatic agent and antioxidant Or it is a variety of.
For the content of above-mentioned additive, there is no particular limitation, can be selected or be answered according to specifically used demand Match, for its amount ratio, can be determined to obtain according to actual needs by those skilled in the art.
In order to further ensure the color developing effect of color masterbatch, in the present invention, it is preferable that the partial size of the pigment is 1-30 μm； It is highly preferred that the partial size of the pigment is 1-20 μm.
Preferably, the pigment is organic pigment and/or inorganic pigment.
Preferably, the organic pigment is selected from that phthalocyanine is red, phthalocyanine blue, phthalocyanine green, everbright fast red, macromolecular are red, macromolecular One of Huang, permanent yellow, permanent violet, pigment yellow, pigment blue and azophloxine are a variety of.
Preferably, the inorganic pigment in cadmium red, cadmium yellow, titanium dioxide, carbon black, iron oxide red and iron oxide yellow one Kind is a variety of.
Preferably, the polyethylene is low density polyethylene (LDPE).
Preferably, the density of the POE is 0.85-1.20g/cm3And/or there is 20% crystallinity below.
In order to further enhance the dispersion performance and color developing effect of color masterbatch, in the present invention, it is preferred to, the carrier is poly- The mixture of one of ethylene, polypropylene, polyvinyl chloride, polycarbonate, ABS and EVA or a variety of and POE.It such as can be 2 The mixture of kind component: the mixture of polyethylene and POE；The mixture of polypropylene and POE；The mixture of polyvinyl chloride and POE Perhaps the mixture of polycarbonate and POE or the mixture for 3 kinds of components, will not enumerate herein.
In the present invention, in order to further enhance the dispersion performance of color masterbatch and color developing effect, it is preferable that in the mixture The content of POE is 30-70 weight %.For the content of the POE of said mixture, when it is more than maximum level range, The dispersion performance and the synergy in terms of color developing effect for promoting color masterbatch are not substantially improved, when its content deficiency minimum content range When, dispersion performance and color developing effect for color masterbatch can have an adverse effect, can also according to properties of product and production it is comprehensive at Considering for this, adjusts accordingly.
In the present invention, the preparation method of Masterbatch can be prepared using the various methods of this field routine, in this hair In bright specific embodiment, Masterbatch after mixing each component through mixer stirring and single screw extrusion machine by melting, squeezing Out, pelletizing is made.
For the partial size of above-mentioned Masterbatch, there is no particular limitation, the actual conditions according to Masterbatch production equipment consider with And the convenience of later use is considered, in the method for the invention, it is preferable that the partial size of the Masterbatch is 10-30 μ m。
In the present invention, for said products, there is no particular limitation, such as can be blow-molded article, injection-molded item, extrusion molding Product or foaming product.
The present invention is described in detail below by embodiment, but the present invention is not limited in following embodiments.
All raw materials used in embodiment are commercially available unless otherwise specified.
Performance test methods are as follows:
Tensile strength, tearing strength, anti-Charpy impact, puncture strength test, heat seal strength: it is surveyed according to respective country standard Method for testing is tested.
Tensile property test: testing according to GB/T 1040.3-2006, and sample uses 2 types, length 150mm, and width is 15mm, test speed 200mm/min, the data of test sample vertical and horizontal both direction；
Tearing strength test: it is carried out by the regulation of GB/T 16578.2-2009.Test sample vertical and horizontal both direction Data；
Heat seal strength test:
Anti- Charpy impact: it is tested by GB/T 8809-2015 standard；
Puncture strength: it is tested by GB/T 10004-2008 standard；
Breaking unit of force is N, and tensile strength unit is MPa, and elongation at break unit is %, and anti-Charpy impact unit is J, Puncture strength unit is N.
Embodiment 1
20 weight % of POE, 14 parts by weight of pigment, 2 parts by weight of polyethylene wax, 1 parts by weight of antioxidant.
Embodiment 2
80 parts by weight of POE, 56 parts by weight of pigment, 8 parts by weight of polyethylene wax, 4 parts by weight of antioxidant.
Embodiment 3
60 parts by weight of POE, 36 parts by weight of pigment, 6 parts by weight of polyethylene wax, 3 parts by weight of antioxidant.
Embodiment 4
90 parts by weight of POE, 45 parts by weight of pigment, 3 parts by weight of polyethylene wax, 3 parts by weight of EBS, 3 parts by weight of antioxidant.
Embodiment 5
20 parts by weight of POE, 50 parts by weight of polyethylene, 50 parts by weight of pigment, 8 parts by weight of EBS, 3 parts by weight of antioxidant.
Embodiment 6
80 parts by weight of POE, 50 parts by weight of polyethylene, 40 parts by weight of pigment, 4 parts by weight of EBS, 2 parts by weight of antioxidant.
Embodiment 7
20 parts by weight of POE, EVA50 parts by weight, pigment red 149 parts by weight, 5 parts by weight of polyethylene wax, 3 parts by weight of EBS resist 3 parts by weight of oxygen agent.
Embodiment 8
80 parts by weight of POE, EVA50 parts by weight, 33 parts by weight of pigment, 3 parts by weight of polyethylene wax, 3 parts by weight of EBS resist 1 parts by weight of oxygen agent.
Embodiment 9
20 parts by weight of POE, 60 parts by weight of polyvinyl chloride, 42 parts by weight of pigment, 6 parts by weight of polyethylene wax, 4 weight of EBS Part, 2 parts by weight of antioxidant.
Embodiment 10
80 parts by weight of POE, 60 parts by weight of polyvinyl chloride, 35 parts by weight of pigment, 3 parts by weight of polyethylene wax, 3 weight of EBS Part, 1 parts by weight of antioxidant.
Comparative example 1
100 parts by weight of POE, 80 parts by weight of pigment, 4 parts by weight of EBS, 1 parts by weight of antioxidant.
Comparative example 2
40 parts by weight of POE, 60 parts by weight of polyethylene, 32 parts by weight of pigment, 6 parts by weight of polyethylene wax, 2 weight of antioxidant Part.
Prepare Masterbatch M1-M10 and D1-D2
Through mixer stirring and single screw extrusion machine after the Masterbatch component of embodiment 1-10 and comparative example 1-2 is mixed Melting squeezes out, pelletizing, obtains the Masterbatch, the specific method is as follows:
A. mixing
Above-mentioned carrier weighed by weight and processing aid are added in mixer, premix 5 minutes, are added by weight The amount weighed pigment of part discharges after continueing to mix 3 minutes.
B. it squeezes out
The mixed material of step A is moved into single screw extrusion machine, each warm area temperature of extruder is 85 DEG C, 105- DEG C, 125 DEG C, 135 DEG C, 120 DEG C, extruder die temperature is 125 DEG C.
C. it is granulated, packs
It by the material strip of extrusion after cooling water is cooling, is granulated through pelletizer, the particle length of granulation is no more than 3cm, is granulated After be cooled to room temperature packaging.
Prepare plastic product S1-S10 and SD1-SD2
Masterbatch M1-M10 and D1-D2 (15 parts by weight) obtained above and PE (25 parts by weight) are taken respectively, and starch is female Grain (Suzhou Hanfeng New Material Co., Ltd.) (60 parts by weight) prepares plastics in the following manner.
After raw material is mixed put into inflation film manufacturing machine blown film, be arranged each area's temperature of inflation film manufacturing machine are as follows: 140 DEG C of an area, 160 DEG C of 2nd area, Three 165 DEG C of areas, 165 DEG C of 4th area, 170 DEG C of 5th area, 170 DEG C of upper die head, 165 DEG C of lower die head, obtain plastic product S1-S10 with SD1-SD2。
Above-mentioned S1-S10 and SD1-SD2 is tested, test result sees below table 1.
Table 1
As above-mentioned table 1 it is found that using the film product containing starch made from starch Masterbatch of the invention, have excellent Good toughness and good intensity.
Starch master batch used in above-described embodiment, pigment are specially titanium dioxide/carbon black) density of POE is 0.89g/cm3 And/or there is 20% following crystallization degree.
The film toughness of S1-S10 is good, and elongation at break is greater than 300%, and anti-pendulum and puncture resistance are excellent；Add color Imperial mother, for the film surface of S1-S10 without white point, surface is smooth, is uniformly dispersed, and white point occurs in the surface SD1- SD2；S1-S10's is aobvious Color excellent effect, this low Masterbatch of addition content, starch base courier bag obscurity is excellent, and SD1-SD2 performance is poor.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to Protection scope of the present invention.

Claims (11)

1. a kind of Masterbatch is preparing the application in plastic products, which is characterized in that the Masterbatch contains pigment and carrier, with On the basis of the carrier of 100 parts by weight, the content of the pigment is 20-80 parts by weight.
2. application according to claim 1, wherein the carrier be polyethylene, polypropylene, polyvinyl chloride, polycarbonate, One of POE, ABS and EVA or a variety of.
3. application according to claim 1 or 2, wherein the Masterbatch also contains processing aid.
4. application according to claim 3, wherein on the basis of the carrier of 100 parts by weight, the processing aid Content is 3-20 parts by weight.
5. application according to claim 4, wherein the processing aid is selected from one of dispersing agent or additive or more Kind；
Preferably, the dispersing agent is selected from one of polyethylene low-molecular-weight wax, stearate and phosphate or a variety of；
Preferably, the additive is selected from one of fire retardant, brightener, antibacterial agent, antistatic agent and antioxidant or more Kind.
6. application described in any one of -5 according to claim 1, wherein the partial size of the pigment is 1-30 μm.
7. application according to claim 6, wherein the pigment is organic pigment and/or inorganic pigment；
Preferably, the organic pigment is selected from phthalocyanine is red, phthalocyanine blue, phthalocyanine green, everbright fast red, macromolecular is red, macromolecular is yellow, forever Gu one of Huang, permanent violet, pigment yellow, pigment blue and azophloxine are a variety of；
Preferably, the inorganic pigment be selected from one of cadmium red, cadmium yellow, titanium dioxide, carbon black, iron oxide red and iron oxide yellow or It is a variety of.
8. application according to claim 2, wherein the polyethylene is low density polyethylene (LDPE).
9. application according to claim 2, wherein the density of the POE is 0.85-1.20g/cm3And/or have 20% Crystallinity below.
10. application according to claim 8 or claim 9, wherein the carrier is polyethylene, polypropylene, polyvinyl chloride, poly- carbon The mixture of one of acid esters, ABS and EVA or a variety of and POE；
Preferably, the content of POE is 30-70 weight % in the mixture.
11. application according to claim 1, wherein the partial size of the Masterbatch is 10-30 μm.
CN201910659952.7A 2019-07-22 2019-07-22 A kind of Masterbatch is preparing the application in plastic products Withdrawn CN110294889A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114685910A (en) * 2022-03-18 2022-07-01 金发科技股份有限公司 Coloring agent, coloring material and preparation method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114685910A (en) * 2022-03-18 2022-07-01 金发科技股份有限公司 Coloring agent, coloring material and preparation method
CN114685910B (en) * 2022-03-18 2024-02-23 金发科技股份有限公司 Colorant, coloring material and preparation method

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Application publication date: 20191001