CN115637004B - High-adhesion scratch-resistant master batch as well as preparation method and application thereof - Google Patents
High-adhesion scratch-resistant master batch as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN115637004B CN115637004B CN202211331744.2A CN202211331744A CN115637004B CN 115637004 B CN115637004 B CN 115637004B CN 202211331744 A CN202211331744 A CN 202211331744A CN 115637004 B CN115637004 B CN 115637004B
- Authority
- CN
- China
- Prior art keywords
- parts
- hollow glass
- master batch
- scratch
- glass beads
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 39
- 230000003678 scratch resistant effect Effects 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000011521 glass Substances 0.000 claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011324 bead Substances 0.000 claims abstract description 46
- 239000010439 graphite Substances 0.000 claims abstract description 41
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 41
- 239000004743 Polypropylene Substances 0.000 claims abstract description 40
- -1 polypropylene Polymers 0.000 claims abstract description 40
- 229920001155 polypropylene Polymers 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000853 adhesive Substances 0.000 claims abstract description 9
- 230000001070 adhesive effect Effects 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 16
- 238000001125 extrusion Methods 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 8
- 239000012745 toughening agent Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 239000004005 microsphere Substances 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 39
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 23
- 239000003973 paint Substances 0.000 description 14
- 238000005520 cutting process Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a high-adhesion scratch-resistant master batch, and a preparation method and application thereof. The high-adhesion scratch-resistant master batch comprises the following components in parts by weight: 40-60 parts of polypropylene, 10-40 parts of crystalline flake graphite and 10-40 parts of hollow glass beads; the true density of the hollow glass beads is 0.35-0.60 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The carbon content of the flake graphite is more than or equal to 95 percent. According to the invention, through the interaction of the flake graphite and the hollow glass beads, the integrity of the hollow glass beads can be protected, so that the adhesive force is improved, and meanwhile, the flake graphite can better act on the surface of a material under the action of the hollow glass beads, so that the scratch resistance is remarkably improved. In addition, the raw materials selected in the invention are convenient and easy to obtain, and the production process is simple and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a high-adhesion scratch-resistant master batch, and a preparation method and application thereof.
Background
Among automobile parts, polypropylene materials are widely used in various systems such as bumpers, dashboards, door panels and the like. In many SUV vehicles, exterior trim pieces exist in combination with exterior trim bare pieces and spray coated pieces. With the development of spraying technology, automobile parts gradually develop to integration, and after some parts are integrally formed, part areas are sprayed, and part areas are directly exposed, so that the sprayed parts are required to have good spraying performance, and the exposed parts have excellent scratch resistance. In the existing scratch-resistant polypropylene material, a small molecular auxiliary agent is generally added into a system and migrates to the surface of the material to form a lubricating layer, so that the scratch-resistant effect is achieved. However, the formation of small molecules in the lubricant layer may instead form stress defects between the paint and the polypropylene, resulting in a reduced spray adhesion.
Patent document CN111234387a discloses a method for preparing modified scratch resistant agents to obtain scratch resistant, low-fogging polypropylene materials, which involves a chain extension reaction, is relatively complex in process, and does not involve adhesion between the material and the paint. Patent document CN113789012a achieves high adhesion performance by adding a small molecule capturing agent and a dyne value enhancing agent to a polypropylene and glass fiber system, and can meet performance requirements of automobile host factories, but the scheme does not consider scratch resistance of materials. Therefore, there is still a need in the art to develop a scratch-resistant polypropylene material with simple preparation and high adhesion.
Disclosure of Invention
The invention aims to provide a scratch-resistant master batch with high adhesive force, and a preparation method and application thereof. The polypropylene material prepared from the high-adhesion scratch-resistant master batch has higher paint adhesion and scratch resistance.
In order to achieve the above purpose, the present invention adopts the following technical scheme: the high-adhesion scratch-resistant master batch comprises the following components in parts by weight: 40-60 parts of polypropylene, 10-40 parts of crystalline flake graphite and 10-40 parts of hollow glass beads;
the true density of the hollow glass beads is 0.35-0.60 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The carbon content of the flake graphite is more than or equal to 95 percent.
Preferably, the high-adhesion scratch-resistant master batch comprises the following components in parts by weight: 45-50 parts of polypropylene, 25-30 parts of crystalline flake graphite and 20-25 parts of hollow glass beads.
Preferably, the true density of the hollow glass beads is between 0.45 and 0.50g/cm 3 。
The preparation method of the high-adhesion scratch-resistant master batch comprises the following steps: and (3) carrying out melt blending, extrusion, granulation, drying and cooling on the polypropylene, the flake graphite and the hollow glass beads to obtain the high-adhesion scratch-resistant master batch.
Preferably, the extrusion temperature is 190-230 ℃.
The polypropylene composition comprises the following components in parts by weight:
60-80 parts of polypropylene, 4-10 parts of the high-adhesion scratch-resistant master batch, 10-20 parts of a toughening agent, 10-20 parts of a filler and 1-3 parts of other auxiliary agents.
Preferably, the polypropylene composition comprises at least one of the following (1) to (3):
(1) The toughening agent includes one or more of POE, EVA, SEBS, EPDM;
(2) The filler comprises one or more of talcum powder, calcium carbonate, mica, wollastonite, whisker and barium sulfate;
(3) The other auxiliary agents comprise an antioxidant (such as an antioxidant 1010, an antioxidant 168 and the like), a toner (such as carbon black and the like) and the like which are commonly used in the field.
A method for preparing the polypropylene composition, comprising the steps of:
the polypropylene, the toughening agent, the filler, the scratch-resistant master batch with high adhesive force and other auxiliary agents are mixed, and the polypropylene composition is prepared through melt extrusion, granulation, drying and cooling.
Preferably, the melt extrusion temperature is 190-230 ℃.
An application of the high-adhesion scratch-resistant master batch in preparing automobile parts (such as bumpers, instrument panels and the like) is provided.
In the present invention, the hollow glass microspheres have a density lower than that of the polypropylene material (about 0.90g/cm 3 ) Under the melt state, the density difference between the hollow glass beads and the polypropylene generates larger buoyancy, so that the hollow glass beads float to the surface of a workpiece, and a large number of hydroxyl groups are arranged on the surface of the hollow glass beads, thereby causing enrichment of surface hydroxyl groups. The hydroxyl groups on the surface can strengthen the wetting of the paint on the nonpolar polypropylene material on the one hand, and on the other hand, the hydroxyl groups can have intermolecular actions with some components in the paint, so that the hollow glass beads can realize the effect of riveting the paint and the polypropylene material.
According to the invention, the flake graphite and the hollow glass beads are prepared into master batches in advance, so that the contact opportunity of the flake graphite and the hollow glass beads can be greatly increased, and the multiple synergistic effect of the flake graphite and the hollow glass beads is exerted. The flake graphite has good lubricity, so that on one hand, the hollow glass beads can be protected from being cut off by strong shear, the low density of the hollow glass is ensured, and the high adhesive force of the material is further ensured; on the other hand, the lubricity of the flake graphite can also bring better scratch resistance. In addition, the hollow glass beads move to the surface with the crystalline flake graphite contacted with the hollow glass beads under the driving of buoyancy, so that the scratch performance is improved, the hollow glass beads floating to the surface can exert a ball effect, and the scratch resistance of the material is improved.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, through the interaction of the flake graphite and the hollow glass beads, the integrity of the hollow glass beads can be protected, so that the adhesive force is improved, and meanwhile, the flake graphite can better act on the surface of a material under the action of the hollow glass beads, so that the scratch resistance is remarkably improved.
(2) The raw materials selected in the invention are convenient and easy to obtain, and the production process is simple and is suitable for large-scale production.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples and comparative examples, the experimental methods used were conventional methods unless otherwise specified, and the toughening agent, filler and other auxiliary agents were all commercially available and the same was used in parallel experiments.
The carbon content testing method of the flake graphite comprises the following steps: 0.5g of flake graphite powder is weighed, the original weight of the powder is measured to be 0.1mg, the powder is placed in a quartz boat with constant weight, the temperature is kept constant for 1h at about 105 ℃, the powder is cooled to room temperature in a dryer, the total weight m2 of the flake graphite powder and the quartz boat is measured, the quartz boat containing the flake graphite is placed in a pyrolysis furnace with nitrogen gas at 950 ℃ for 30min, the powder is taken out after being treated, the powder is cooled to room temperature in the dryer, and the total weight m3 of residual ash and the quartz boat is measured. Carbon content of flake graphite= (m 2-m 3)/m 1.
The raw materials used in the examples and comparative examples are described in Table 1.
TABLE 1
High-adhesion scratch-resistant master batch and preparation method thereof
The components and parts by weight of the high adhesion scratch resistant master batch are shown in Table 2.
The preparation method of the high-adhesion scratch-resistant master batch comprises the following steps: mixing polypropylene, crystalline flake graphite and hollow glass beads, mixing for 1 minute at 50rpm, adding into a single screw extruder, carrying out melt blending, extrusion, granulation, drying and cooling to obtain the high-adhesion scratch-resistant master batch. Wherein the extrusion temperature of the single screw extruder is 200 ℃.
TABLE 2 masterbatch component amounts (parts by weight)
Polypropylene composition and preparation method thereof
The polypropylene compositions of examples 1 to 10 and comparative examples 1 to 12 were prepared as shown in tables 3 to 4 in terms of components and parts by weight.
The preparation method of the polypropylene compositions of examples 1 to 10 and comparative examples 1 to 12 comprises the following steps:
mixing polypropylene, a toughening agent, a filler, the high-adhesion scratch-resistant master batch and other auxiliary agents, mixing for 1 minute at 50rpm, adding into a double-screw extruder, and carrying out melt extrusion, granulation, drying and cooling to obtain the polypropylene composition. Wherein the melt extrusion temperature was 210 ℃.
Table 3 amounts of the components (parts by weight) in the examples
Table 4 amounts of the components (parts by weight) in the comparative examples
Performance testing
The polypropylene compositions prepared in examples 1 to 10 and comparative examples 1 to 12 were subjected to scratch resistance and paint adhesion tests, the specific test methods and standards are as follows, and the results of the performance tests are shown in Table 5.
Paint adhesion was measured using GB/T9286-1998 and was differentiated by the proportion of coating drop after paint-cross-hatch-glue, the rating obtained being of the order 0-5, with 0 being the best, 5 being the worst, and customers generally requiring adhesion up to 0. The concrete expression is as follows:
0 level, the cutting edge is completely smooth, and 1 lattice falling does not exist;
1 grade, a little coating is dropped at the intersection of the incisions, but the cross cutting area is affected and cannot be obviously more than 5%;
2, coating is peeled off at the intersection of the incisions and/or along the edges of the incisions, wherein the affected intersection cutting area is obviously more than 5 percent, but not more than 15 percent;
stage 3, coating is peeled off with big fragments along the cutting edge part or all, and/or is peeled off on different parts of the grid part or all, the affected cross cutting area is obviously more than 15 percent, but not obviously more than 35 percent;
stage 4, coating falling off along the large fragments of the cutting edge and/or partial or complete falling off at some places, wherein the affected cross cutting area is obviously more than 35 percent, but not obviously more than 65 percent;
grade 5, degree of exfoliation exceeding grade 4.
The scratch resistance test method comprises the following steps: and (3) carrying out scratch resistance test on the injection-molded Ford Stucco leather pattern plate by adopting a cross scratch instrument, wherein the scratch load is 10N. The scratch resistance of the material is judged according to the color difference value delta L before and after scratch, and the lower the delta L value is, the harder the scratch is found, and the better the scratch resistance is. For scratch resistant materials, it is generally desirable that the Δl values of the material before and after scratching be below 1.5.
TABLE 5 Performance test results
As can be seen from the data in Table 4, the polypropylene composition prepared in the examples of the present invention has good adhesion and scratch resistance. Therefore, the invention proves that the adhesion and scratch resistance of the polypropylene composition can be effectively improved by preparing the hollow glass microspheres and the crystalline flake graphite into the master batch and adding the master batch into the polypropylene composition, wherein the adhesion grade can be 0 grade, and the scratch color difference delta L can be kept within the range of 0.32-0.88.
In comparative example 1, no high-adhesion scratch-resistant master batch was added, and the adhesion of the obtained material was very low (grade 3), and the scratch resistance was very poor (scratch color difference Δl > 6).
The carbon content of the crystalline flake graphite used in comparative example 2 is less than 95%, the spray adhesion of the obtained material is low (adhesion grade 2), and scratch resistance cannot meet the customer requirements (DeltaL > 1.5). The method is characterized in that the crystalline flake graphite with lower carbon content has lower purity and cannot effectively protect the hollow glass beads, so that the synergistic effect of the crystalline flake graphite and the hollow glass beads on the spraying adhesive force and scratch resistance is damaged to a certain extent.
The density of the hollow glass beads in the comparative example 3 is low, and the synergistic effect of the crystalline flake graphite and the hollow glass beads is obviously destroyed, so that the adhesive force is obviously reduced (grade 3), and the scratch resistance can not meet the requirements of customers (the scratch color difference value DeltaL is more than 1.5); in comparative example 4, the density of the hollow glass beads was high, so that the floating action of the hollow glass beads was also adversely affected, and although the paint adhesion and scratch resistance were remarkably improved as compared with those of comparative example 1, the paint adhesion (grade 2) and scratch resistance (scratch color difference DeltaL > 1.5) still failed to meet the customer's requirements.
The hollow glass beads in the high-adhesion scratch-resistant master batch of the comparative example 5 are few, so that the hollow glass beads which can float up to the surface are few, the adhesion of the material is low, and meanwhile, the scale graphite which floats up to the surface along with the hollow glass beads is less, and the scratch resistance of the material is also poor; the master batch in comparative example 6 has less crystalline flake graphite and cannot effectively protect the hollow glass microspheres, so that the adhesive force and scratch resistance of the material are poor.
Compared with comparative example 1, the scratch resistance of the material is improved, but the material still cannot meet the requirements of customers, and the lubricating effect of the flake graphite even worsens the paint adhesion of the material due to the lack of the riveting effect of the hollow glass microspheres with hydroxyl groups; compared with comparative example 1, the paint adhesion and scratch resistance of the material are not obviously improved by only adding the hollow glass beads into the master batch of comparative example 8, which indicates that the protection of crystalline flake graphite is lacking, and the hollow glass is difficult to produce the effect of improving the paint adhesion and the scratch resistance.
Comparative example 9 used a different amount of the commonly used small molecule lubricant erucamide, the resulting material had very poor spray adhesion (adhesion rating 5).
The high-adhesion scratch-resistant master batch of comparative example 10 was added to a small amount, so that the high-adhesion and scratch-resistant properties of the material were not fully exhibited. The high-adhesion scratch-resistant master batch of comparative example 11 is added more, so that the damage proportion of the hollow glass microspheres is increased, and the high-adhesion and scratch-resistant properties of the material are also negatively affected.
Comparative example 12 (equivalent addition amount is the same as example 2) did not directly add flake graphite and hollow glass beads to the material by the mastering process, and although the paint adhesion and scratch resistance of the resulting material were improved over comparative example 1 without the addition of flake graphite and hollow glass beads, the customer's needs were not met. The scratch resistance of the material obtained by adding the master batch prepared by the flake graphite alone (comparative example 7, deltaL=2.03) or adding the hollow glass beads without the master batch (comparative example 12, deltaL=2.02) is much lower than that of the material obtained by the flake graphite and the hollow glass beads after the master batch (example 2, deltaL=0.32). This is because, the lack of the driving of hollow glass beads, the limited movement capability of the flake graphite itself, and the limited ability of the flake graphite to provide scratch resistance on the surface of the material, is poor in scratch resistance. The scratch resistance of the obtained material is much poorer than the spraying performance of the material obtained after mother granulating the flake graphite and the hollow glass beads (example 2, adhesion grade 0 grade). This is because, due to the lack of protection of the flake graphite, the hollow glass beads are sheared in large amounts, so that they cannot float up to the surface of the material, and cannot provide sufficient hydroxyl groups for the spray adhesion, so that the spray adhesion of the material is poor.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (10)
1. The high-adhesion scratch-resistant master batch is characterized by comprising the following components in parts by weight: 40-60 parts of polypropylene, 10-40 parts of crystalline flake graphite and 10-40 parts of hollow glass beads;
the true density of the hollow glass beads is 0.35-0.60 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The carbon content of the flake graphite is more than or equal to 95 percent.
2. The high-adhesion scratch-resistant master batch according to claim 1, which comprises the following components in parts by weight: 45-50 parts of polypropylene, 25-30 parts of crystalline flake graphite and 20-25 parts of hollow glass beads.
3. The high adhesion scratch resistant masterbatch of claim 1 wherein said hollow glass microspheres have a true density of 0.45 to 0.50g/cm 3 。
4. A method for preparing the high-adhesion scratch-resistant master batch according to any one of claims 1 to 3, comprising the following steps: and (3) carrying out melt blending, extrusion, granulation, drying and cooling on the polypropylene, the flake graphite and the hollow glass beads to obtain the high-adhesion scratch-resistant master batch.
5. The process according to claim 4, wherein the extrusion temperature is 190 to 230 ℃.
6. The polypropylene composition is characterized by comprising the following components in parts by weight:
60-80 parts of polypropylene, 4-10 parts of the high-adhesion scratch-resistant master batch according to any one of claims 1-3, 10-20 parts of toughening agent, 10-20 parts of filler and 1-3 parts of other auxiliary agents.
7. The polypropylene composition according to claim 6, comprising at least one of the following (1) to (3):
(1) The toughening agent includes one or more of POE, EVA, SEBS, EPDM;
(2) The filler comprises one or more of talcum powder, calcium carbonate, mica, wollastonite, whisker and barium sulfate;
(3) The other auxiliary agent comprises at least one of an antioxidant and toner.
8. A process for the preparation of a polypropylene composition according to claim 6 or 7, comprising the steps of:
the polypropylene, the toughening agent, the filler, the scratch-resistant master batch with high adhesive force and other auxiliary agents are mixed, and the polypropylene composition is prepared through melt extrusion, granulation, drying and cooling.
9. The method of claim 8, wherein the melt extrusion temperature is 190 to 230 ℃.
10. The use of the high-adhesion scratch-resistant master batch according to any one of claims 1 to 3 for the production of automotive parts.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211331744.2A CN115637004B (en) | 2022-10-28 | 2022-10-28 | High-adhesion scratch-resistant master batch as well as preparation method and application thereof |
| PCT/CN2023/117120 WO2024087893A1 (en) | 2022-10-28 | 2023-09-05 | High-adhesion and scratch-resistant masterbatch, and preparation method therefor and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211331744.2A CN115637004B (en) | 2022-10-28 | 2022-10-28 | High-adhesion scratch-resistant master batch as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115637004A CN115637004A (en) | 2023-01-24 |
| CN115637004B true CN115637004B (en) | 2023-08-22 |
Family
ID=84946980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211331744.2A Active CN115637004B (en) | 2022-10-28 | 2022-10-28 | High-adhesion scratch-resistant master batch as well as preparation method and application thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN115637004B (en) |
| WO (1) | WO2024087893A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115637004B (en) * | 2022-10-28 | 2023-08-22 | 金发科技股份有限公司 | High-adhesion scratch-resistant master batch as well as preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087703A (en) * | 2019-12-26 | 2020-05-01 | 浙江普利特新材料有限公司 | High-brightness black scratch-resistant thin-walled polypropylene composite material and preparation method thereof |
| CN112457595A (en) * | 2020-12-08 | 2021-03-09 | 金发科技股份有限公司 | Polypropylene composition and preparation method thereof |
| CN112480551A (en) * | 2020-11-30 | 2021-03-12 | 金发科技股份有限公司 | Polypropylene composition and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6838804B2 (en) * | 2013-12-30 | 2021-03-03 | スリーエム イノベイティブ プロパティズ カンパニー | Polyolefin composition containing hollow glass microspheres and its usage |
| KR20170143260A (en) * | 2016-06-21 | 2017-12-29 | (주)켐코정밀 | Talc master batch resin composition with scratch resistant for interior or exterior material of automobile |
| CN107200947B (en) * | 2017-05-22 | 2019-08-20 | 成都新柯力化工科技有限公司 | A kind of graphene microchip conducting masterbatch and preparation method thereof |
| CN109135055A (en) * | 2018-07-27 | 2019-01-04 | 重庆会通科技有限公司 | A kind of low-density nickel plating hollow glass micropearl/polypropylene conductive composite material and preparation method |
| CN110437594B (en) * | 2019-08-26 | 2021-10-22 | 中山市鸿盛新材料有限公司 | Preparation method of golden pigment master batch, polypropylene composite material and preparation method thereof |
| CN112662054B (en) * | 2020-12-09 | 2022-10-21 | 武汉金发科技有限公司 | Polypropylene composite material and preparation method thereof |
| CN113862759B (en) * | 2021-10-29 | 2024-05-10 | 昆明理工大学 | Titanium-based gradient lead dioxide composite electrode material for copper electrodeposition and preparation method thereof |
| CN115637004B (en) * | 2022-10-28 | 2023-08-22 | 金发科技股份有限公司 | High-adhesion scratch-resistant master batch as well as preparation method and application thereof |
-
2022
- 2022-10-28 CN CN202211331744.2A patent/CN115637004B/en active Active
-
2023
- 2023-09-05 WO PCT/CN2023/117120 patent/WO2024087893A1/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087703A (en) * | 2019-12-26 | 2020-05-01 | 浙江普利特新材料有限公司 | High-brightness black scratch-resistant thin-walled polypropylene composite material and preparation method thereof |
| CN112480551A (en) * | 2020-11-30 | 2021-03-12 | 金发科技股份有限公司 | Polypropylene composition and preparation method thereof |
| CN112457595A (en) * | 2020-12-08 | 2021-03-09 | 金发科技股份有限公司 | Polypropylene composition and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 聚丙烯材料划伤耐久性能研究;李志平，卢先博，谭亚辉，陈延安，孙刚，杨波;合成材料老化与应用;第47卷(第4期);20-25 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115637004A (en) | 2023-01-24 |
| WO2024087893A1 (en) | 2024-05-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115637004B (en) | High-adhesion scratch-resistant master batch as well as preparation method and application thereof | |
| CN107501714B (en) | A kind of polypropene composition and preparation method thereof | |
| CN110791015B (en) | Special material for micro-foaming polypropylene for vehicles and preparation method and application thereof | |
| CN110951163B (en) | High-surface-tension low-density polypropylene composite material and preparation method thereof | |
| CN107629314A (en) | A kind of polypropene composition and preparation method thereof | |
| CN112457585A (en) | Polypropylene composition and preparation method thereof | |
| CN111286122A (en) | Polypropylene modified material | |
| CN111944237A (en) | Anti-virus and low-haze automotive interior polypropylene material and preparation method thereof | |
| KR102197586B1 (en) | A paint composition using oyster shell | |
| CN111995857B (en) | Antiviral vehicle-mounted entertainment panel PC/ABS alloy material and preparation method thereof | |
| CN109111712B (en) | Low-odor flame-retardant PC material and preparation method thereof | |
| CN110591335A (en) | High-flame-retardance low-smoke-toxicity weather-resistant cable sheath material and preparation method thereof | |
| CN108586944B (en) | Wollastonite/polypropylene composite material and preparation method thereof | |
| CN102559023B (en) | Scratch resistance waterborne polyurethane coating and preparation method thereof | |
| CN103030877B (en) | Impact-resistant polypropylene composite and preparation method thereof | |
| CN112409860A (en) | Decorative fluorocarbon powder coating and preparation process thereof | |
| CN112852249A (en) | Preparation and use methods of graphene polyether-ether-ketone anticorrosive high-temperature-resistant powder coating | |
| CN109554067A (en) | A kind of selfreparing powdery paints and its preparation and application | |
| CN114891301A (en) | Polypropylene composition and preparation method and application thereof | |
| KR20200037927A (en) | Coating Composition for Manufacturing Pre-Coated Metal Color Sheet of Fluorin Mat Type and Color Sheet Using the Same | |
| CN112321948B (en) | Silica aerogel-polypropylene light heat-insulating material and preparation method thereof | |
| CN112831132B (en) | Flame-retardant color master batch for XPS (extruded polystyrene) foaming insulation board and preparation method thereof | |
| JP2002146134A (en) | Polypropylene resin composition | |
| CN114736456A (en) | Polypropylene composition and preparation method and application thereof | |
| CN112679861A (en) | Flame-treatment-free polypropylene composition for automobile bumpers and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |