CN114851671A - Paint-spraying-free intelligent healing automobile exterior trimming part and preparation method thereof - Google Patents
Paint-spraying-free intelligent healing automobile exterior trimming part and preparation method thereof Download PDFInfo
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- 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
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/584—Scratch resistance
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Abstract
The invention relates to a paint-spraying-free intelligent healing automobile exterior trimming part and a preparation method thereof, wherein the paint-spraying-free intelligent healing automobile exterior trimming part comprises the following steps: thermoplastic resin alloy layer, dyed layer, anti-scratch layer and intelligent healing layer. The invention integrates the functions of high gloss, intelligent healing, mechanical property and appearance color; can meet the requirements of automobile exterior decoration without a coating process, and can be directly applied as an exterior decoration product. The healing layer realizes intelligent healing based on a reversible covalent bond mechanism, and when the surface is scratched, the scratched surface can be heated by hot air at the temperature of 110-140 ℃ for 10-60 min, so that the intelligent healing crosslinking reaction of the surface layer is stimulated, and the effective healing of the surface scratch is realized.
Description
Technical Field
The invention belongs to the field of automobile exterior trim, and particularly relates to a paint-spraying-free intelligent healing automobile exterior trim and a preparation method thereof.
Background
The main structure of the traditional exterior trim of the motor vehicle is a metal plate, and along with the development of the trend of light weight of the automobile, part of parts or an automobile body are replaced by plastic injection molding parts or SMC composite materials, so that a certain weight reduction effect is achieved. The sheet metal automobile body exterior trimming part is adopted, the processes of stamping, welding, coating and final assembly are required, and the coating process with complex flow and serious pollution is avoided by adopting injection molding and SMC composite materials. As is well known, the coating process generally includes surface treatment, primer, basecoat, and topcoat processes. The single surface treatment process comprises oil removal, rust removal, dust removal, phosphating, polarization treatment and the like. The processes of priming paint, intermediate paint and finish paint all comprise links of high pollution and high energy consumption, such as spraying, baking and the like. The main defects of the existing coating process are that the process is multiple, the flow is long, the energy consumption is high, the pollution is high, and the hardware investment cost of the coating process is huge.
As the appearance surface, surface painting is required to have excellent appearance quality and also excellent weather resistance and scratch resistance. However, once the paint surface is scratched, the paint surface must be healed through a plurality of complicated coating processes, the healing period is long, and the quality of the healed paint surface is often lower than that of the original factory vehicle paint. The healing process has the defects of complex process, long period, high pollution and high cost.
Disclosure of Invention
The invention aims to solve the technical problem of providing a paint-spraying-free intelligent healing automobile exterior trimming part and a preparation method thereof, wherein the exterior trimming part integrates the functions of high gloss, intelligent healing, mechanical property and appearance color; can meet the requirements of automobile exterior decoration without a coating process, and can be directly applied as an exterior decoration product. The healing layer realizes intelligent healing based on a reversible covalent bond mechanism, and the intelligent healing crosslinking reaction of the surface layer is stimulated by heating the scratched surface through hot air, so that the effective healing of the surface scratch is realized.
The invention provides a paint-spraying-free intelligent healing automobile exterior trimming part, which comprises the following components in percentage by thickness:
the thermoplastic resin alloy layer comprises the following components in percentage by mass:
the coloring layer comprises the following components in percentage by mass:
the scratch-proof layer comprises the following components in percentage by mass:
the intelligent healing layer is an intelligent healing polyurethane thin layer.
The preparation method of the intelligent healing polyurethane thin layer comprises the following steps:
respectively preparing polyether polyimide and a polyurethane prepolymer containing furyl groups, dissolving two polymers with a molar ratio of 1.05:1 in DMF by adopting a one-step reaction method, fully stirring, continuously reacting for 2-3h at the temperature of 60 ℃ to obtain a target polymer, and concentrating and separating most of solvent to obtain a high-concentration polymer solution; then a thin layer casting machine with a devolatilization function is used for preparing the intelligent healing polyurethane thin layer.
The reaction equation of the intelligent healing polyurethane thin layer is as follows:
the invention also provides a preparation method of the paint-spraying-free intelligent healing automobile exterior composite board, which comprises the following steps:
according to the proportion, the material particles of the thermoplastic resin alloy, the coloring layer and the scratch-proof layer are prepared by a double-screw extruder, and then the composite board containing the thermoplastic resin alloy, the coloring layer, the scratch-proof layer and the intelligent healing layer is prepared by a multi-layer online continuous compounding process, so that the paint-spraying-free intelligent healing automobile exterior composite board is obtained.
The invention also provides a preparation method of the paint-spraying-free intelligent healing automobile exterior trimming part, which comprises the following steps:
and drying the composite board, and then obtaining the paint-spraying-free intelligent healing automobile exterior trimming part through full-automatic vacuum thermal forming and CNC procedures.
The invention also provides application of the paint-spraying-free intelligent healing automobile exterior trimming part in an automobile.
The thermoplastic resin alloy layer integrates the performance advantages of various high polymer materials, has excellent mechanical strength and impact resistance, and can be processed very conveniently by adopting a known forming process, such as thermoplastic forming.
The coloring layer in the invention has gorgeous color, and can freely and flexibly design colors, such as metallic silver, champagne gold and pearl flashing effect, because the material dispersion is needed in advance, the uniformity and stability of the color can be controlled to the maximum extent.
The scratch-proof layer is composed of raw materials with excellent gloss and high surface hardness, and after the scratch-proof layer is attached to the coloring layer, the three-dimensional aesthetic effect of a product can be effectively improved, and meanwhile, the scratch-proof layer has the characteristic of high surface hardness, and the damage of external force to an internal base material can be effectively avoided.
The intelligent healing layer is composed of high molecular resin (acrylic resin and polyurethanes) capable of realizing crack healing, and a healing functional group system of the resin comprises a disulfide bond, an acylhydrazone bond or a Diels-Alder reaction system based on a reversible covalent bond intelligent healing mechanism. Under the stimulation of specific external conditions, the crack can be effectively healed.
Advantageous effects
The invention integrates the functions of mechanical property, appearance color, high gloss and intelligent healing; the high gloss, uniform color, surface quality and mechanical property required by the automobile exterior can be achieved without a coating process, and the coating can be directly applied as an exterior product, so that the production cost and energy consumption are greatly reduced, and pollution emission is avoided. When the surface is scratched, the scratched surface can be heated by hot air at the temperature of 110-140 ℃ for 10-60 min, the intelligent healing crosslinking reaction of the surface layer is stimulated, the effective healing of the surface scratch is realized, and the maintenance cost is saved.
Drawings
FIG. 1 is a gloss comparison of examples and comparative examples;
FIGS. 2 and 3 are graphs comparing the scratch residual depth with heating time for examples and comparative examples;
FIGS. 4 and 5 are graphs comparing the scratch residual length with heating time for examples and comparative examples;
fig. 6 is a photograph showing variations in scratches according to example 1.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Preparation of the compositions (the following composition components are all examples, and the actual production process includes and is not limited to the specific components described below)
1. The thermoplastic resin alloy layer is a mixture of branched polycarbonate (branched PC), linear polycarbonate (linear PC), acrylonitrile-butadiene-styrene copolymer (ABS), organosilicon/acrylic acid copolymer with a core-shell structure, titanium dioxide, silicon-containing polycarbonate copolymer, flaky inorganic mineral, ultraviolet absorbent, antioxidant, lubricant, organic toner and inorganic toner; the raw materials are mixed and extruded and granulated by a double-screw extruder to prepare the Compound A.
Preferred ratios (in mass fraction):
mitsubishi chemical
M7027BF 18.09％
Mitsubishi chemical Ipiplon TM S-1000R 20％
High-bridged petrochemical ABS 351330%
Mitsubishi yang S-20305%
Sabic
EXL9330 20％
5000 meshes of talcum powder 5%
Basf TINUVIN 234 0.3％
Basf Irganox 1010 0.3％
0.3 percent of lubricant EBS
Dupont titanium dioxide R1031%
Ultramarine blue 0.01%
2. The coloring layer is a mixture of polymethyl methacrylate, a core-shell type impact modifier, an antioxidant, a lubricant, a hindered amine light stabilizer, an ultraviolet absorbent, titanium dioxide, organic toner and effect powder. The raw materials are mixed and then extruded and granulated by a double-screw extruder. Named Compound B.
Preferred ratios (in mass fraction):
mitsubishi VH 600191.3%
5 percent of core-shell type impact modifier
Basf TINUVIN 234 0.3％
Basf TINUVIN 770 0.3％
Basf Irganox 1010 0.3％
0.3 percent of lubricant EBS
Dupont titanium dioxide R1031%
0.5 percent of effect powder
1 percent of inorganic ultramarine
3. The scratch-proof layer is a mixture of polymethyl methacrylate resin, an antioxidant, a lubricant, a hindered amine light stabilizer, an ultraviolet absorbent, organic toner and inorganic toner. The raw materials are mixed and then extruded and granulated by a double-screw extruder. Named Compound C.
Preferred ratios (in mass fraction):
mitsubishi VH 600198.5%
Basf TINUVIN 234 0.3％
Basf TINUVIN 770 0.3％
Basf Irganox 1010 0.3％
0.3 percent of lubricant EBS
Dupont titanium pigment R1030.3%
2R blue 0.0001%
4. The intelligent healing layer is an intelligent healing material with temperature response, and after the surface of the intelligent healing layer is scratched, the material at the scratched part is triggered to perform intelligent healing reaction through external environment temperature stimulation. The polymer based on Diels-Alder reversible reaction is adopted, and the following synthesis and manufacturing process are adopted for obtaining:
the intelligent healing layer thin layer material is prepared by adopting a one-step synthesis process. Respectively preparing polyether polyimide and a polyurethane prepolymer containing furyl groups, and carrying out a one-step reaction on the polyether polyimide and the polyurethane prepolymer containing furyl groups prepared in advance according to a molar ratio of 1.05: dissolving the 1 in DMF, fully stirring, continuously reacting for 2-3h at the temperature of 60 ℃ to obtain a target polymer, concentrating and separating most of solvent to obtain a high-concentration polymer solution, and then preparing the intelligent healing polyurethane thin layer by a thin layer casting machine with a devolatilization function. Named Self-healing 1.
Preparation of composite boards
A composite panel having a total thickness of 5mm was prepared, and each functional layer was designed in accordance with the following thickness (mm).
TABLE 1 examples and comparative examples
Example 1
The composite board is produced by adopting a BREYER optical board intelligent manufacturing system, wherein the manufacturing system comprises an intelligent central control system, a ten-thousand-level dust-free workshop, a high-precision automatic feeding system, 3 combined single-screw extruders (the diameters of the screws are respectively 1#135mm, 2#120mm and 3#90mm), a three-runner in-mold composite die head with the width of 2100mm, a film sticking device, a mirror surface roller, an online flaw detection system, an online thickness measurement system, an online color difference monitoring system, an unqualified product automatic marking and screening system, a traction tempering system, a film covering and automatic packaging system.
Compound A, Compound B and Compound C are respectively added into 1#, 2#, 3# single screw extruders through automatic feeding systems to be melted and extruded, and are tightly compounded in a die, the thickness of the three layers is respectively adjusted to be 4.25mm, 0.3mm and 0.3mm through the feeding amount, and the extrusion temperature process is as follows: the temperature range of the No. 1 extruder is 160-240 ℃, the temperature range of the No. 2 extruder is 160-230 ℃, the temperature range of the No. 3 extruder is 160-230 ℃, the temperature range of the die is 180-220 ℃, and the temperature of the roller is 110-145 ℃. And (4) after compounding the melt, putting the melt into a roller for calendaring. The thickness and the surface evenness of the composite melt are adjusted through the mirror roller. The composite board is prepared by adopting Self-healing 1 with the thickness of 0.15mm through an online multilayer composite process. And then continuously passing through an online flaw detection device, a thickness measurement device and a color difference monitoring device, and when the detected flaws, thickness or color difference exceed the standard range of the product, automatically starting an unqualified product automatic marking system by a central control system, and carrying out laser spraying marking at the unqualified position. The defective products are selected in the automatic packaging system. And directly packaging, sealing and marking qualified products, and entering the next forming workshop.
Placing the composite board in a dehumidification drying box at the temperature of 90 ℃ for more than 6 hours, fully dewatering, then transferring to a Geiss full-automatic vacuum thermoforming machine system, automatically fixing the composite board to a clamp by the equipment, preheating and softening the composite board by using an infrared heating box for 60 seconds at the temperature of 70 ℃, then automatically moving the mould, vacuumizing for forming, cooling and demoulding. The whole process is completed by the operation of an automatic control system. And transferring the hot-formed semi-finished product into a CNC (computerized numerical control) machining center, and performing finish machining and component mounting combination according to a product design drawing to obtain an automobile exterior trim finished product.
Testing the glossiness of the surface of the exterior trimming part by adopting a BYK-Gardner BYK4563 triangular glossiness instrument, calculating the glossiness value of 20 degrees according to a test standard ISO 2813, and respectively taking 10 different positions;
testing the color difference value delta E of the surface of the exterior trimming part by adopting an Alice X-rite Ci7800 spectrophotometer, and respectively taking 10 different positions by adopting a CIE D65/10-degree test condition;
scribing 2 scratches with depth of 0.12mm and length of 5cm on the surface of the outer decoration by an art designing knife, heating the scratches by a 130 deg.C temperature control fan for 5min, 10min, 30min and 60min, respectively, and measuring the depth and length of the residual scratches.
Example 2
The composite board is produced by adopting a BREYER optical board intelligent manufacturing system, wherein the manufacturing system comprises an intelligent central control system, a ten-thousand-level dust-free workshop, a high-precision automatic feeding system, 3 combined single-screw extruders (the diameters of the screws are respectively 1#135mm, 2#120mm and 3#90mm), a three-runner in-mold composite die head with the width of 2100mm, a film sticking device, a mirror surface roller, an online flaw detection system, an online thickness measurement system, an online color difference monitoring system, an unqualified product automatic marking and screening system, a traction tempering system, a film covering and automatic packaging system.
Compound A, Compound B and Compound C are respectively added into 1#, 2#, and 3# single-screw extruders through automatic feeding systems to be melted and extruded, and are tightly compounded in a die, the thickness of the three layers is respectively adjusted to be 4.4mm, 0.3mm and 0.3mm through the feeding amount, and the extrusion temperature process is as follows: the temperature range of the No. 1 extruder is 160-240 ℃, the temperature range of the No. 2 extruder is 160-230 ℃, the temperature range of the No. 3 extruder is 160-230 ℃, the temperature range of the die is 180-220 ℃, and the temperature of the roller is 110-145 ℃. And (4) after compounding the melt, putting the melt into a roller for calendaring. The thickness and the surface evenness of the composite melt are adjusted through the mirror roller. And then continuously passing through an online flaw detection device, a thickness measurement device and a color difference monitoring device, and when the detected flaws, thickness or color difference exceed the standard range of the product, automatically starting an unqualified product automatic marking system by a central control system, and carrying out laser spraying marking at the unqualified position. The defective products are selected in the automatic packaging system. And directly packaging, sealing and marking qualified products, and entering the next forming workshop.
Placing the composite board in a dehumidification drying box at the temperature of 90 ℃ for more than 6 hours, fully dewatering, then transferring to a Geiss full-automatic vacuum thermoforming machine system, automatically fixing the composite board to a clamp by the equipment, preheating and softening the composite board by using an infrared heating box for 60 seconds at the temperature of 70 ℃, then automatically moving the mould, vacuumizing for forming, cooling and demoulding. The whole process is completed by the operation of an automatic control system. And transferring the hot-formed semi-finished product into a CNC (computerized numerical control) machining center, and performing finish machining and component mounting combination according to a product design drawing to obtain an automobile exterior trim finished product.
The test conditions were the same as in example 1.
Example 3
The composite board is produced by adopting a BREYER optical board intelligent manufacturing system, wherein the manufacturing system comprises an intelligent central control system, a ten-thousand-level dust-free workshop, a high-precision automatic feeding system, 3 combined single-screw extruders (the diameters of the screws are respectively 1#135mm, 2#120mm and 3#90mm), a three-runner in-mold composite die head with the width of 2100mm, a film sticking device, a mirror surface roller, an online flaw detection system, an online thickness measurement system, an online color difference monitoring system, an unqualified product automatic marking and screening system, a traction tempering system, a film covering and automatic packaging system.
Compound A and Compound B are respectively added into 1# and 2# single screw extruders through automatic feeding systems to be melted and extruded, tight compounding is carried out in a die, the thickness of two layers is adjusted to be 4.4mm and 0.45mm respectively through feeding amount, and the extrusion temperature process is as follows: the temperature range of the No. 1 extruder is 160-240 ℃, the temperature range of the No. 2 extruder is 160-230 ℃, the temperature range of the die is 180-220 ℃, and the temperature of the roller is 110-145 ℃. And (4) after compounding the melt, putting the melt into a roller for calendaring. The thickness and the surface evenness of the composite melt are adjusted through the mirror roller. The composite board is prepared by adopting Self-healing 1 with the thickness of 0.15mm through an online multilayer composite process. And then continuously passing through an online flaw detection device, a thickness measurement device and a color difference monitoring device, and when the detected flaws, thickness or color difference exceed the standard range of the product, automatically starting an unqualified product automatic marking system by a central control system, and carrying out laser spraying marking at the unqualified position. The defective products are selected in the automatic packaging system. And directly packaging, sealing and marking qualified products, and entering the next forming workshop.
Placing the composite board in a dehumidification drying box at the temperature of 90 ℃ for more than 6 hours, fully dewatering, then transferring to a Geiss full-automatic vacuum thermoforming machine system, automatically fixing the composite board to a clamp by the equipment, preheating and softening the composite board by using an infrared heating box for 60 seconds at the temperature of 70 ℃, then automatically moving the mould, vacuumizing for forming, cooling and demoulding. The whole process is completed by the operation of an automatic control system. And transferring the hot-formed semi-finished product into a CNC (computerized numerical control) machining center, and performing finish machining and component mounting combination according to a product design drawing to obtain an automobile exterior trim finished product.
The test conditions were the same as in example 1.
Example 4
The composite board is produced by adopting a BREYER optical board intelligent manufacturing system, wherein the manufacturing system comprises an intelligent central control system, a ten-thousand-level dust-free workshop, a high-precision automatic feeding system, 3 combined single-screw extruders (the diameters of the screws are respectively 1#135mm, 2#120mm and 3#90mm), a three-runner in-mold composite die head with the width of 2100mm, a film sticking device, a mirror surface roller, an online flaw detection system, an online thickness measurement system, an online color difference monitoring system, an unqualified product automatic marking and screening system, a traction tempering system, a film covering and automatic packaging system.
Compound A and Compound C are respectively added into 1# and 3# single screw extruders through automatic feeding systems to be melted and extruded, tight compounding is carried out in a die, the thickness of two layers is adjusted to be 4.25mm and 0.45mm respectively through feeding amount, and the extrusion temperature process is as follows: the temperature range of the No. 1 extruder is 160-240 ℃, the temperature range of the No. 2 extruder is 160-230 ℃, the temperature range of the No. 3 extruder is 160-230 ℃, the temperature range of the die is 180-220 ℃, and the temperature of the roller is 110-145 ℃. And (4) after compounding the melt, putting the melt into a roller for calendaring. The thickness and the surface evenness of the composite melt are adjusted through the mirror roller. The composite board is prepared by adopting Self-healing 1 with the thickness of 0.15mm through an online multilayer composite process. And then continuously passing through an online flaw detection device, a thickness measurement device and a color difference monitoring device, and when the detected flaws, thickness or color difference exceed the standard range of the product, automatically starting an unqualified product automatic marking system by a central control system, and carrying out laser spraying marking at the unqualified position. The defective products are selected in the automatic packaging system. And (5) directly packaging, sealing and marking qualified products, and entering the next forming workshop.
Placing the composite board in a dehumidification drying box at the temperature of 90 ℃ for more than 6 hours, fully dewatering, then transferring to a Geiss full-automatic vacuum thermoforming machine system, automatically fixing the composite board to a clamp by the equipment, preheating and softening the composite board by using an infrared heating box for 60 seconds at the temperature of 70 ℃, then automatically moving the mould, vacuumizing for forming, cooling and demoulding. The whole process is completed by the operation of an automatic control system. And transferring the hot-formed semi-finished product into a CNC (computerized numerical control) machining center, and performing finish machining and component mounting combination according to a product design drawing to obtain an automobile exterior trim finished product.
The test conditions were the same as in example 1.
Example 5
The composite board is produced by adopting a BREYER optical board intelligent manufacturing system, wherein the manufacturing system comprises an intelligent central control system, a ten-thousand-level dust-free workshop, a high-precision automatic feeding system, 3 combined single-screw extruders (the diameters of the screws are respectively 1#135mm, 2#120mm and 3#90mm), a three-runner in-mold composite die head with the width of 2100mm, a film sticking device, a mirror surface roller, an online flaw detection system, an online thickness measurement system, an online color difference monitoring system, an unqualified product automatic marking and screening system, a traction tempering system, a film covering and automatic packaging system.
Compound A is added into a 1# single screw extruder through an automatic feeding system for melt extrusion, tight compounding is carried out in a die, the thickness is respectively adjusted to be 4.85mm through the feeding amount, and the extrusion temperature process is as follows: the temperature range of the No. 1 extruder is 160-240 ℃, the temperature range of the die is 180-220 ℃, and the temperature of the roller is 110-145 ℃. And (4) after compounding the melt, putting the melt into a roller for calendaring. The thickness and the surface evenness of the composite melt are adjusted through the mirror roller. The composite board is prepared by adopting Self-healing 1 with the thickness of 0.15mm through an online multilayer composite process. And then continuously passing through an online flaw detection device, a thickness measurement device and a color difference monitoring device, and when the detected flaws, thickness or color difference exceed the standard range of the product, automatically starting an unqualified product automatic marking system by a central control system, and carrying out laser spraying marking at the unqualified position. The defective products are selected in the automatic packaging system. And directly packaging, sealing and marking qualified products, and entering the next forming workshop.
Placing the composite board in a dehumidification drying box at the temperature of 90 ℃ for more than 6 hours, fully dewatering, then transferring to a Geiss full-automatic vacuum thermoforming machine system, automatically fixing the composite board to a clamp by the equipment, preheating and softening the composite board by using an infrared heating box for 60 seconds at the temperature of 70 ℃, then automatically moving the mould, vacuumizing for forming, cooling and demoulding. The whole process is completed by the operation of an automatic control system. And transferring the hot-formed semi-finished product into a CNC (computerized numerical control) machining center, and performing finish machining and component mounting combination according to a product design drawing to obtain an automobile exterior trim finished product.
The test conditions were the same as in example 1.
Comparative example 1
The composite board is produced by adopting a BREYER optical board intelligent manufacturing system, wherein the manufacturing system comprises an intelligent central control system, a ten-thousand-level dust-free workshop, a high-precision automatic feeding system, 3 combined single-screw extruders (the diameters of the screws are respectively 1#135mm, 2#120mm and 3#90mm), a three-runner in-mold composite die head with the width of 2100mm, a film sticking device, a mirror surface roller, an online flaw detection system, an online thickness measurement system, an online color difference monitoring system, an unqualified product automatic marking and screening system, a traction tempering system, a film covering and automatic packaging system.
Compound A is added into a 1# single screw extruder through an automatic feeding system for melt extrusion, the thickness is adjusted to be 5mm through the feeding amount, and the extrusion temperature process is as follows: the temperature range of the No. 1 extruder is 160-240 ℃, the temperature range of the die is 180-220 ℃, and the temperature of the roller is 110-145 ℃. And (4) after compounding the melt, putting the melt into a roller for calendaring. The thickness and the surface evenness of the composite melt are adjusted through the mirror roller. And then continuously passing through an online flaw detection device, a thickness measurement device and a color difference monitoring device, and when the detected flaws, thickness or color difference exceed the standard range of the product, automatically starting an unqualified product automatic marking system by a central control system, and carrying out laser spraying marking at the unqualified position. The defective products are selected in the automatic packaging system. And directly packaging, sealing and marking qualified products, and entering the next forming workshop.
Placing the composite board in a dehumidification drying box at the temperature of 90 ℃ for more than 6 hours, fully dewatering, then transferring to a Geiss full-automatic vacuum thermoforming machine system, automatically fixing the composite board to a clamp by the equipment, preheating and softening the composite board by using an infrared heating box for 60 seconds at the temperature of 70 ℃, then automatically moving the mould, vacuumizing for forming, cooling and demoulding. The whole process is completed by the operation of an automatic control system. And transferring the hot-formed semi-finished product into a CNC (computerized numerical control) machining center, and performing finish machining and component mounting combination according to a product design drawing to obtain an automobile exterior trim finished product.
The test conditions were the same as in example 1.
Comparative example 2
A comparison test is carried out by using SMC (sheet molding compound) car body door plates of certain brands of car enterprises.
The test conditions were the same as in example 1.
Comparative example 3
A sheet metal car body door plate of a certain brand of car rabbet is used for carrying out a contrast test.
The test conditions were the same as in example 1.
Table 2 comparison of test data of different examples
As can be seen from the results of table 2 and fig. 1 to 6, the composite panel (example 1) prepared by the present invention has a high gloss appearance satisfying the exterior of the automobile without the surface spray process, and has more uniform color, Δ E of the surface of different regions is less than 0.1, and the scratch can be rapidly healed by the air gun heating process, thereby greatly saving the maintenance cost and time, and having excellent performance and cost advantages.
In example 2, comparative examples 1 to 3, in which the surface healing layer was not added, the surface scratches could not be healed by the heating process.
In example 3 without the scratch-resistant layer, the healing time of the surface scratch was prolonged, indicating that the scratch-resistant layer promotes healing. And simultaneously, the device can bear larger external force impact and scraping.
Example 4, in which no colored layer was added, had a worse color uniformity, Δ E of 0.5, indicating that the colored layer contributed to provide color uniformity of the entire product.
In both example 5 and comparative example 1, in which no coloring layer and no scratch-resistant layer were added, the 20 ° surface gloss was less than 60, and the high gloss surface requirement could not be satisfied.
Claims (9)
1. The utility model provides an intelligent healing car exterior trimming part of exempting from to spray paint which characterized in that: according to the thickness proportion, the method comprises the following steps:
2. the exterior trim according to claim 1, wherein: the thermoplastic resin alloy layer comprises the following components in percentage by mass:
3. the exterior trim according to claim 1, wherein: the coloring layer comprises the following components in percentage by mass:
4. the exterior trim according to claim 1, wherein: the scratch-proof layer comprises the following components in percentage by mass:
5. the exterior trim according to claim 1, wherein: the intelligent healing layer is realized based on a reversible covalent bond mechanism and is made of polyurethane.
6. The exterior trim according to claim 5, wherein: the preparation method of the intelligent healing polyurethane comprises the following steps:
respectively preparing polyether polyimide and a polyurethane prepolymer containing furyl groups, dissolving two polymers in DMF by adopting a one-step reaction method, fully stirring, continuously reacting for 2-3h at the temperature of 60 ℃, concentrating and separating most of solvent after obtaining a target polymer, and obtaining a high-concentration polymer solution; then a thin layer casting machine with a devolatilization function is used for preparing the intelligent healing polyurethane thin layer.
7. A preparation method of a paint-spraying-free intelligent healing automobile exterior composite board comprises the following steps:
according to the proportion of any one of claims 2 to 4, the material particles of the thermoplastic resin alloy, the coloring layer and the scratch-proof layer are prepared by a double-screw extruder, and then the composite plate containing the thermoplastic resin alloy, the coloring layer, the scratch-proof layer and the intelligent healing layer is prepared by a multi-layer online continuous composite process.
8. A preparation method of paint-spraying-free intelligent healing automobile exterior trimming parts comprises the following steps:
drying the composite board according to claim 7, and then obtaining the paint-free intelligent healing automobile exterior trimming part through a full-automatic vacuum thermoforming and CNC process.
9. Use of the paint-free intelligent healing automotive exterior trim part of claim 1 in an automobile.
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| US5885662A (en) * | 1997-01-31 | 1999-03-23 | Atoma International, Inc. | Decorative automotive interior trim articles with integral light stable polyurethane elastomer covering and process for making the same |
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