WO2019080456A1 - A modified plastic for laser welding and its preparation method - Google Patents

A modified plastic for laser welding and its preparation method

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Publication number
WO2019080456A1
WO2019080456A1 PCT/CN2018/081960 CN2018081960W WO2019080456A1 WO 2019080456 A1 WO2019080456 A1 WO 2019080456A1 CN 2018081960 W CN2018081960 W CN 2018081960W WO 2019080456 A1 WO2019080456 A1 WO 2019080456A1
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WIPO (PCT)
Prior art keywords
modified plastic
modified
laser
black toner
laser welding
Prior art date
Application number
PCT/CN2018/081960
Other languages
French (fr)
Inventor
Yujie QIN
Jun Wang
Original Assignee
Yanfeng Plastic Omnium Automotive Exterior Systems Co., Ltd.
Compagnie Plastic Omnium
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Yanfeng Plastic Omnium Automotive Exterior Systems Co., Ltd., Compagnie Plastic Omnium filed Critical Yanfeng Plastic Omnium Automotive Exterior Systems Co., Ltd.
Publication of WO2019080456A1 publication Critical patent/WO2019080456A1/en

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    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3437—Six-membered rings condensed with carbocyclic rings
    • 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
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08J3/201—Pre-melted polymers
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    • 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
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
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    • 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
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    • 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
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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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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—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
    • C08J2323/04—Homopolymers or copolymers of ethene
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—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
    • C08J2323/10—Homopolymers or copolymers of propene
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    • 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
    • C08J2423/10—Homopolymers or copolymers of propene
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    • C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
    • C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

Definitions

  • the invention relates to the field of materials, and more particularly, to a modified plastic that can be used for laser welding and its preparation method.
  • laser welding is a technology that makes thermoplastic sheets, films, or molded parts to bond together by melting plastic contact surfaces through the heat produced by a laser beam.
  • laser transmission welding The most commonly used form of laser welding is called “laser transmission welding. ”
  • the process of the technology of laser transmission welding consists in:first, clamping two plastic parts to be welded together; then, directing a laser beam in the short-wave infrared region to the site to be bonded, wherein, the laser beam passes through an upper-layer material and then is absorbed by a lower-layer material.
  • the energy of the laser is absorbed so that the temperature of the lower-layer material rises, melting the plastics of the upper layer and the lower layer, so as to achieve welding.
  • the upper-layer material may be transparent or colored, but must be capable of ensuring that sufficient laser passes through.
  • modified materials currently used for automobile interior and external trim parts generally present a black aspect.
  • Traditional black modified materials are, for example, modified PP (Polypropylene) and modified PC (Polycarbonate) , but those materials provide very low laser transmittance due to the use of carbon black as a pigment, thus resulting in the impossibility of applying laser welding to those materials.
  • aniline black begins to be added as a dye to a 30%glass fiber reinforced nylon. Although this material can achieve a selective transmittance of the near-infrared wavelength range, this type of dye cannot be used in automobile parts that will be exposed to the exterior for a long period of time due to its strong toxicity, impossibility to be applied to modified PP, and its high migration.
  • An objective of the invention is to provide a modified plastic that can be used for laser welding and its preparation method so as to solve the problem of the modified materials in the prior art with either low laser transmittance or strong toxicity and high migration.
  • the invention adopts the following technical solution:
  • a modified plastic is provided, wherein, the modified plastic is prepared by adding a perylene black toner into a laser-permeable matrix, the mass percentage of the perylene black toner in the modified plastic being 0.05-5%, and the modified material is permeable to laser in the range of 800-1100 nm.
  • the perylene black toner is a black perylene pigment.
  • the pigment is a black pigment different from carbon black, aniline black, black iron oxide, black chrome oxide, and tri-color pigment mixtures.
  • the inventor of the invention after significant experimenting, proposes to obtain a modified plastic by adding perylene black toner to a matrix permeable to laser. Not only does the pigment meet the basic coloring requirement and present low toxicity and migrability, but also it almost does not affect the laser transmittance of the matrix.
  • a modified plastic that can be used for laser welding is provided, and expanded application of laser welding in the field of automobile interior and exterior trim parts is achieved.
  • the mass percentage of the perylene black toner in the modified plastic is 0.05-2%.
  • the laser-permeable matrix can be any one commonly used in the field.
  • it mainly includes: modified Polypropylene (hereinafter referenced as PP) and modified Polycarbonate (hereinafter referenced as PC) .
  • the invention provides a modified plastic that can be used for laser welding, the modified plastic comprising, by percentage in mass, the following components: 48-98%PP, 0-25%flexibilizer, 0-50%glass fiber, and 0.05-2%perylene black toner, with the sum of the components being 100%.
  • the modified plastic comprises, by percentage in mass, the following components: 50-84%PP, 0-19%flexibilizer, 0-20%glass fiber, and 0.05-2%perylene black toner, with the sum of the components being 100%.
  • the modified plastic comprises, by percentage in mass, the following components: 50-80%PP, 0-19%flexibilizer, 0-20%glass fiber, and 0.05-2%perylene black toner, with the sum of the components being 100%.
  • the flexibilizer is selected from any one of an ethylene-propylene copolymer, an ethylene-butene copolymer, or an ethylene-octene copolymer.
  • the glass fiber is conventional round glass fiber or flat glass fiber.
  • the quantity of the glass fiber to be added can be selected, or no glass fiber is added, according to the performance requirements of the material.
  • the invention provides another modified plastic that can be used for laser welding, the modified plastic comprising, by percentage in mass, the following components: 20-80%PC, 15-75%modified resin, 0.1-5%interface compatilizer, and 0.05-5%perylene black toner, with the sum of the components being 100%.
  • the modified plastic comprises, by percentage in mass, the following components: 45-80%PC, 15-50%modified resin, 0.1-5%interface compatilizer, and 0.05-5%perylene black toner, with the sum of the components being 100%.
  • the modified plastic comprises, by percentage in mass, the following components: 45-65%PC, 30-50%modified resin, 0.1-5%interface compatilizer, and 0.1-0.2%perylene black toner, with the sum of the components being 100%.
  • the polycarbonate (PC) is a bisphenol A polycarbonate.
  • the modified resin can be any one of Acrylonitrile Butadiene Styrene (ABS) , Polyethylene Terephthalate (PET) , or Polybutylene Terephthalate (PBT) .
  • ABS Acrylonitrile Butadiene Styrene
  • PET Polyethylene Terephthalate
  • PBT Polybutylene Terephthalate
  • the polypropylene can be one type of polypropylene or a mixture of multiple types of polypropylene.
  • the melt flow indexes of different types of polypropylene are different. This is mainly for the matrix to have good processability and relatively balanced mechanical properties that meet the regulations of exterior trim part materials. It is also for the matrix to have a certain degree of laser transmittance.
  • ABS Acrylonitrile Butadiene Styrene
  • ABS can be an ABS polymerized via emulsion or bulk polymerization, in which the proporation of segments can be combined according to performance requirements.
  • the modified plastic further comprises at least one of an antioxidant, a lubricant, and a weatherability additive.
  • a preparation method of the modified plastic that can be used for laser welding as described above comprising the following steps: the perylene black toner and the matrix being introduced and mixed together in a high-speed mixer, then being melted, mixed and scatted in a twin-screw extruder under an extruding temperature of 200-250°C, and proceeding granulation by extruding so as to obtain final products.
  • the preparation method comprises the following steps: the materials other than the glass fiber being introduced and mixed together in a high-speed mixer, then being melted, mixed and scatted, together with the glass fiber fed laterally, in a twin-screw extruder, under an extruding temperature of 200-250°C, and proceeding granulation by extruding so as to obtain final products.
  • a modified plastic that can be used for laser welding is provided.
  • the inventiveness of the invention mainly lies in the facts: first, a laser-permeable matrix is provided through optimized formulation; and based on this laser permeability of the matrix itself, a perylene black toner that almost does not decrease the laser transmittance of the matrix is added, so as to obtain a modified plastic that can be used for laser welding.
  • the modified plastic overcome the lack of laser transmittance of conventional black materials, but also it can overcome the disadvantages of aniline-type dyes of being incapable to dye modified materials such as PP, prone to migration, of poor weatherability, and incapable to meet the performance and aspect requirements for long period exposure.
  • the invention provides a modified plastic that presents high laser transmittance, ease for dyeing, low migration, good weatherability, and accordance with the performance and aspect requirements for long term external exposure, thereby greatly expanding the applicability of laser welding technology in the field of automobile interior and exterior trim parts.
  • Figure 1 is a graph comparing the laser transmittance curves in the 400-1100 nm range of materials prepared according to, respectively, a preferred embodiment of the invention and a comparison embodiment.
  • the perylene black toner includes a series of perylene pigments, which can, respectively, meet requirements of different coloring and aging under light. All grades of the perylene black toner are suitable for the invention. Therefore, it should be understood that the grade of toner used in the following embodiments are merely for illustration and not for limitation.
  • Embodiment 2 consists in replacing the single grade of polypropylene with a mixture of two grades of polypropylene, which are respectively, a copolymer and a homopolymer of polypropylenes with different melt flow rate.
  • the combination of those two components in addition to conferring on the material a certain processability and mechanical performance, ensures that the matrix presents higher laser transmittance than Embodiment 1. Even the same content of the perylene black toner is added, its laser transmittance is still higher than that of Embodiment 1.
  • Embodiment 4 it can be seen from comparing Embodiment 4 with Embodiment 3 that, the addition of the perylene pigment does not result in a substantial decrease of the transmittance of the matrix as conventional carbon black does, although with the increase of the quantity of the perylene pigment added, the transmittance tends to decrease.
  • the granules produced by the granulation in the examples above are molded by injection into sample sheets of 2 mm thickness under the same molding conditions.
  • the transmittance of the sample sheets in the 450-1100 nm wavelength range is tested by using the professional color measurement spectrophotometer -Hunterlab Ultrascan PRO. The results are as shown in Figure 1.
  • the modified plastics obtained by the invention such as flexibilized polypropylene (Embodiments 2, 3, and 4) , glass-fiber-reinforced polypropylene (Embodiment 5) , PC+ABS (Embodiment 6) , and PC+PBT (Embodiment 7) , present relatively good transmittance in the laser emission wavelength range of 800-1100 nm, and can meet the requirements of laser welding.
  • the material obtained by using carbon black presents almost zero transmittance in the laser emission wavelength range of 800-1100 nm, which is significantly lower than that of the modified plastics obtained by using the perylene black toner (Embodiments 1, 2, 3, 4, and 5) ;
  • the material obtained by using the conventional organic azo dye presents a certain degree of transmittance in the laser emission wavelength range of 800-1100 nm, but it is also significantly lower than that of the modified plastic obtained by using the perylene black toner (Embodiment 6) .
  • the modified plastic according to the invention by adding a perylene black toner into the matrix, is endowed with not only very good transmittance in the laser emission wavelength range of 800-1100 nm, but also accordance to the requirements of laser welding.
  • the modified polypropylene material can also meet the requirements of the SAE J 2527 irradiance standard of 2500KJ/m2, in conformance with the requirements of the service environment of automobile exterior trim parts.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Lining Or Joining Of Plastics Or The Like (AREA)
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Abstract

The invention provides a modified plastic that can be used for laser welding. The modified plastic is prepared by adding a perylene black toner to a matrix permeable to laser. The mass percentage of the perylene black toner in the modified plastic is 0.05-5%. The modified plastic is permeable to laser in the range of 800-1100 nm. The invention also provides a preparation method of the modified plastic that can be used for laser welding. According to the invention, a modified plastic that presents high laser transmittance, ease for dyeing, low migration, good weatherability, and accordance with the performance and aspect requirements for long term external exposure is provided, thereby greatly expanding the applicability of laser welding technology in the field of automobile interior and exterior trim parts.

Description

A modified plastic for laser welding and its preparation method
Technical Field of the Invention
The invention relates to the field of materials, and more particularly, to a modified plastic that can be used for laser welding and its preparation method.
Background of the Invention
The technology of laser welding is a technology that makes thermoplastic sheets, films, or molded parts to bond together by melting plastic contact surfaces through the heat produced by a laser beam. The most commonly used form of laser welding is called “laser transmission welding. ”
The process of the technology of laser transmission welding consists in:first, clamping two plastic parts to be welded together; then, directing a laser beam in the short-wave infrared region to the site to be bonded, wherein, the laser beam passes through an upper-layer material and then is absorbed by a lower-layer material. The energy of the laser is absorbed so that the temperature of the lower-layer material rises, melting the plastics of the upper layer and the lower layer, so as to achieve welding. The upper-layer material may be transparent or colored, but must be capable of ensuring that sufficient laser passes through.
However, the modified materials currently used for automobile interior and external trim parts generally present a black aspect. Traditional black modified materials are, for example, modified PP (Polypropylene) and modified PC (Polycarbonate) , but those materials provide very low laser transmittance due to the use of carbon black as a  pigment, thus resulting in the impossibility of applying laser welding to those materials. In recent years, aniline black begins to be added as a dye to a 30%glass fiber reinforced nylon. Although this material can achieve a selective transmittance of the near-infrared wavelength range, this type of dye cannot be used in automobile parts that will be exposed to the exterior for a long period of time due to its strong toxicity, impossibility to be applied to modified PP, and its high migration.
The problems described above greatly limit the application of laser welding in the field of automobile interior and exterior trim parts. Therefore, it is very necessary to develop a black modified plastic with a certain degree of weatherability and a dye that is not prone to migration, which not only meets the requirements of performance and aspect of an automobile, but also presents a certain degree of transmittance of laser in the near-infrared wavelength range, thereby achieving expanded application of laser welding in the field of automobile interior and exterior trim parts.
Summary of the Invention
An objective of the invention is to provide a modified plastic that can be used for laser welding and its preparation method so as to solve the problem of the modified materials in the prior art with either low laser transmittance or strong toxicity and high migration.
To solve the above-described problem, the invention adopts the following technical solution:
According to a first aspect of the invention, a modified plastic is provided, wherein, the modified plastic is prepared by adding a perylene black toner into a laser-permeable matrix, the mass percentage of the perylene black toner in the modified plastic being 0.05-5%, and the  modified material is permeable to laser in the range of 800-1100 nm.
The perylene black toner is a black perylene pigment. For its specific structure, one can refer to the Chinese invention patent application ZL20058004522.8. The pigment is a black pigment different from carbon black, aniline black, black iron oxide, black chrome oxide, and tri-color pigment mixtures.
The inventor of the invention, after significant experimenting, proposes to obtain a modified plastic by adding perylene black toner to a matrix permeable to laser. Not only does the pigment meet the basic coloring requirement and present low toxicity and migrability, but also it almost does not affect the laser transmittance of the matrix. Thus, a modified plastic that can be used for laser welding is provided, and expanded application of laser welding in the field of automobile interior and exterior trim parts is achieved.
Particularly preferably, the mass percentage of the perylene black toner in the modified plastic is 0.05-2%.
The laser-permeable matrix can be any one commonly used in the field. Here, for example but without limitation, it mainly includes: modified Polypropylene (hereinafter referenced as PP) and modified Polycarbonate (hereinafter referenced as PC) .
Particularly preferably, the invention provides a modified plastic that can be used for laser welding, the modified plastic comprising, by percentage in mass, the following components: 48-98%PP, 0-25%flexibilizer, 0-50%glass fiber, and 0.05-2%perylene black toner, with the sum of the components being 100%.
Also preferably, the modified plastic comprises, by percentage in  mass, the following components: 50-84%PP, 0-19%flexibilizer, 0-20%glass fiber, and 0.05-2%perylene black toner, with the sum of the components being 100%.
Particularly preferably, the modified plastic comprises, by percentage in mass, the following components: 50-80%PP, 0-19%flexibilizer, 0-20%glass fiber, and 0.05-2%perylene black toner, with the sum of the components being 100%.
Preferably, the flexibilizer is selected from any one of an ethylene-propylene copolymer, an ethylene-butene copolymer, or an ethylene-octene copolymer.
The glass fiber is conventional round glass fiber or flat glass fiber. The quantity of the glass fiber to be added can be selected, or no glass fiber is added, according to the performance requirements of the material.
Preferably, the invention provides another modified plastic that can be used for laser welding, the modified plastic comprising, by percentage in mass, the following components: 20-80%PC, 15-75%modified resin, 0.1-5%interface compatilizer, and 0.05-5%perylene black toner, with the sum of the components being 100%.
Also preferably, the modified plastic comprises, by percentage in mass, the following components: 45-80%PC, 15-50%modified resin, 0.1-5%interface compatilizer, and 0.05-5%perylene black toner, with the sum of the components being 100%.
Particularly preferably, the modified plastic comprises, by percentage in mass, the following components: 45-65%PC, 30-50%modified resin, 0.1-5%interface compatilizer, and 0.1-0.2%perylene black toner, with the sum of the components being 100%.
Preferably, the polycarbonate (PC) is a bisphenol A polycarbonate.
The modified resin can be any one of Acrylonitrile Butadiene Styrene (ABS) , Polyethylene Terephthalate (PET) , or Polybutylene Terephthalate (PBT) .
The polypropylene can be one type of polypropylene or a mixture of multiple types of polypropylene. The melt flow indexes of different types of polypropylene are different. This is mainly for the matrix to have good processability and relatively balanced mechanical properties that meet the regulations of exterior trim part materials. It is also for the matrix to have a certain degree of laser transmittance.
The Acrylonitrile Butadiene Styrene (ABS) can be an ABS polymerized via emulsion or bulk polymerization, in which the proporation of segments can be combined according to performance requirements.
Preferably, the modified plastic further comprises at least one of an antioxidant, a lubricant, and a weatherability additive.
According to a second aspect of the invention, a preparation method of the modified plastic that can be used for laser welding as described above is further provided, the method comprising the following steps: the perylene black toner and the matrix being introduced and mixed together in a high-speed mixer, then being melted, mixed and scatted in a twin-screw extruder under an extruding temperature of 200-250℃, and proceeding granulation by extruding so as to obtain final products.
Preferably, in the case where the components of the modified plastic include glass fiber, the preparation method comprises the following steps: the materials other than the glass fiber being introduced and mixed  together in a high-speed mixer, then being melted, mixed and scatted, together with the glass fiber fed laterally, in a twin-screw extruder, under an extruding temperature of 200-250℃, and proceeding granulation by extruding so as to obtain final products.
According to the invention, a modified plastic that can be used for laser welding is provided. The inventiveness of the invention mainly lies in the facts: first, a laser-permeable matrix is provided through optimized formulation; and based on this laser permeability of the matrix itself, a perylene black toner that almost does not decrease the laser transmittance of the matrix is added, so as to obtain a modified plastic that can be used for laser welding. Not only can the modified plastic overcome the lack of laser transmittance of conventional black materials, but also it can overcome the disadvantages of aniline-type dyes of being incapable to dye modified materials such as PP, prone to migration, of poor weatherability, and incapable to meet the performance and aspect requirements for long period exposure.
In summary, the invention provides a modified plastic that presents high laser transmittance, ease for dyeing, low migration, good weatherability, and accordance with the performance and aspect requirements for long term external exposure, thereby greatly expanding the applicability of laser welding technology in the field of automobile interior and exterior trim parts.
Brief Description of the Drawings
Figure 1 is a graph comparing the laser transmittance curves in the 400-1100 nm range of materials prepared according to, respectively, a preferred embodiment of the invention and a comparison embodiment.
Detailed Description of the Invention
The invention is further described below in connection with specific embodiments. It should be understood that the following embodiments are used merely to illustrate the invention and not to limit the scope of the invention.
The perylene black toner includes a series of perylene pigments, which can, respectively, meet requirements of different coloring and aging under light. All grades of the perylene black toner are suitable for the invention. Therefore, it should be understood that the grade of toner used in the following embodiments are merely for illustration and not for limitation.
Embodiment 1
84 kg of polypropylene H9018, 15 kg of ethylene-octene copolymer 8137, 0.2 kg of perylene black toner L480, 0.3 kg of antioxidant 1010, 0.2 kg of a lubricant (of the stearic acid family) , and 0.3 kg of a weatherability additive, are melted, mixed, and scattered in a twin-screw extruder with a length/diameter ratio of 40: 1, under an extruding temperature of 200℃. The final product is obtained through granulation by extrusion.
Embodiment 2
54 kg of polypropylene K9017, 27 kg of polypropylene BX3900, 18 kg of ethylene-butene copolymer 7467, 0.2 kg of perylene black toner L480, 0.3 kg of antioxidant 1010, 0.2 kg of a lubricant (of the stearic acid family) , and 0.3 kg of a weatherability additive, are melted, mixed, and scattered in a twin-screw extruder with a length/diameter ratio of 40: 1, under an extruding temperature of 200℃. The final product is obtained through granulation by extrusion.
Based on Embodiment 1, Embodiment 2 consists in replacing the single grade of polypropylene with a mixture of two grades of polypropylene, which are respectively, a copolymer and a homopolymer of polypropylenes with different melt flow rate. The combination of those two components, in addition to conferring on the material a certain processability and mechanical performance, ensures that the matrix presents higher laser transmittance than Embodiment 1. Even the same content of the perylene black toner is added, its laser transmittance is still higher than that of Embodiment 1.
Embodiment 3
50 kg of polypropylene K9017, 30 kg of polypropylene BX3900, 19 kg of ethylene-butene copolymer 7467, 0.05 kg of perylene black toner L480, 0.3 kg of antioxidant 1010, 0.3 kg of a lubricant (of the stearic acid family) , and 0.35 kg of a weatherability additive, are melted, mixed, and scattered in a twin-screw extruder with a length/diameter ratio of 40: 1, under an extruding temperature of 200℃. The final product is obtained through granulation by extrusion.
Embodiment 4
50 kg of polypropylene K9017, 30 kg of polypropylene BX3900, 17 kg of ethylene-butene copolymer 7467, 2 kg of perylene black toner L480, 0.3 kg of antioxidant 1010, 0.3 kg of a lubricant (of the stearic acid family) , and 0.35 kg of a weatherability additive, are melted, mixed, and scattered in a twin-screw extruder with a length/diameter ratio of 40: 1, under an extruding temperature of 200℃. The final product is obtained through granulation by extrusion.
It can be seen from comparing Embodiment 4 with Embodiment 3 that, the addition of the perylene pigment does not result in a substantial  decrease of the transmittance of the matrix as conventional carbon black does, although with the increase of the quantity of the perylene pigment added, the transmittance tends to decrease.
Embodiment 5
78 kg of polypropylene EP548R, 0.5 kg of perylene black toner L480, 0.3 kg of antioxidant 1010, 0.2 kg of a lubricant (of the stearic acid family) , 0.3 kg of a weatherability additive, and 0.5 kg of an interface property modifier, after having been mixed at high speed, are melted, mixed, and scattered, together with 20 kg of glass fiber fed laterally, in a twin-screw extruder with a length/diameter ratio of 40: 1, under an extruding temperature of 200℃. The final product is obtained through granulation by extrusion.
Embodiment 6
45 kg of polycarbonate Lexan 141, 50 kg of ABS GP22, 4 kg of an interface compatilizer, 0.3 kg of antioxidant 1010, 0.5 kg of a lubricant, and 0.2 kg of perylene black toner S0084 are melted, mixed, and scattered in a twin-screw extruder with a length/diameter ratio of 35: 1, under an extruding temperature of 250℃. The final product is obtained through granulation by extrusion.
Embodiment 7
65 kg of polycarbonate Lexan 141, 30 kg of PBT GX121, 4 kg of an interface compatilizer, 0.3 kg of antioxidant 1010, 0.5 kg of a lubricant, and 0.1 kg of perylene black toner S0084 are melted, mixed, and scattered in a twin-screw extruder with a length/diameter ratio of 35: 1, under an extruding temperature of 250℃. The final product is obtained through granulation by extrusion.
Comparison Example 1
50 kg of PP K9017, 30 kg of PP BX3900, 19 kg of ethylene-butene copolymer 7467, 5 kg of perylene black toner L480, 0.3 kg of antioxidant 1010, 0.3 kg of a lubricant (of the stearic acid family) , and 0.35 kg of a weatherability additive, are melted, mixed, and scattered in a twin-screw extruder with a length/diameter ratio of 40: 1, under an extruding temperature of 200℃. The final product is obtained through granulation by extrusion.
Comparison Example 2
50 kg of PP K9017, 30 kg of PP BX3900, 19 kg of ethylene-butene copolymer 7467, 0.3 kg of antioxidant 1010, 0.3 kg of a lubricant (of the stearic acid family) , and 0.40 kg of a weatherability additive, are melted, mixed, and scattered in a twin-screw extruder with a length/diameter ratio of 40: 1, under an extruding temperature of 200℃. The final product is obtained through granulation by extrusion.
Comparison Example 3
84 kg of PP H9018, 15 kg of ethylene-octene copolymer 8137, 0.2 kg of carbon black, 0.3 kg of antioxidant 1010, 0.2 kg of a lubricant (of the stearic acid family) , and 0.3 kg of a weatherability additive, are melted, mixed, and scattered in a twin-screw extruder with a length/diameter ratio of 40: 1, under an extruding temperature of 200℃. The final product is obtained through granulation by extrusion.
Comparison Example 4
45 kg of PC Lexan 141, 50 kg of ABS GP22, 4 kg of an interface compatilizer, 0.3 kg of antioxidant 1010, 0.5 kg of a lubricant, and 0.2 kg  of a conventional organic azo dye are melted, mixed, and scattered in a twin-screw extruder with a length/diameter ratio of 35: 1, under an extruding temperature of 250℃. The final product is obtained through granulation by extrusion.
The granules produced by the granulation in the examples above are molded by injection into sample sheets of 2 mm thickness under the same molding conditions. The transmittance of the sample sheets in the 450-1100 nm wavelength range is tested by using the professional color measurement spectrophotometer -Hunterlab Ultrascan PRO. The results are as shown in Figure 1.
Among the examples, the modified plastics obtained by the invention, such as flexibilized polypropylene (Embodiments 2, 3, and 4) , glass-fiber-reinforced polypropylene (Embodiment 5) , PC+ABS (Embodiment 6) , and PC+PBT (Embodiment 7) , present relatively good transmittance in the laser emission wavelength range of 800-1100 nm, and can meet the requirements of laser welding. With the same matrix used: the material obtained by using carbon black (Comparison Example 3) presents almost zero transmittance in the laser emission wavelength range of 800-1100 nm, which is significantly lower than that of the modified plastics obtained by using the perylene black toner ( Embodiments  1, 2, 3, 4, and 5) ; the material obtained by using the conventional organic azo dye (Comparison Example 4) presents a certain degree of transmittance in the laser emission wavelength range of 800-1100 nm, but it is also significantly lower than that of the modified plastic obtained by using the perylene black toner (Embodiment 6) .
According to the invention, from Embodiments 3 and 4 and Comparison Examples 1, 2, and 3, it is not difficult to understand that the addition of the perylene black toner does not result in a substantial  decrease of the transmittance of the matrix as conventional carbon black does, although with the increase of the quantity of the perylene pigment added, the transmittance tends to decrease. Therefore, the optimal quantity to be added is within 2%.
Thus, it can be understood that, the modified plastic according to the invention, by adding a perylene black toner into the matrix, is endowed with not only very good transmittance in the laser emission wavelength range of 800-1100 nm, but also accordance to the requirements of laser welding. In particular, the modified polypropylene material can also meet the requirements of the SAE J 2527 irradiance standard of 2500KJ/m2, in conformance with the requirements of the service environment of automobile exterior trim parts.
What has been described above are merely preferred embodiments of the invention, and not used to limit the scope of the invention. The above-described embodiments of the invention can be further subject to various modifications. That is, all simple, equivalent modifications and embellishments made according to the claims and the specification of the invention application fall within the scope of protection claimed by the invention. What has not been described in the invention belongs to conventional technologies.

Claims (10)

  1. A modified plastic for laser welding, characterized in that, the modified plastic is prepared by adding a perylene black toner into a laser-permeable matrix, the mass percentage of the perylene black toner in the modified plastic being 0.05-5%, the modified material being permeable to laser in the range of 800-1100 nm.
  2. The modified plastic according to claim 1, wherein the laser-permeable matrix includes: modified polypropylene or modified polycarbonate.
  3. The modified plastic according to claim 2, wherein the modified plastic comprises, by percentage in mass, the following components: 48-98%polypropylene, 0-25%flexibilizer, 0-50%glass fiber, and 0.05-2%perylene black toner, with the sum of the components being 100%.
  4. The modified plastic according to claim 3, wherein the flexibilizer is selected from any one of an ethylene-propylene copolymer, an ethylene-butene copolymer, or an ethylene-octene copolymer.
  5. The modified plastic according to claim 2, wherein the modified plastic comprises, by percentage in mass, the following components: 20-80%polycarbonate, 15-75%modified resin, 0.1-5%interface compatilizer, and 0.05-5%perylene black toner, with the sum of the components being 100%.
  6. The modified plastic according to claim 5, wherein the polycarbonate is a bisphenol A polycarbonate.
  7. The modified plastic according to claim 5, wherein the modified  resin is any one of acrylonitrile butadiene styrene, polyethylene terephthalate, or polybutylene terephthalate.
  8. The modified plastic according to claim 3 or 5, wherein the modified plastic further comprises at least one of an antioxidant, a lubricant, and a weatherability additive.
  9. A preparation method of the modified plastic for laser welding according to any one of claims 1 to 8, characterized in that, the method comprises the following steps: the perylene black toner and the matrix being introduced and mixed together in a high-speed mixer, then being melted, mixed and scattered in a twin-screw extruder under an extruding temperature of 200-250℃, and proceeding granulation by extruding so as to finally obtain the modified plastic that can be used for laser welding, the modified plastic being permeable to laser in the range of 800-1100 nm.
  10. The preparation method according to claim 9, wherein when the components of the modified plastic include glass fiber, the preparation method comprises the following steps: the materials other than the glass fiber being introduced and mixed together in a high-speed mixer, then being melted, mixed and scattered, together with the glass fiber fed laterally, in a twin-screw extruder, under an extruding temperature of 200-250℃, and proceeding granulation by extruding so as to fianlly obtain the modified plastic that can be used for laser welding.
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CN113527845A (en) * 2021-07-06 2021-10-22 漯河医学高等专科学校 Full-biodegradable plastic component for laser welding
CN114350134A (en) * 2022-01-19 2022-04-15 上海金山锦湖日丽塑料有限公司 High-toughness transparent PC/PP resin composition and preparation method and application thereof
CN114456553A (en) * 2022-03-01 2022-05-10 上海聚威新材料股份有限公司 Anti-warping laser welding PC/PBT composite material and preparation method thereof
CN115109341A (en) * 2022-07-04 2022-09-27 广东圆融新材料有限公司 Laser-weldable polypropylene modified material and preparation method and application thereof
CN115490953A (en) * 2022-09-06 2022-12-20 烽火通信科技股份有限公司 Black polyolefin material and preparation method thereof
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CN113337109B (en) * 2021-06-07 2022-07-08 上海锦湖日丽塑料有限公司 Reinforced polyamide composition with high laser transmittance and low water absorption performance as well as preparation method and application thereof
CN113337109A (en) * 2021-06-07 2021-09-03 上海锦湖日丽塑料有限公司 Reinforced polyamide composition with high laser transmittance and low water absorption performance as well as preparation method and application thereof
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CN114350134B (en) * 2022-01-19 2023-10-17 上海金山锦湖日丽塑料有限公司 High-toughness transparent PC/PP resin composition, and preparation method and application thereof
CN114350134A (en) * 2022-01-19 2022-04-15 上海金山锦湖日丽塑料有限公司 High-toughness transparent PC/PP resin composition and preparation method and application thereof
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CN114456553B (en) * 2022-03-01 2024-01-19 上海聚威新材料股份有限公司 Anti-warp laser welding PC/PBT composite material and preparation method thereof
CN115109341A (en) * 2022-07-04 2022-09-27 广东圆融新材料有限公司 Laser-weldable polypropylene modified material and preparation method and application thereof
CN115109341B (en) * 2022-07-04 2023-11-07 广东圆融新材料有限公司 Polypropylene modified material capable of being welded by laser as well as preparation method and application thereof
CN115490953A (en) * 2022-09-06 2022-12-20 烽火通信科技股份有限公司 Black polyolefin material and preparation method thereof
CN115490953B (en) * 2022-09-06 2023-11-03 烽火通信科技股份有限公司 Black polyolefin material and preparation method thereof
CN116144109A (en) * 2023-02-13 2023-05-23 南京聚隆科技股份有限公司 Low-density low-warpage automobile bottom guard board material and preparation method thereof

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