CN102939195A - 包含有机添加剂的激光透明性pbt - Google Patents

包含有机添加剂的激光透明性pbt Download PDF

Info

Publication number
CN102939195A
CN102939195A CN2011800287701A CN201180028770A CN102939195A CN 102939195 A CN102939195 A CN 102939195A CN 2011800287701 A CN2011800287701 A CN 2011800287701A CN 201180028770 A CN201180028770 A CN 201180028770A CN 102939195 A CN102939195 A CN 102939195A
Authority
CN
China
Prior art keywords
laser
mechanograph
purposes
weight
alkyl
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.)
Granted
Application number
CN2011800287701A
Other languages
English (en)
Other versions
CN102939195B (zh
Inventor
R·冯本特恩
P·艾贝克
W·海克曼
J·库里科夫
M·S·帕贝尔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of CN102939195A publication Critical patent/CN102939195A/zh
Application granted granted Critical
Publication of CN102939195B publication Critical patent/CN102939195B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/15Heterocyclic compounds having oxygen in the ring
    • C08K5/151Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535Five-membered rings
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16Laser beams
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16Laser beams
    • B29C65/1629Laser beams characterised by the way of heating the interface
    • B29C65/1635Laser beams characterised by the way of heating the interface at least passing through one of the parts to be joined, i.e. laser transmission welding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7392General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7392General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic
    • B29C66/73921General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic characterised by the materials of both parts being thermoplastics
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12Chemical modification
    • C08J7/123Treatment by wave energy or particle radiation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098Metal salts of carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/32Compounds containing nitrogen bound to oxygen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415Five-membered rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/36Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41Compounds containing sulfur bound to oxygen
    • C08K5/42Sulfonic acids; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/36Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45Heterocyclic compounds having sulfur in the ring
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16Laser beams
    • B29C65/1603Laser beams characterised by the type of electromagnetic radiation
    • B29C65/1612Infrared [IR] radiation, e.g. by infrared lasers
    • B29C65/1616Near infrared radiation [NIR], e.g. by YAG lasers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16Laser beams
    • B29C65/1629Laser beams characterised by the way of heating the interface
    • B29C65/1664Laser beams characterised by the way of heating the interface making use of several radiators
    • B29C65/1667Laser beams characterised by the way of heating the interface making use of several radiators at the same time, i.e. simultaneous laser welding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16Laser beams
    • B29C65/1629Laser beams characterised by the way of heating the interface
    • B29C65/1674Laser beams characterised by the way of heating the interface making use of laser diodes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16Laser beams
    • B29C65/1696Laser beams making use of masks
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/737General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined
    • B29C66/7377General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined amorphous, semi-crystalline or crystalline
    • B29C66/73771General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined amorphous, semi-crystalline or crystalline the to-be-joined area of at least one of the parts to be joined being amorphous
    • B29C66/73772General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined amorphous, semi-crystalline or crystalline the to-be-joined area of at least one of the parts to be joined being amorphous the to-be-joined areas of both parts to be joined being amorphous
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/737General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined
    • B29C66/7377General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined amorphous, semi-crystalline or crystalline
    • B29C66/73773General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined amorphous, semi-crystalline or crystalline the to-be-joined area of at least one of the parts to be joined being semi-crystalline
    • B29C66/73774General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined amorphous, semi-crystalline or crystalline the to-be-joined area of at least one of the parts to be joined being semi-crystalline the to-be-joined areas of both parts to be joined being semi-crystalline
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7394General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoset

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electromagnetism (AREA)
  • Toxicology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

本发明涉及含有如下组分作为主要组分的热塑性模塑配混物在生产任意类型激光透明性模制体中的用途:A)聚酯,B)20-200mmol/kg聚酯A)的至少一种通式(I)化合物,其中相互独立地在各位置上具有如下相应含义:-A1-为-NR-、-O-、-S-、-CH=A4-,其中R为H或C1-6烷基,A4为N或CH;A2为COOX或OX,其中X为Li、Na、K、Rb、Cs、Mg/2、Ca/2、Sr/2、Ba/2、Al/3;A3为C1-6烷基,C6-12芳基,C7-13烷芳基,C7-13芳烷基,O-C1-6烷基,O-C6-12芳基,O-C7-13烷芳基,O-C7-13芳烷基,其中X'为H或X的COOX'、OX'、SX'、SO3X',S-C1-6烷基,S-C6-12芳基,NR2,卤素,NO2,n为1-4的整数,和m为0至4-n的整数,其中如果A3=NO2,则m=1,条件是只要基团COOX和OX以及SX'存在于通式(I)化合物,mmol数基于这些基团,其中X′=X;以及还有C)基于组分A)重量为0-230重量%其他添加剂。

Description

包含有机添加剂的激光透明性PBT
本发明涉及包含如下组分的热塑性模塑组合物在生产任意类型激光透明性模制品中的用途:
A)聚酯,
B)20-200mmol/kg聚酯A)的至少一种通式(I)化合物,
Figure BDA00002562323100011
其中各自独立地位于任意位置
-A1-为-NR-、-O-、-S-、-CH=A4-,其中R为H或C1-6烷基,A4为N或CH,
A2为COOX或OX,其中X为Li、Na、K、Rb、Cs、Mg/2、Ca/2、Sr/2、Ba/2、Al/3,
A3为C1-6烷基,C6-12芳基,C7-13烷芳基,C7-13芳烷基,O-C1-6烷基,O-C6-12芳基,O-C7-13烷芳基,O-C7-13芳烷基,其中X'为H或X的COOX'、OX'、SX'、SO3X',S-C1-6烷基,S-C6-12芳基,NR2,卤素,NO2
n为1-4的整数,和
m为0至4-n的整数,其中如果A3=NO2,则m=1,
条件是在基团COOX和OX以及SX'存在于通式(I)化合物的情况下mmol数基于这些基团,其中X′=X,以及还有
C)基于组分A)重量为0-230重量%其他添加物质。
本发明进一步涉及激光透明性模制品在借助激光透射熔接方法生产模制品中的用途,生产该类模制品的方法以及其在各种应用领域中的用途。
这类组分B)例如在Polymer Engineering and Science 1990,BO(5),第270页及随后各页和1995,35(17),第1407页及随后各页,Journal ofAppl.Pol.Sci.2004,93,第590页及随后各页以及US 4,393,178和EP-A-0251732中描述为配混PET材料的成核剂。没有研究配混材料的光学性能。
存在各种熔接塑料模制品的现有方法(Kunststoffe 87,(1997),11,1632-1640)。在广泛使用的(例如汽车进气管的)热烙铁熔接方法和振动熔接方法中稳定熔接的前提为在实际连接步骤之前粘附体在接触区中充分软化。
近期激光透射熔接,尤其是使用二极管激光器日益广泛用作一种对振动熔接和热烙铁熔接提供替代方法的方法。
技术文献描述了激光透射熔接的基本原理(Kunststoffe 87,(1997)3,348-350;Kunststoffe 88,(1998),2,210-212;Kunststoffe 87(1997)11,1632-1640;Plastverarbeiter 50(1999)4,18-19;Plastverarbeiter 46(1995)9,42-46)。
使用激光透射熔接的前提是由激光器发射的辐射首先穿透对所用波长的激光具有足够透明度且在本申请中在下文称为激光透明性模制品的模制品,然后在薄层中由与激光透明性模制品接触并在下文称为激光吸收性模制品的第二模制品吸收。在吸收激光的薄层内,激光的能量转化成热,并且这导致在该接触区内熔融并最终导致激光透明性模制品和激光吸收性模制品接合的熔接缝。
激光透射熔接通常使用波长范围为600-1200nm的激光。在用于热塑性材料熔接的激光的波长范围内,常见激光器为Nd:YAG激光器(1064nm)或高功率二极管激光器(800-1000nm)。当在下文使用术语激光透明性和激光吸收性时,它们总是涉及上述波长范围。
与激光吸收性模制品不同,激光透明性模制品要求在优选波长范围内的高激光透明度,从而使得激光束可以在所需能级下尽可能深地穿透熔接区域。用于测量对IR激光的透射能力的方法的实例使用分光光度计和积分光度计球。该测量装置也检测透射辐射的散射比例。该测量不仅在单个波长下进行,而且在包括目前用于该熔接程序的所有激光波长的光谱范围内进行。
用户目前可以使用许多基于透射原理的激光熔接方法变型。例如,周线熔接是一种顺序熔接方法,其中激光束沿着可自由编程的熔接周线传导或者组件相对于静止的激光器移动。在同步熔接方法中,由单个高功率二极管发射的线性辐射沿着熔接缝的周线排列。因此,整个周线同时发生熔融和熔接。准同步熔接方法是周线熔接和同步熔接的组合。电流测定镜(扫描器)用来在非常高的速度下以10m/s或更大沿着熔接缝的周线传导激光束。该高横移速率提供了接合区域的渐进加热和熔融。与同步熔接方法相比,熔接缝的周线改变具有高度灵活性。掩模熔接是一种其中线性激光束横向运动通过粘附体的方法。将掩模用于辐射的受控筛选,并且这仅影响其中要熔接的待接合区域。该方法可以产生非常精确定位的熔接缝。这些方法为本领域熟练技术人员已知且例如描述于“HandbuchKunststoff-Verbindungstechnik”[塑料连接技术手册](G.W.Ehrenstein,Hanser,ISBN 3-446-22668-0)和/或DVS-Richtlinie 2243“Laserstrahlschweiβen thermoplastischer Kunststoffe”[GermanWelding Society Guideline 2243“热塑性材料的激光熔接”]。
与所用方法变型无关,激光熔接方法高度依赖于两种粘附体的材料性能。透明组分的激光透明度(LT)通过每单位时间可以引入的能量的量直接影响该方法的速度。半结晶热塑性材料的固有微结构,大多呈球晶形式,通常使它们具有较低的激光透明度。这些球晶比纯无定形热塑性材料的内部结构更大程度地散射入射的激光:后向散射导致透射能量的总量降低,而漫(侧向)散射通常导致激光束变宽并因此导致熔接精度受损。这些现象在聚对苯二甲酸丁二醇酯(PBT)中特别明显,PBT与其他良好结晶的热塑性材料如PA相比显示出特别低的激光透明度和高的光束展宽程度。因此,PBT一直较少用作激光熔接组件的材料,但其性能特征的其他方面(例如良好的尺寸稳定性和低吸水性)使得其对于这类应用非常具有吸引力。尽管半结晶形态通常对高激光透明度无益,但就其他性能而言提供了优点。例如,半结晶材料一直在玻璃化转变点之上都具有机械强度且通常比无定形材料具有更好的耐化学品性。快速结晶的材料也提供了加工优点,尤其是快速脱模性和因此短循环时间。因此,希望将半结晶性与快速结晶和高激光透明度结合起来。
对于聚酯,尤其是PBT中的激光透明度增加存在各种已知方法。原则上可以将这些分成共混物/混合物和折射率匹配。
使用共混物/混合物的方法基于通过在该共混物/混合物中使用高激光透明度配对“稀释”低激光透明度PBT。其实例在下列说明书中找到:JP2004/315805A1(PBT+PC/PET/SA+填料+弹性体),DE-A1-10330722(半结晶热塑性材料与无定形热塑性材料的广义共混物,以提高LT;具体为PBT+PET/PC+玻璃纤维),JP 2008/106217A(PBT+含1,4-环己烷二甲醇的共聚物;LT由16%增至28%)。此时的缺点是所得聚合物共混物的性能不可避免地显著不同于主要基于PBT作为基体的产品的那些。
折射率匹配方法基于无定形和结晶PBT以及还有填料的不同折射率。例如,这里使用了共聚单体:作为实例可以提到JP 2008/163167(PBT和硅氧烷的共聚物),JP 2007/186584(PBT+双酚A二缩水甘油醚)和JP2005/133087(PBT+PC+弹性体+高折射率硅油)。尽管这导致激光透明度增加,但这在损失机械性能下实现。也可以降低填料和基体之间的折射率差,参见JP 2009/019134(环氧树脂涂敷于玻璃纤维上以在填料和基体之间的光学界面处提供匹配),或JP2007/169358(含有高折射率玻璃纤维的PBT)。然而,这类原料由于其高成本和/或它们在该生产方法内所要求的额外步骤而是不利的。
相对于激光透明度增加所实现的效果总体而言也相对小且因此并不完全令人满意。
因此,本发明的目的是改进聚酯的激光透明度并提供适合用于激光透射熔接的聚酯。因此发现了在引言中所定义的模塑组合物及其用途。从属权利要求给出了优选的实施方案。
本发明模塑组合物包含至少一种热塑性聚酯作为组分A)。
在组分A)中聚酯中的至少一种优选为半结晶聚酯。优选组分A)包含至少50重量%半结晶聚酯。该比例特别优选为至少70重量%(在每种情况下基于100重量%A))。
基于100%由A)-C)构成的模塑组合物(即包括C)在内),这些组合物包含30-100重量%,优选50-100重量%A)+B);0-70重量%,优选0-50重量%C)。
上述相对量级内的基本因子是组分B)的比例总是基于聚酯,因为该比例意欲位于上述范围内。添加物质C)可能影响激光透明度。该影响实质上取决于添加物质的散射和吸收性能。配混材料的光学性能实质上是本发明基体(组分A+B)的光学性能和添加剂(组分C)的那些的总和。
通常所用聚酯A)基于芳族二羧酸和脂族或芳族二羟基化合物。
第一组优选的聚酯是在醇结构部分尤其具有2-10个碳原子的聚对苯二甲酸亚烷基二醇酯。
这类聚对苯二甲酸亚烷基二醇酯本身已知且描述于文献中。它们的主链包含衍生于芳族二羧酸的芳族环。芳族环也可以被卤素,如氯或溴,或被C1-C4烷基,如甲基、乙基、异丙基、正丙基、正丁基、异丁基或叔丁基取代。
这些聚对苯二甲酸亚烷基二醇酯可以通过使芳族二羧酸或其酯或其他成酯衍生物与脂族二羟基化合物以本身已知的方式反应而生产。
优选的二羧酸是2,6-萘二甲酸、对苯二甲酸和间苯二甲酸或这些的混合物。至多30mol%,优选不超过10mol%芳族二羧酸可以被脂族或脂环族二羧酸如己二酸、壬二酸、癸二酸、十二烷二酸和环己烷二甲酸替代。
优选的脂族二羟基化合物是具有2-6个碳原子的二醇,尤其是1,2-乙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、1,4-己二醇、1,4-环己烷二醇、1,4-环己烷二甲醇和新戊二醇,以及这些的混合物。
特别优选的聚酯(A)是衍生于具有2-6个碳原子的链烷二醇的聚对苯二甲酸亚烷基二醇酯。其中特别优选聚对苯二甲酸乙二醇酯、聚对苯二甲酸丙二醇酯和聚对苯二甲酸丁二醇酯,以及这些的混合物。还优选包含至多1重量%,优选至多0.75重量%的1,6-己二醇和/或2-甲基-1,5-戊二醇作为其他单体单元的PET和/或PBT。
聚酯(A)根据ISO 1628的特性粘度通常为50-220,优选80-160(在25°C下在重量比为1:1的苯酚/邻二氯苯混合物中的浓度为0.5重量%的溶液中测定)。
特别优选端羧基含量为0-100meq/kg聚酯,优选10-50meq/kg聚酯,尤其是15-40meq/kg聚酯的聚酯。这类聚酯例如可以通过DE-A 44 01 055的方法生产。端羧基含量通常通过滴定方法(例如电位分析法)测定。
特别优选的模塑组合物包含聚酯混合物作为组分A),其中至少一种为PBT。聚对苯二甲酸乙二醇酯在该混合物中的比例实例优选基于100重量%A)为至多50重量%,尤其是10-35重量%。
还有利的是,如果合适使用PET回收材料(也称为废PET),以与聚对苯二甲酸亚烷基二醇酯如PBT的混合物。
回收材料通常是:
1)已知为工业后回收材料的那些:这些是在缩聚或加工过程中的生产废料,例如来自注塑的浇口废料,来自注塑或挤出的启动材料,或来自挤出片材或膜的边角料。
2)消费后回收材料:这些是在最终消费者使用后收集和处理的塑料物品。矿泉水、软饮料和果汁的吹塑PET瓶子是在数量上容易占主导的物品。
两种类型的回收材料都可以作为再磨料或者以粒料形式使用。在后一种情况下,分离并提纯粗回收材料,然后使用挤出机将其熔融并造粒。这通常有利于处理和自由流动性能,以及有利于在加工的其它步骤中计量加入。
使用的回收材料可以粒化或呈再磨料的形式。其边长不应超过10mm,优选小于8mm。
因为聚酯在加工过程中(由于痕量的水分)经历水解裂解,所以将回收材料预干燥是有利的。干燥后的残余水含量优选<0.2%,特别是<0.05%。
另一组可以提到的聚酯是衍生于芳族二羧酸和芳族二羟基化合物的全芳族聚酯。
合适的芳族二羧酸是前面对聚对苯二甲酸亚烷基二醇酯所述的化合物。优选使用的混合物由5-100mol%间苯二甲酸和0-95mol%对苯二甲酸构成,更特别是约80%对苯二甲酸与20%间苯二甲酸的混合物至这两种酸的近似当量混合物。
芳族二羟基化合物优选具有如下通式:
Figure BDA00002562323100061
其中Z为具有至多8个碳原子的亚烷基或亚环烷基,具有至多12个碳原子的亚芳基,羰基,磺酰基,氧原子或硫原子,或化学键,并且其中m具有0-2的值。这些化合物中的亚苯基也可以被C1-C6烷基或烷氧基以及氟、氯或溴取代。
这些化合物的母体化合物实例是二羟基联苯、二(羟基苯基)链烷烃、二(羟基苯基)环烷烃、二(羟基苯基)硫醚、二(羟基苯基)醚、二(羟基苯基)酮、二(羟基苯基)亚砜、α,α'-二(羟基苯基)二烷基苯、二(羟基苯基)砜、二(羟基苯甲酰基)苯、间苯二酚和氢醌,还有这些的环上烷基化和环上卤化的衍生物。
其中优选4,4'-二羟基联苯、2,4-二(4'-羟基苯基)-2-甲基丁烷、α,α'-二(4-羟基苯基)-对二异丙基苯、2,2-二(3'-甲基-4'-羟基苯基)丙烷和2,2-二(3'-氯-4'-羟基苯基)丙烷、尤其是2,2-二(4'-羟基苯基)丙烷、2,2-二(3',5-二氯二羟基苯基)丙烷、1,1-二(4'-羟基苯基)环己烷,3,4'-二羟基二苯甲酮、4,4'-二羟基二苯基砜和2,2-二(3',5'-二甲基-4'-羟基苯基)丙烷,或这些的混合物。
当然还可以使用聚对苯二甲酸亚烷基二醇酯和全芳族聚酯的混合物。这些通常包含20-98重量%聚对苯二甲酸亚烷基二醇酯和2-80重量%全芳族聚酯。
当然还可以使用聚酯嵌段共聚物,如共聚醚酯。这类产物本身已知且描述于文献中,例如描述于US-A 3 651 014中。相应的产物还可以市购,例如
Figure BDA00002562323100071
(DuPont)。
在本发明中,术语聚酯包括不含卤素的聚碳酸酯。合适的不含卤素的聚碳酸酯实例是基于如下通式的双酚的那些:
Figure BDA00002562323100072
其中Q为单键、C1-C8亚烷基、C2-C3烷叉基、C3-C6环烷叉基、C6-C12亚芳基,或-O-、-S-或-SO2-,以及m为0-2的整数。
该双酚的亚苯基还可以具有取代基,如C1-C6烷基或C1-C6烷氧基。
优选该式的双酚实例是氢醌、间苯二酚、4,4'-二羟基联苯、2,2-二(4-羟基苯基)丙烷、2,4-二(4-羟基苯基)-2-甲基丁烷和1,1-二(4-羟基苯基)环己烷。特别优选2,2-二(4-羟基苯基)丙烷和1,1-二(4-羟基苯基)环己烷,还有1,1-二(4-羟基苯基)-3,3,5-三甲基环己烷。
均聚碳酸酯或共聚碳酸酯都适合作为组分A,且优选双酚A的共聚碳酸酯,以及优选双酚A的均聚物。
合适的聚碳酸酯可以以已知方式支化,具体而言优选通过引入基于所用双酚的总量为0.05-2.0mol%的至少三官能化合物,例如具有三个或更多个酚类OH基团的那些化合物而支化。
已经证实特别合适的聚碳酸酯具有1.10-1.50,尤其是1.25-1.40的相对粘度η相对。这对应于10000-200000g/mol,优选20000-80000g/mol的平均摩尔质量MW(重均)。
该通式的双酚本身是已知的或者可以通过已知方法制备。
聚碳酸酯例如可以通过使双酚与光气在界面工艺中反应,或者使双酚与光气在均相工艺中反应(已知为吡啶工艺)而生产,在每种情况下可以通过使用合适量的已知链终止剂而以已知方式获得所需的分子量。(对于含有聚二有机硅氧烷的聚碳酸酯,例如参见DE-A 3334782。)
合适链终止剂的实例是苯酚,对叔丁基苯酚,或者如DE-A 2842005中的长链烷基苯酚如4-(1,3-四甲基丁基)苯酚,或者如DE-A-3506472中的在烷基取代基中共计具有8-20个碳原子的单烷基苯酚或二烷基苯酚,例如对壬基苯基、3,5-二叔丁基苯酚、对叔辛基苯酚、对十二烷基苯酚、2-(3,5-二甲基庚基)苯酚和4-(3,5-二甲基庚基)苯酚。
对于本发明而言,不含卤素的聚碳酸酯是由不含卤素的双酚、不含卤素的链终止剂和如果合适,不含卤素的支化剂构成的聚碳酸酯,其中在ppm水平的少量可水解氯含量(例如用光气在界面工艺中生产聚碳酸酯而产生)对于本发明而言不认为配得上术语“含卤素”。具有在ppm水平的可水解氯含量的这类聚碳酸酯对于本发明而言是不含卤素的聚碳酸酯。
可以提到的其它合适组分A)是无定形的聚酯碳酸酯,其中在制备过程中光气由芳族二羧酸单元如间苯二甲酸和/或对苯二甲酸单元替代。对此可以参考EP-A 711810以得到其它细节。
EP-A 365916描述了具有环烷基作为单体单元的其他合适共聚碳酸酯。
还可以用双酚TMC替代双酚A。这类聚碳酸酯可以由Bayer以商标
Figure BDA00002562323100091
得到。
本发明模塑组合物包含20-200mmol/kg聚酯A),优选25-140mmol/kg聚酯A),尤其是30-110mmol/kg聚酯A)的至少一种通式(I)化合物作为组分B)。
组分B)的mmol数在此基于通式(I)化合物的基团A2和任选A3基团中的COOX和OX以及SX',其中X′=X。一个基团COOX或OX或SX'(其中X′=X)分别对应于一当量或一摩尔。mmol数据因此整体上给出了基团COOX和OX以及SX'(其中X′=X)的摩尔量(即其之和)。成核剂数对聚酯的激光透明度而言是重要的。这是为什么要使用的成核剂B)的量以基于摩尔浓度的盐基团而不是重量%的形式说明。成核剂或成核试剂的量在实施例中以重量%和mmol/kg聚酯二者说明。
可以参考使用当量测定摩尔量的1998年12月的DIN 32625。
还可以参考J.S.Fritz,G.H.Schenk,Quantitative AnalytischeChemie[Quantitative Analytical Chemistry],Viehweg,1989,第8-9页及随后各页。
还可能的是游离羧基(COOH)或羟基(OH)或相应硫体系以基团A3存在于通式(I)化合物中。这些对成核作用贡献很少或没有贡献,并且该量因此不包括在测定mmol/kg聚酯A)的计算中。在部分中和的羧基或羟基的情况下,仅中和部分包括在计算中。
聚酯A)通常与盐化合物B)反应,此时化合物B)的金属阳离子转移至聚酯的端羧基。组分B)的成核作用甚至在非常小的浓度下也可检测。惊人的是,激光透明度在组分B)的浓度非常小时下降,并且仅在浓度较高时激光透明度上升。
组分B)为选自一种或多种通式I)化合物的组分:
Figure BDA00002562323100092
其中各自独立地位于任意位置
-A1-为-NR-、-O-、-S-、-CH=A4-,其中R为H或C1-6烷基,A4为N或CH,
A2为COOX或OX,其中X为Li、Na、K、Rb、Cs、Mg/2、Ca/2、Sr/2、Ba/2、Al/3,
A3为C1-6烷基,C6-12芳基,C7-13烷芳基,C7-13芳烷基,O-C1-6烷基,O-C6-12芳基,O-C7-13烷芳基,O-C7-13芳烷基,其中X'为H或X的COOX'、OX'、SX'、SO3X',S-C1-6烷基、S-C6-12芳基、NR2、卤素、NO2
n为1-4的整数,和
m为0至4-n的整数,其中如果A3=NO2,则m=1,
条件是在基团COOX和OX以及SX'存在于通式(I)化合物的情况下mmol数基于这些基团,其中X′=X。
该化合物因此可以为5员或6员芳族环体系。5员环体系为杂环,而6员环可以为氮杂环或仅包含碳的芳族环状化合物且因此形式上由苯衍生。
优选通式(I)化合物中的n的值为1或2。
优选通式(I)化合物中的m的值为0或1或2。
在此特别优选n的值为1。特别优选m的值为0或1。
因此特别优选n=1与m=0以及n=1与m=1的组合。
X优选为Li、Na、K、Rb或Cs,特别是Li、Na或K,具体为Na。还可能的是存在这些抗衡离子中的两种或更多种的混合物。
A3特别优选C1-6烷基、OX、SO3X、卤素或NO2
通式(I)化合物中的R优选为H。
措辞Mg/2、Ca/2、Sr/2、Ba/2、Al/3指中和一个基团COOH或OH或SH或SO3H所需的1当量金属或金属离子。由于镁、钙、锶和钡是二价的,一个相应离子足以中和两个羧基或羟基或SH或SO3H。一个铝离子足以中和三个羧基或羟基。当存在所述抗衡离子时,环状有机化合物的量因此必须加倍或加两倍以获得整数的金属原子或离子数。
优选的通式(I)化合物列在下文和实施例中。
优选钠盐。通式(I)化合物优选由水杨酸、苯甲酸或酚得到,其中芳族环可以带有其他取代基,但是不存在其他羟基或羧基。
实例为苯甲酸钠、4-叔丁基苯甲酸钠、水杨酸二钠、异烟酸钠、2-噻吩甲酸钠、吡咯-2-甲酸钠、苯酚钠、4-羟基苯磺酸二钠、5-磺基间苯二甲酸锂、2-硝基苯甲酸钠、2-氯苯甲酸钠、2,4-二氯苯甲酸钠和苯基乙酸钠。
优选通式(I)化合物中所有羧基和羟基均被中和。
组分B)的重量比例可以基于组分A)近似限定为优选0.3-2.0重量%,特别优选0.4-1.5重量%,其中特别优选0.5-1重量%。然而,mmol/kg聚酯A)的以上数据由于成核盐基团COOX、OX、SX'(其中X′=X)的分子量和当量不同而更可靠。
本发明模塑组合物可以包含基于组分A)重量为0-230重量%,尤其是至多100重量%的不同于B)和/或A)的其他添加物质和加工助剂作为组分C)。
例如,常规添加物质C)是量至多为66重量%,优选至多18重量%的弹性体聚合物(也常称为抗冲改性剂、弹性体或橡胶)。
这些非常一般地涉及优选由下列单体中的至少两种构成的共聚物:乙烯、丙烯、丁二烯、异丁烯、异戊二烯、氯丁二烯、乙酸乙烯酯、苯乙烯、丙烯腈和在醇组分中具有1-18个碳原子的丙烯酸酯或甲基丙烯酸酯。
这类聚合物例如描述于Houben-Weyl,Methoden der organischenChemie,第14/1卷(Georg Thieme Verlag,Stuttgart,1961),第392-406页以及C.B.Bucknall的单行本“增韧塑料”(Applied Science Publishers,London,UK,1977)中。
这类弹性体中的某些优选类型如下所述。
优选的弹性体类型是已知为乙烯-丙烯橡胶(EPM)和乙烯-丙烯-二烯橡胶(EPDM)的那些。
EPM橡胶通常基本没有残留双键,而EPDM橡胶可以具有1-20个双键/100个碳原子。
可以提到用于EPDM橡胶的二烯烃单体实例是共轭二烯,例如异戊二烯和丁二烯,具有5-25个碳原子的非共轭二烯,例如1,4-戊二烯、1,4-己二烯、1,5-己二烯、2,5-二甲基-1,5-己二烯和1,4-辛二烯,环状二烯,例如环戊二烯、环己二烯、环辛二烯和二聚环戊二烯,还有链烯基降冰片烯,例如5-乙叉基-2-降冰片烯、5-丁叉基-2-降冰片烯、2-甲代烯丙基-5-降冰片烯和2-异丙烯基-5-降冰片烯,以及三环二烯,例如3-甲基三环[5.2.1.02,6]-3,8-癸二烯,或这些的混合物。优选1,5-己二烯、5-乙叉基降冰片烯和二聚环戊二烯。EPDM橡胶中的二烯含量基于橡胶的总重量优选为0.5-50重量%,特别是1-8重量%。
EPM和EPDM橡胶还可以优选用反应性羧酸或者用这些的衍生物接枝。这些化合物的实例是丙烯酸、甲基丙烯酸及其衍生物如(甲基)丙烯酸缩水甘油酯,还有马来酸酐。
乙烯与丙烯酸和/或甲基丙烯酸和/或与这些酸的酯的共聚物是另一类优选的橡胶。该橡胶还可以包含二羧酸如马来酸和富马酸,或这些酸的衍生物如酯和酸酐,和/或含有环氧基团的单体。优选通过将包含二羧酸基团和/或环氧基团且具有通式I或II或III或IV的单体加入单体混合物中而将这些包含二羧酸衍生物或包含环氧基团的单体掺入橡胶中:
R1C(COOR2)=C(COOR3)R4                         (I)
Figure BDA00002562323100121
其中R1-R9为氢或具有1-6个碳原子的烷基,m为0-20的整数,g为0-10的整数且p为0-5的整数。
R1-R9优选为氢,其中m为0或1且g为1。对应的化合物是马来酸、富马酸、马来酸酐、烯丙基缩水甘油醚和乙烯基缩水甘油醚。
优选的式I、II和IV化合物是马来酸、马来酸酐和包含环氧基团的(甲基)丙烯酸酯,如丙烯酸缩水甘油酯和甲基丙烯酸缩水甘油酯,以及与叔醇的酯,如丙烯酸叔丁酯。尽管后者没有游离羧基,但它们的行为类似于游离酸且因此将它们称为具有潜在羧基的单体。
共聚物有利地由50-98重量%的乙烯、0.1-20重量%的包含环氧基团的单体和/或甲基丙烯酸和/或包含酸酐基团的单体构成,剩余量为(甲基)丙烯酸酯。
特别优选由下列物质构成的共聚物:
50-98重量%,特别是55-95重量%的乙烯,
0.1-40重量%,特别是0.3-20重量%的丙烯酸缩水甘油酯和/或甲基丙烯酸缩水甘油酯、(甲基)丙烯酸和/或马来酸酐,和
1-45重量%,特别是10-40重量%的丙烯酸正丁酯和/或丙烯酸2-乙基己酯。
其他优选的(甲基)丙烯酸酯是甲酯、乙酯、丙酯、异丙酯、异丁酯和叔丁酯。
除了这些以外,还可以使用的共聚单体是乙烯基酯和乙烯基醚。
上述乙烯共聚物可以通过本身已知的方法生产,优选通过在高压和升高的温度下无规共聚而生产。合适的方法是众所周知的。
其他优选的弹性体是乳液聚合物,其生产例如由Blackley描述于单行本“乳液聚合”中。可以使用的乳化剂和催化剂本身是已知的。
原则上可以使用具有均匀结构的弹性体或具有壳结构的弹性体。壳结构类型通过各个单体的加入顺序确定。该聚合物的形态也受到加入顺序的影响。
这里可以仅作为实例提到的用于生产弹性体的橡胶部分的单体是丙烯酸酯如丙烯酸正丁酯和丙烯酸2-乙基己酯、相应的甲基丙烯酸酯、丁二烯和异戊二烯,还有这些的混合物。这些单体可以与其他单体如苯乙烯、丙烯腈、乙烯基醚和其他丙烯酸酯或甲基丙烯酸酯如甲基丙烯酸甲酯、丙烯酸甲酯、丙烯酸乙酯或丙烯酸丙酯共聚。
弹性体的柔软或橡胶相(玻璃化转变温度低于0°C)可以是核、外部壳或中间壳(在弹性体结构具有2个以上壳的情况下)。具有1个以上壳的弹性体还可以具有1个以上由橡胶相构成的壳。
如果在弹性体的结构中除了橡胶相以外还涉及一种或多种硬组分(玻璃化转变温度高于20°C),则这些硬组分通常通过聚合作为主要单体的苯乙烯、丙烯腈、甲基丙烯腈、α-甲基苯乙烯、对甲基苯乙烯或者丙烯酸酯或甲基丙烯酸酯如丙烯酸甲酯、丙烯酸乙酯或甲基丙烯酸甲酯而生产。除此以外,在这里还可以使用较少比例的其他共聚单体。
在某些情况下证实有利的是使用在表面上具有反应性基团的乳液聚合物。这类基团的实例是环氧基团、羧基、潜在羧基、氨基和酰胺基,还有可以通过同时使用如下通式的单体而引入的官能基团:
Figure BDA00002562323100141
其中各取代基的定义可以如下所述:
R10是氢或C1-C4烷基,
R11是氢、C1-C8烷基或芳基,特别是苯基,
R12是氢、C1-C10烷基、C6-C12芳基或-OR13
R13是C1-C8烷基或C6-C12芳基,如果合适被含有O或N的基团取代,X是化学键或C1-C10亚烷基或C6-C12亚芳基,或
Figure BDA00002562323100142
Y是O-Z或NH-Z,和
Z是C1-C10亚烷基或C6-C12亚芳基。
EP-A 208187中描述的接枝单体也适合在表面引入反应性基团。
可以提到的其他实例是丙烯酰胺、甲基丙烯酰胺和取代的丙烯酸酯或甲基丙烯酸酯,例如甲基丙烯酸(N-叔丁基氨基)乙酯、丙烯酸(N,N-二甲氨基)乙酯、丙烯酸(N,N-二甲氨基)甲酯和丙烯酸(N,N-二乙氨基)乙酯。
橡胶相的颗粒也可以被交联。交联单体的实例是1,3-丁二烯、二乙烯基苯、邻苯二甲酸二烯丙酯和丙烯酸二氢二聚环戊二烯基酯,还有EP-A 50265中描述的化合物。
还可以使用已知为接枝连接单体的单体,即具有两个或更多个在聚合过程中以不同速率反应的可聚合双键的单体。优选使用其中至少一个反应性基团以大约与其他单体相同的速率聚合,而其他反应性基团(或多个反应性基团)例如显著更慢地聚合的这类化合物。不同的聚合速率在橡胶中产生特定比例的不饱和双键。若随后将另一相接枝到这类橡胶上,则橡胶中存在的至少某些双键与接枝单体发生反应形成化学键,即被接枝的相至少与接枝基质具有某种程度的化学键合。
这类接枝连接单体的实例是含有烯丙基的单体,特别是烯属不饱和羧酸的烯丙酯,例如丙烯酸烯丙酯、甲基丙烯酸烯丙酯、马来酸二烯丙酯、富马酸二烯丙酯和衣康酸二烯丙酯,以及这些二羧酸的相应单烯丙酯化合物。除了这些以外还有各种其他合适接枝连接单体。进一步的细节在此可以参考例如US-A 4148846。
基于抗冲改性聚合物,这些交联单体在抗冲改性聚合物中的比例通常是至多5重量%,优选不超过3重量%。
一些优选的乳液聚合物列举如下。在此首先可以提到具有核和至少一个外壳且具有下列结构的接枝聚合物:
Figure BDA00002562323100151
这些接枝聚合物,特别是ABS聚合物和/或ASA聚合物优选对于PBT的抗冲改性以至多40重量%的量使用,如果合适以与至多40重量%的聚对苯二甲酸乙二醇酯的混合物使用。合适的共混产品可以以商标
Figure BDA00002562323100152
S(以前是
Figure BDA00002562323100153
S,来自BASF AG)得到。
代替其结构具有一个以上壳的接枝聚合物,还可以使用由1,3-丁二烯、异戊二烯和丙烯酸正丁酯,或者由这些的共聚物构成的均匀(即单壳)弹性体。这些产物也可以通过同时使用交联单体或具有反应性基团的单体而生产。
优选的乳液聚合物实例是丙烯酸正丁酯-(甲基)丙烯酸共聚物,丙烯酸正丁酯-丙烯酸缩水甘油酯或者丙烯酸正丁酯-甲基丙烯酸缩水甘油酯共聚物,具有由丙烯酸正丁酯构成或基于丁二烯的内部核且具有由上述共聚物构成的外部壳的接枝聚合物,以及乙烯与提供反应性基团的共聚单体的共聚物。
所述弹性体还可以通过其他常规方法如经由悬浮聚合而制备。
同样优选硅橡胶,如DE-A 3725576、EP-A 235690、DE-A 3800603和EP-A 319290中所述。
当然还可以使用以上列举的各类橡胶的混合物。
可提到的纤维状或颗粒状填料C)是玻璃纤维、玻璃珠、无定形二氧化硅、石棉、硅酸钙、偏硅酸钙、碳酸镁、高岭土、白垩、粉末石英、云母、硫酸钡和长石。纤维状填料C)的用量基于组分A)的量至多为150重量%,特别是至多50重量%,且颗粒状填料的用量至多为45重量%,特别是至多10重量%。
可以提到的优选纤维状填料是芳族聚酰胺纤维和钛酸钾纤维,在此特别优选E玻璃形式的玻璃纤维。这些材料可以作为粗纱或以市售的短切玻璃纤维形式使用。
具有高激光吸收性的填料,例如碳纤维、碳黑、石墨、石墨烯或碳纳米管的用量基于组分A)的量优选小于1重量%,特别优选小于0.05重量%。
纤维状填料可以用硅烷化合物进行表面预处理以改进与热塑性材料的相容性。
合适的硅烷化合物是如下通式的那些:
(X-(CH2)n)k-Si–(O–CmH2m+1)4–k
其中各取代基的定义如下所述:
X是NH2-、HO-,
n是2-10,优选3-4的整数,
m是1-5,优选1-2的整数,和
k是1-3,优选1的整数。
优选的硅烷化合物是氨基丙基三甲氧基硅烷、氨基丁基三甲氧基硅烷、氨基丙基三乙氧基硅烷和氨基丁基三乙氧基硅烷,还有包含缩水甘油基作为取代基X的相应硅烷。
用于表面涂覆的硅烷化合物的用量通常为0.05-5重量%,优选0.1-1.5重量%,特别是0.2-0.5重量%(基于C)。
针状矿物填料也是合适的。
对于本发明而言,针状矿物填料是具有显著针状特征的矿物填料。可以提到的实例是针状硅灰石。该矿物填料优选具有8:1-35:1,优选8:1-11:1的L/D比(长径比)。该矿物填料如果合适可以用上述硅烷化合物预处理;然而,预处理不是必需的。
本发明的热塑性模塑组合物可以包含常规加工助剂,例如稳定剂、氧化抑制剂、用于抵抗热分解和紫外光分解的试剂、润滑剂和脱模剂、着色剂如染料和颜料、增塑剂等作为组分C)。
可以提到的氧化抑制剂和热稳定剂的实例是空间位阻酚和/或亚磷酸酯、氢醌类、芳族仲胺如二苯胺,以及这些组的各种取代代表,以及这些的混合物,其浓度基于热塑性模塑组合物的重量为至多1重量%。
可以提到的基于模塑组合物通常以至多2重量%的量使用的UV稳定剂是各种取代的间苯二酚、水杨酸酯、苯并三唑类和二苯甲酮类。
可以加入的着色剂是无机和有机颜料,还有染料,例如苯胺黑和蒽醌。特别合适的着色剂例如在EP 1722984B1,EP 1353986B1或DE 10054859A1中提到。
进一步优选具有10-40个,优选16-22个碳原子的饱和或不饱和脂族羧酸与包含2-40个,优选2-6个碳原子的饱和脂族醇或胺的酯或酰胺。
羧酸可以是一元或二元的。可以提到的实例是壬酸、棕榈酸、月桂酸、十七烷酸、十二烷二酸、山
Figure BDA00002562323100171
酸,特别优选硬脂酸、癸酸以及褐煤酸(具有30-40个碳原子的脂肪酸混合物)。
脂族醇可以是一元至四元的。醇的实例是正丁醇、正辛醇、硬脂醇、乙二醇、丙二醇、新戊二醇和季戊四醇,在此优选甘油和季戊四醇。
脂族胺可以是单至三官能的。这些的实例是硬脂胺、乙二胺、丙二胺、六亚甲基二胺和二(6-氨基己基)胺,在此特别优选乙二胺和六亚甲基二胺。相应地,优选的酯或酰胺是甘油二硬脂酸酯、甘油三硬脂酸酯、乙二胺二硬脂酸酰胺、甘油单棕榈酸酯、甘油三月桂酸酯、甘油单山酸酯和季戊四醇四硬脂酸酯。
还可以以任何所需混合比使用各种酯或酰胺的混合物,或者酯和酰胺的组合。
其他润滑剂和脱模剂的常用量通常基于组分A)的量为至多1重量%。优选使用长链脂肪酸(例如硬脂酸或山萮酸),这些的盐(例如硬脂酸钙或硬脂酸锌),或褐煤蜡(由链长为28-32个碳原子的直链饱和羧酸构成的混合物)或褐煤酸钙或褐煤酸钠,或低分子量聚乙烯蜡或低分子量聚丙烯蜡。
可以提到的增塑剂实例是邻苯二甲酸二辛酯、邻苯二甲酸二苄酯、邻苯二甲酸丁基·苄基酯、烃油和N-(正丁基)苯磺酰胺。
本发明的模塑组合物还可以包含基于组分A)的量为0-2重量%的含氟乙烯聚合物。这些是氟含量为55-76重量%,优选70-76重量%的乙烯聚合物。
这里的实例是聚四氟乙烯(PTFE)、四氟乙烯-六氟丙烯共聚物或具有较小比例(通常至多50重量%)的可共聚烯属不饱和单体的四氟乙烯共聚物。这些例如由Schildknecht描述于“乙烯基聚合物和相关聚合物”,WileyVerlag,1952,第484-494页中且由Wall描述于“氟聚合物”(WileyInterscience,1972)中。
这些含氟乙烯聚合物在模塑组合物中均匀分布,且优选具有0.05-10μm,特别是0.1-5μm的d50粒度(数均)。特别优选这些小粒度可以经由使用含氟乙烯聚合物的水分散体并将这些掺入聚酯熔体中而实现。
本发明的热塑性模塑组合物可以通过本身已知的方法,通过在常规混合设备如螺杆挤出机、Brabender混合机或Banbury混合机中混合起始组分,随后将其挤出而生产。然后可以将挤出物冷却并粉碎。还可以预混合各组分(例如将组分B)施用于粒料,例如在转鼓中),然后单独和/或在同样将它们混合之后加入剩余的原料。混合温度通常为230-290°C。组分B)也可以优选通过热进料或直接方法加入挤出机入口中。
在另一优选操作方法中,组分B)和如果合适C)可以与聚酯预聚物混合、配混并造粒。然后在惰性气体中在低于组分A)熔点的温度下将所得粒料连续或分批地进行固相缩合直至达到所需粘度。
可以用于本发明中的模塑组合物适合生产激光透明性模制品。这些的激光透明度优选为至少33%,尤其是至少40%,特别是至少50%(在1064nm下通过实施例中所述测试方法对厚度为2mm的模制品进行测量)。
在本发明中借助激光透射熔接方法使用该类激光透明性模制品生产模制品。
该用途优选经由激光透射熔接用于生产模制品。激光透射熔接在此优选用于使激光透明性模制品与激光吸收性模制品结合。
由任何激光吸收性材料制成的模制品通常可以用作激光吸收性模制品。例如,在此可以使用复合材料或热固性材料,或优选由特定热塑性模塑组合物制成的模制品。合适的热塑性模塑组合物是在所用波长范围内具有足够激光吸收的模塑组合物。合适的热塑性模塑组合物优选可以例如为因加入无机颜料如碳黑和/或因加入有机颜料或其他添加剂而呈激光吸收性的热塑性材料。适合实现激光吸收的有机颜料实例优选是IR吸收性有机化合物,例如DE 19916104A1中所述那些。
本发明进一步提供了已经通过激光透射熔接接合本发明的模制品的模制品和/或模制品组合。
本发明的模制品对于通过激光透射熔接方法而与激光吸收性模制品耐久且稳定地连接具有优异的适合性。因此,它们特别适合用于覆盖层、外壳、添加组件和传感器的材料,例如用于汽车、电子产品、电信、信息技术、计算机、家用、运动、医疗或娱乐领域中的应用。
实施例
组分A/1:
特性粘度为130ml/g且端羧基含量为34meq/kg的聚对苯二甲酸丁二醇酯(来自BASF SE的
Figure BDA00002562323100191
B 4500)(在25°C下在浓度为0.5重量%的1:1苯酚/邻二氯苯混合物溶液中测量的IV)。组分B)
E1 苯甲酸钠
E2 4-叔丁基苯甲酸钠
E3 水杨酸二钠
E4 4-羟基苯磺酸二钠
E5 5-磺基间苯二甲酸锂
E6 2-硝基苯甲酸钠
E7 2-氯苯甲酸钠
E8 2,4-二氯苯甲酸钠
E9 苯基乙酸钠
E10 异烟酸钠
E11 2-噻吩甲酸钠
E12 吡咯-2-甲酸钠
E13 苯酚钠
组分C
玻璃纤维:直径10μm,根据聚酯筛分,来自3B的DS3185。
在250-260°C、均匀温度分布和造粒下在ZSK25中生产模塑组合物。
激光透明度测量
激光透过率借助热电功率测量(thermoelektrischen Leistungsmessung)在波长1064nm下测量。测量几何结构按如下设置:使用光束分配器(来自Laseroptik GmbH的SQ2无偏振光束分配器)以90°的角度由总功率为2瓦的激光束(波长为1064nm的二极管抽运Nd-YAG激光器,FOBA DP50)分出功率为1瓦的基准光束。该基准光束冲击基准传感器。通过光束分配器的那部分原始光束提供了功率同样为1瓦的测量光束。该光束经由在该光束分配器后面的波型孔(modenblende)(5.0)聚焦成0.18μm的焦点直径。激光透明度(LT)测量传感器位于焦点以下80mm。测试片材位于LT测量传感器以上2mm。使用尺寸为60*60*2mm3且具有压边浇口的注塑测试片材。在片材中央(两条对角线的交点)进行测量。注塑参数设定为下列值:
        熔体温度[℃]    模具温度[℃]    注射速率[cm3/s]    保压压力[巴]
未增强材料     260              60                 48                 600
增强材料       260              80                 48                 600
总测量时间为30秒,并且测量结果在最后5秒测定。同时记录来自基准传感器和测量传感器的信号。该测量方法由插入样品开始。
由下列公式得到透射率并因此得到激光透明度:
LT=(信号(测量传感器)/信号(基准传感器))×100%。
该测量方法排除了激光器系统的变化和主观读取误差。
片材的平均LT值由至少5个测量值计算。对于每种材料,平均值基于10块片材计算。使用来自各片材的测量值的平均值对该材料计算平均值并还计算标准偏差。
透射光谱(Ulbricht测量)
透射光谱使用Ulbricht球测量几何结构在300-2500nm波长范围内测量。Ulbricht球为中空球,其内表面提供在宽光谱范围内的高且非取向(漫)反射。当辐射线冲击该球的内表面时,它发生多重反射,直到在该球内具有完全均匀分布。辐射线的该积分由于入射角、遮蔽、波型、偏振和其他性能而对所有效果平均。作为Ulbricht球的构造的函数,连接在该球内的检测器仅记录漫透射率,或者定向和漫透射率的总和(=总透射率)。
以透射模式使用具有连接的DRA 2500 Ulbricht系统的Varian Cary5000分光计(样品在辐射源和Ulbricht球之间)。为了测量总透射率,使用白色反射器(Labsphere Spectralon Standard)来封闭与样品相对的反射端口。为了测量漫透射比例,使用黑色光阱(DRA 2500标准光阱)来封闭该反射端口。透射率相对于入射辐射的强度表示。取向透射率以总透射率和漫透射率之间的差值计算。取向透射率相对于总透射率表示:
Figure BDA00002562323100211
表1
组分 B的量[重量%] B的量[mmol/kgPBT] LT1064nm[%T]
基准 0 0 30
E1 0.5 34.7 55
E2 0.5 25.0 42
E3 0.5 27.05 61
E4 0.5 22.9 36
E5 0.5 19.8 35
E6 0.5 26.4 41
E7 0.5 31.9 43
E8 0.5 23.5 39
E9 0.5 31.6 49
E10 0.5 34.5 51
E11 0.5 33.3 45
E12 0.5 37.6 60
E13 0.5 43.1 51
表2
选取的未增强配方的机械性能:
100重量%A/1,基准 99.5%A/1+0.5%B1
弹性模量 [MPa] 2511 2882
拉伸强度 [MPa] 56.4 57.2
断裂拉伸应变 [%] 170 2.4
无缺口冲击强度 [kJ/m^2] 不断裂 31.3
拉伸测试根据ISO 527。冲击强度测试根据ISO 179。
表3
组分 B的量[重量%] B的量[mmol/kgPBT] LT1064nm[%T]
基准 0 30
E1 0.01 0.7 30
E1 0.1 6.9 25
E1 0.2 13.9 30
E1 0.3 20.8 41
E1 0.4 27.8 47
E1 0.5 34.7 50
E1 0.75 52.0 56
E1 1 69.4 58
E1 1.5 104.1 55
E1 2 138.8 44
表4
对选取配方的Ulbricht透射率测量:
Figure BDA00002562323100221
abs:吸收依赖性透明度变化(谱带)
表5:
浓度系列,增强的(B4500+30重量%玻璃纤维)
组分 B的量[重量%] B的量[mmol/kgPBT] LT1064nm[%T]
基准 0 0 27
E1 0.01 0.9 27
E1 0.1 9.2 18
E1 0.3 27.7 36
E1 0.5 46.1 47
E1 0.75 69.2 52
表6
选取的增强配方的机械性能:
基准 +0.5%B1
弹性模量 [MPa] 9564 10485
拉伸强度 [MPa] 136 140
断裂拉伸应变 [%] 3.4 2.2
缺口冲击强度 [kJ/m2] 9.8 8.1
基准:70重量%A/1+30重量%C

Claims (13)

1.包含如下组分作为主要组分的热塑性模塑组合物在生产任意类型激光透明性模制品中的用途:
A)聚酯,
B)20-200mmol/kg聚酯A)的至少一种通式(I)化合物,
Figure FDA00002562323000011
其中各自独立地位于任意位置
-A1-为-NR-、-O-、-S-、-CH=A4-,其中R为H或C1-6烷基,A4为N或CH,
A2为COOX或OX,其中X为Li、Na、K、Rb、Cs、Mg/2、Ca/2、Sr/2、Ba/2、Al/3,
A3为C1-6烷基,C6-12芳基,C7-13烷芳基,C7-13芳烷基,O-C1-6烷基,O-C6-12芳基,O-C7-13烷芳基,O-C7-13芳烷基,其中X'为H或X的COOX'、OX'、SX'、SO3X',S-C1-6烷基,S-C6-12芳基,NR2,卤素,NO2
n为1-4的整数,和
m为0至4-n的整数,其中如果A3=NO2,则m=1,
条件是在基团COOX和OX以及SX'存在于通式(I)化合物的情况下mmol数基于这些基团,其中X′=X,以及还有
C)基于组分A)重量为0-230重量%其他添加物质。
2.根据权利要求1的用途,其中所述模塑组合物包含25-140mmol/kg聚酯A的组分B)。
3.根据权利要求1或2的用途,其中所述模制品的激光透明度为至少33%(对厚度为2mm的模制品在1064nm下测量)。
4.根据权利要求1-3中任一项的用途,其中在通式(I)化合物中,n的值为1或2,且m的值为0或1或2。
5.根据权利要求4的用途,其中n的值为1且m的值为0或1。
6.根据权利要求1-5中任一项的用途,其中X为Li、Na、K、Rb或Cs。
7.根据权利要求6的用途,其中X为Li、Na或K。
8.根据权利要求1-7中任一项的用途,其中A3为C1-6烷基、OX、SO3X、卤素或NO2
9.根据权利要求1-8中任一项的激光透明性模制品在借助激光透射熔接方法生产模制品中的用途。
10.根据权利要求1-8中任一项的用途,其用于经由激光透射熔接生产模制品。
11.根据权利要求10的用途,其中使用激光透射熔接将激光透明性模制品与激光吸收性模制品接合。
12.一种生产熔接模制品的方法,包括使用激光透射熔接将根据权利要求1-8中任一项的用途的激光透明性模制品与激光吸收性模制品接合。
13.一种可以根据权利要求12的方法得到的熔接模制品,所述模制品适合在电气、电子、电信、信息技术、计算机、家用、运动、医疗、汽车或娱乐领域中的应用。
CN201180028770.1A 2010-06-11 2011-06-10 包含有机添加剂的激光透明性pbt Active CN102939195B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10165713.8 2010-06-11
EP10165713 2010-06-11
PCT/EP2011/059673 WO2011154518A1 (de) 2010-06-11 2011-06-10 Lasertransparentes pbt mit organischen additiven

Publications (2)

Publication Number Publication Date
CN102939195A true CN102939195A (zh) 2013-02-20
CN102939195B CN102939195B (zh) 2015-12-02

Family

ID=44627860

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201180028770.1A Active CN102939195B (zh) 2010-06-11 2011-06-10 包含有机添加剂的激光透明性pbt

Country Status (6)

Country Link
EP (1) EP2580047B1 (zh)
JP (1) JP5843852B2 (zh)
KR (1) KR101889111B1 (zh)
CN (1) CN102939195B (zh)
BR (1) BR112012031483B1 (zh)
WO (1) WO2011154518A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116003975A (zh) * 2022-12-29 2023-04-25 江苏金发科技新材料有限公司 一种高激光焊接强度的pbt复合材料及其制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2963489B1 (en) 2014-06-30 2019-06-19 Samsung Display Co., Ltd. Curved display device
KR102189455B1 (ko) * 2018-12-21 2020-12-14 주식회사 삼양사 내열 치수 안정성이 뛰어난 백색 불투명한 레이저 용접가능한 열가소성 조성물
WO2024017700A1 (en) 2022-07-21 2024-01-25 Basf Se Molding composition comprising black colorant

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4393178A (en) * 1979-06-19 1983-07-12 Imperial Chemical Industries Plc Fast crystallizing polyester compositions
CN1320067A (zh) * 1998-10-01 2001-10-31 焊接研究院 焊接方法
US20040084140A1 (en) * 2002-08-29 2004-05-06 Toshikazu Kobayashi Process for laser welding poly(ethylene terephthalate)
CN1839031A (zh) * 2003-08-22 2006-09-27 E.I.内穆尔杜邦公司 把聚烯烃模塑制品激光焊接到其它热塑性树脂模塑制品的方法,以及由此方法制备的焊接制品
CN101511944A (zh) * 2006-06-30 2009-08-19 东丽株式会社 热塑性树脂组合物和它的模制品

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3651014A (en) 1969-07-18 1972-03-21 Du Pont Segmented thermoplastic copolyester elastomers
US4148846A (en) 1970-09-10 1979-04-10 Rohm And Haas Company Acrylic modifiers for polycarbonamides
DE2842005A1 (de) 1978-09-27 1980-04-10 Bayer Ag Polycarbonate mit alkylphenyl-endgruppen, ihre herstellung und ihre verwendung
DE3039114A1 (de) 1980-10-16 1982-05-13 Bayer Ag, 5090 Leverkusen Thermoplastische polyester-formmassen mit verbesserter zaehigkeit
DE3334782A1 (de) 1983-04-19 1984-10-25 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von polydiorganosiloxanen mit hydroxyaryloxy-endgruppen
DE3506472A1 (de) 1985-02-23 1986-08-28 Bayer Ag, 5090 Leverkusen Neue polydiorganosiloxan-polycarbonat-blockcopolymere
DE3524234A1 (de) 1985-07-06 1987-01-08 Bayer Ag Neue pfropfpolymerisate und deren abmischungen mit polyamiden
DE3606982A1 (de) 1986-03-04 1987-09-10 Bayer Ag Pfropfpolymerisate auf kautschukpolymeren mit blockartiger struktur
HU196394B (en) 1986-06-27 1988-11-28 Richter Gedeon Vegyeszet Process for preparing 2-halogenated ergoline derivatives
DE3725576A1 (de) 1987-08-01 1989-02-09 Bayer Ag Formmassen aus aromatischem polyester und gepfropftem silikonkautschuk
JPH01146958A (ja) 1987-12-04 1989-06-08 Polyplastics Co 熱可塑性樹脂組成物
DE3800603A1 (de) 1988-01-12 1989-07-20 Bayer Ag Formmassen aus aromatischen polyestern, vinyl-copolymerisaten und gepfropftem siliconkautschuk
DE3836176A1 (de) 1988-10-24 1990-05-03 Bayer Ag Polymermischungen
DE4401055A1 (de) 1994-01-15 1995-07-20 Basf Ag Verfahren zur Herstellung von thermoplastischen Polyestern mit niedrigem Carboxylendgruppengehalt
US5521258A (en) 1994-11-14 1996-05-28 General Electric Company Autoclave resistant blends of poly(ester-carbonate) and polyetherimide resins
US6151180A (en) 1998-04-15 2000-11-21 Samsung Electronics Co., Ltd. Method and apparatus for detecting defects on a disk in a hard disk drive
DE10054859A1 (de) 2000-11-06 2002-05-08 Basf Ag Verfahren zum Verbinden von Formteilen
CN1244620C (zh) 2000-11-13 2006-03-08 纳幕尔杜邦公司 适合激光焊接的着色热塑性树脂组合物,其所用蒽醌着色剂及其模塑制品
JP4456392B2 (ja) 2003-03-28 2010-04-28 ウィンテックポリマー株式会社 レーザー溶着用樹脂組成物及び成形品
DE10330722A1 (de) 2003-07-08 2005-02-10 Bayer Ag Laserdurchstrahlschweißbare thermoplastische Formmassen auf Basis einer Mischung von mindestens zwei Thermoplasten
JP4565958B2 (ja) 2003-10-07 2010-10-20 ウィンテックポリマー株式会社 レーザ溶着用樹脂組成物及び成形品
BRPI0508433B1 (pt) 2004-03-04 2012-12-25 materiais plÁsticos tingidos por corantes de modo transparente, translécido ou opaco, uso de partÍculas em nanoescala e processos para produÇço e solda do mesmo.
JP2007169358A (ja) 2005-12-20 2007-07-05 Mitsubishi Engineering Plastics Corp レーザー溶着用ポリエステル樹脂組成物およびこれを用いた成形品
JP2007186584A (ja) 2006-01-13 2007-07-26 Mitsubishi Engineering Plastics Corp レーザー溶着用ポリエステル樹脂組成物およびこれを用いた成形品
JP2008050578A (ja) * 2006-07-28 2008-03-06 Teijin Ltd 樹脂組成物およびその成形品
JP5245265B2 (ja) 2006-09-27 2013-07-24 東レ株式会社 レーザー溶着用ポリエステル樹脂組成物および複合成形体
JP2008163167A (ja) 2006-12-28 2008-07-17 Toray Ind Inc レーザー溶着用変性ポリエステル樹脂組成物およびそれを用いた複合成形体
JP2009019134A (ja) 2007-07-12 2009-01-29 Mitsubishi Engineering Plastics Corp レーザー溶着用ポリエステル樹脂組成物及びそれを用いた成形品
JP5155075B2 (ja) * 2008-09-16 2013-02-27 帝人株式会社 ポリ乳酸含有組成物及びその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4393178A (en) * 1979-06-19 1983-07-12 Imperial Chemical Industries Plc Fast crystallizing polyester compositions
CN1320067A (zh) * 1998-10-01 2001-10-31 焊接研究院 焊接方法
US20040084140A1 (en) * 2002-08-29 2004-05-06 Toshikazu Kobayashi Process for laser welding poly(ethylene terephthalate)
CN1839031A (zh) * 2003-08-22 2006-09-27 E.I.内穆尔杜邦公司 把聚烯烃模塑制品激光焊接到其它热塑性树脂模塑制品的方法,以及由此方法制备的焊接制品
CN101511944A (zh) * 2006-06-30 2009-08-19 东丽株式会社 热塑性树脂组合物和它的模制品

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DANA GARCIA: "《Hetrogeneous Nucleation of Poly(ethylene Terephthalate)》", 《JOURNAL OF POLYMER SCIENCE: POLYMER PHYSICS EDITION》 *
J.W.GILMER ET AL: "《The Use of Sodium Salts as Nucleation Agents for Polyethylene Terephthalate With Minimal Molecuar Weight Reduction》", 《POLYMER ENGINEERING AND SCIENCE》 *
R.LEGRAS ET AL: "《Chemical nucleation, a new concept applied to the mechanism of action of organic acid salts on the crystallization of polyethylene terephthalate and bisphenol-A polycarbonate》", 《POLYMER》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116003975A (zh) * 2022-12-29 2023-04-25 江苏金发科技新材料有限公司 一种高激光焊接强度的pbt复合材料及其制备方法

Also Published As

Publication number Publication date
BR112012031483B1 (pt) 2020-01-07
KR20130087491A (ko) 2013-08-06
JP5843852B2 (ja) 2016-01-13
EP2580047B1 (de) 2018-06-06
JP2013529688A (ja) 2013-07-22
BR112012031483A2 (pt) 2016-11-01
WO2011154518A1 (de) 2011-12-15
EP2580047A1 (de) 2013-04-17
CN102939195B (zh) 2015-12-02
KR101889111B1 (ko) 2018-08-16

Similar Documents

Publication Publication Date Title
US8889768B2 (en) Laser-transparent PBT with organic additives
US8318843B2 (en) Laser-transparent polyesters
CN102892819B (zh) 激光透明性聚酯
CN102939195B (zh) 包含有机添加剂的激光透明性pbt
CN103415565A (zh) 含有羧酸盐的激光透明聚酯
CN103619931A (zh) 含有碱金属亚硝酸盐的激光透明聚酯
CN103415563B (zh) 含有无机盐的激光透明聚酯
CN103415566B (zh) 激光透明性聚酯

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant