WO2017146196A1 - レーザー溶着用樹脂組成物及びその溶着体 - Google Patents
レーザー溶着用樹脂組成物及びその溶着体 Download PDFInfo
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- WO2017146196A1 WO2017146196A1 PCT/JP2017/007036 JP2017007036W WO2017146196A1 WO 2017146196 A1 WO2017146196 A1 WO 2017146196A1 JP 2017007036 W JP2017007036 W JP 2017007036W WO 2017146196 A1 WO2017146196 A1 WO 2017146196A1
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- WIPO (PCT)
- Prior art keywords
- mass
- laser
- resin
- resin composition
- polybutylene terephthalate
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
- B29C65/14—Joining 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
- B29C65/16—Laser beams
- B29C65/1603—Laser beams characterised by the type of electromagnetic radiation
- B29C65/1612—Infrared [IR] radiation, e.g. by infrared lasers
- B29C65/1616—Near infrared radiation [NIR], e.g. by YAG lasers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/20—Bonding
- B23K26/21—Bonding by welding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
- B29C65/14—Joining 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
- B29C65/16—Laser beams
- B29C65/1629—Laser beams characterised by the way of heating the interface
- B29C65/1632—Laser beams characterised by the way of heating the interface direct heating the surfaces to be joined
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
- B29C65/14—Joining 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
- B29C65/16—Laser beams
- B29C65/1629—Laser beams characterised by the way of heating the interface
- B29C65/1635—Laser 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
- B29C65/14—Joining 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
- B29C65/16—Laser beams
- B29C65/1629—Laser beams characterised by the way of heating the interface
- B29C65/1654—Laser beams characterised by the way of heating the interface scanning at least one of the parts to be joined
- B29C65/1658—Laser beams characterised by the way of heating the interface scanning at least one of the parts to be joined scanning once, e.g. contour laser welding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
- B29C65/14—Joining 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
- B29C65/16—Laser beams
- B29C65/1677—Laser beams making use of an absorber or impact modifier
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/78—Means for handling the parts to be joined, e.g. for making containers or hollow articles, e.g. means for handling sheets, plates, web-like materials, tubular articles, hollow articles or elements to be joined therewith; Means for discharging the joined articles from the joining apparatus
- B29C65/7802—Positioning the parts to be joined, e.g. aligning, indexing or centring
- B29C65/782—Positioning the parts to be joined, e.g. aligning, indexing or centring by setting the gap between the parts to be joined
- B29C65/7823—Positioning the parts to be joined, e.g. aligning, indexing or centring by setting the gap between the parts to be joined by using distance pieces, i.e. by using spacers positioned between the parts to be joined and forming a part of the joint
- B29C65/7826—Positioning the parts to be joined, e.g. aligning, indexing or centring by setting the gap between the parts to be joined by using distance pieces, i.e. by using spacers positioned between the parts to be joined and forming a part of the joint said distance pieces being non-integral with the parts to be joined, e.g. particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/82—Testing the joint
- B29C65/8207—Testing the joint by mechanical methods
- B29C65/8215—Tensile tests
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/01—General aspects dealing with the joint area or with the area to be joined
- B29C66/05—Particular design of joint configurations
- B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
- B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
- B29C66/112—Single lapped joints
- B29C66/1122—Single lap to lap joints, i.e. overlap joints
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/01—General aspects dealing with the joint area or with the area to be joined
- B29C66/05—Particular design of joint configurations
- B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
- B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
- B29C66/114—Single butt joints
- B29C66/1142—Single butt to butt joints
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
- B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
- B29C66/43—Joining a relatively small portion of the surface of said articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General 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
- B29C66/71—General 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General 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
- B29C66/73—General 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
- B29C66/733—General 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 optical properties of the material of the parts to be joined, e.g. fluorescence, phosphorescence
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General 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
- B29C66/73—General 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
- B29C66/733—General 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 optical properties of the material of the parts to be joined, e.g. fluorescence, phosphorescence
- B29C66/7332—General 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 optical properties of the material of the parts to be joined, e.g. fluorescence, phosphorescence at least one of the parts to be joined being coloured
- B29C66/73321—General 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 optical properties of the material of the parts to be joined, e.g. fluorescence, phosphorescence at least one of the parts to be joined being coloured both parts to be joined being coloured
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/80—General aspects of machine operations or constructions and parts thereof
- B29C66/81—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps
- B29C66/812—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the composition, by the structure, by the intensive physical properties or by the optical properties of the material constituting the pressing elements, e.g. constituting the welding jaws or clamps
- B29C66/8122—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the composition, by the structure, by the intensive physical properties or by the optical properties of the material constituting the pressing elements, e.g. constituting the welding jaws or clamps characterised by the composition of the material constituting the pressing elements, e.g. constituting the welding jaws or clamps
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/80—General aspects of machine operations or constructions and parts thereof
- B29C66/81—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps
- B29C66/812—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the composition, by the structure, by the intensive physical properties or by the optical properties of the material constituting the pressing elements, e.g. constituting the welding jaws or clamps
- B29C66/8126—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the composition, by the structure, by the intensive physical properties or by the optical properties of the material constituting the pressing elements, e.g. constituting the welding jaws or clamps characterised by the intensive physical properties or by the optical properties of the material constituting the pressing elements, e.g. constituting the welding jaws or clamps
- B29C66/81266—Optical properties, e.g. transparency, reflectivity
- B29C66/81267—Transparent to electromagnetic radiation, e.g. to visible light
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/80—General aspects of machine operations or constructions and parts thereof
- B29C66/83—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools
- B29C66/832—Reciprocating joining or pressing tools
- B29C66/8322—Joining or pressing tools reciprocating along one axis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/90—Measuring or controlling the joining process
- B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
- B29C66/919—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/90—Measuring or controlling the joining process
- B29C66/92—Measuring or controlling the joining process by measuring or controlling the pressure, the force, the mechanical power or the displacement of the joining tools
- B29C66/929—Measuring or controlling the joining process by measuring or controlling the pressure, the force, the mechanical power or the displacement of the joining tools characterized by specific pressure, force, mechanical power or displacement values or ranges
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/90—Measuring or controlling the joining process
- B29C66/93—Measuring or controlling the joining process by measuring or controlling the speed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/90—Measuring or controlling the joining process
- B29C66/95—Measuring or controlling the joining process by measuring or controlling specific variables not covered by groups B29C66/91 - B29C66/94
- B29C66/959—Measuring or controlling the joining process by measuring or controlling specific variables not covered by groups B29C66/91 - B29C66/94 characterised by specific values or ranges of said specific variables
- B29C66/9592—Measuring or controlling the joining process by measuring or controlling specific variables not covered by groups B29C66/91 - B29C66/94 characterised by specific values or ranges of said specific variables in explicit relation to another variable, e.g. X-Y diagrams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
- C08K5/08—Quinones
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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
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- 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
- C08K5/3462—Six-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Definitions
- the present invention relates to a laser-welded resin composition and a welded body, and a welded body obtained by laser welding a molded product obtained from a laser-welded resin composition has high welding strength and has a black coloring power. It is a polyester resin composition for laser welding that is high, excellent in heat discoloration resistance, and further excellent in laser welding processability.
- Thermoplastic polyester resin has excellent mechanical strength, chemical resistance, electrical insulation, etc., and has excellent heat resistance, moldability, and recyclability, so it is widely used in various equipment parts. It has been. In recent years, parts for automobiles have been reduced in weight in particular, and a high level of heat resistance is often demanded due to resin conversion of parts that have conventionally used metals, miniaturization of resin products, and the like. For this reason, reinforced thermoplastic resins containing fillers such as glass fibers are often used. Among them, thermoplastic polyester resins such as polybutylene terephthalate are excellent in mechanical strength and moldability, and are used in automotive electronic component cases and motor component cases. Widely used.
- Patent Document 1 a method using a copolymerized polybutylene terephthalate (Patent Document 1), a method of alloying a polybutylene terephthalate with a polycarbonate resin or a styrene resin (Patent Documents 2 and 3), Furthermore, a method of adding a specific oligomer (Patent Document 4) has been proposed. However, in these methods, sufficient weldability may not be obtained due to a gap between welding members caused by warpage deformation of a molded product. In addition, a method for improving weldability by adding a laser transmission absorbent such as nigrosine to a thermoplastic resin has been proposed (Patent Document 5), but a polyester resin composition suitable for laser welding has not been described. Absent.
- An object of the present invention is to provide a laser-welded polyester-based resin composition having excellent welding processability by laser, excellent black coloring power and heat discoloration, and excellent welding strength of a welded body obtained by laser welding. It is in.
- the present inventors have found that the above problems can be solved by using a specific thermoplastic polyester resin material in combination with nigrosine and a specific colorant, and have reached the present invention.
- the present invention relates to the following laser-welded resin composition, laser-welded molded body, and laser-welded body.
- the thermoplastic polyester resin material includes a polybutylene terephthalate homopolymer and a polybutylene terephthalate copolymer, and the content of the polybutylene terephthalate copolymer is 5 to 70% by mass with respect to a total of 100% by mass of both.
- thermoplastic polyester resin material includes a polybutylene terephthalate homopolymer and a polyethylene terephthalate resin, and the content of the polyethylene terephthalate resin is 5 to 50% by mass relative to the total of 100% by mass of both.
- thermoplastic polyester resin material includes a polybutylene terephthalate homopolymer and a polycarbonate resin, and the content of the polycarbonate resin is 5 with respect to a total of 100% by mass of the polybutylene terephthalate homopolymer and the polycarbonate resin.
- a molded article for laser welding comprising the resin composition for laser welding according to any one of [1] to [7].
- the laser welded body according to the above [9] wherein the welded body has a gap of 0.1 mm or more when the welded body is welded at least at a part of the welded portion.
- the laser welded body according to [9] or [10] in which the compacts are butted and welded together.
- the laser welded body according to [9] or [10] wherein the molded bodies are overlapped and welded together.
- the resin composition for laser welding of the present invention has excellent black coloring power and heat discoloration, has suitable laser welding processability, and a welded body obtained by laser welding a molded product of the resin composition has a welding strength and a black coloring. Also excellent in heat discoloration.
- FIG. 1 is an ultraviolet-visible spectroscopic spectrum diagram of each dye used in Production Example 1 of a colorant.
- FIG. 2 is a diagram showing an example of manufacturing a laser welded body by abutting a plurality of molded bodies and performing laser welding.
- FIG. 3 is a diagram showing an example of manufacturing a laser welded body by laminating a plurality of molded bodies and performing laser welding.
- FIG. 4 is a conceptual diagram showing a method of butt laser welding in the embodiment.
- FIG. 5 is a conceptual diagram showing a method of superposition laser welding in the embodiment.
- Nigrosine acts as a dye having laser light absorption, and has gentle absorption in the range of 800 nm to 1200 nm laser light.
- Nigrosine is C.I. I. Solvent Black 5 and C.I. I. It is a black azine-based condensation mixture as described in Color Index as Solvent Black 7. This can be synthesized, for example, by oxidation and dehydration condensation of aniline, aniline hydrochloride and nitrobenzene at a reaction temperature of 160 to 190 ° C. in the presence of iron chloride.
- Examples of commercially available nigrosine include “NUBIAN (registered trademark) BLACK series” (trade name, manufactured by Orient Chemical Industry Co., Ltd.).
- the content of (B) nigrosine is 0.0005 to 0.5 parts by mass with respect to 100 parts by mass of (A) the thermoplastic polyester resin material. Suitable conditions for controlling the calorific value are 0.001 to The amount is 0.1 part by mass, more preferably 0.003 to 0.05 part by mass, and still more preferably 0.005 to 0.03 part by mass. In addition, the said content is the quantity with respect to a total of 100 mass parts of these resin, when (A) thermoplastic polyester-type resin material which mentions later contains polycarbonate resin and / or aromatic vinyl resin together. .
- the incidence rate K of the resin composition for laser welding can be 20 to 80%, more preferably 25 to 75%, and particularly preferably 30 to 70%.
- the incident rate K is an incident rate with respect to a laser beam having a wavelength of 940 nm when the molded body is 1 mm thick.
- the gate part is 1.5 mm thick side
- the molded body is manufactured under the conditions of a cylinder temperature of 260 ° C., a mold temperature of 80 ° C., an injection speed of 120 mm / sec, an injection rate of 51 cm 3 / sec, and a surface progression coefficient of 405 cm 3 / sec ⁇ cm.
- the resin composition for laser welding may contain the other absorptive dye with respect to a laser beam, or a laser beam absorber in the effective range which can implement this invention.
- the maximum absorption wavelength is defined as the wavelength that exhibited the maximum absorption in an absorption spectrum obtained by measuring a solution dissolved in dimethylformamide (DMF) using an ultraviolet-visible spectrophotometer.
- the colorant has absorption in the visible region, (A) has good compatibility with the thermoplastic polyester resin material, and requires a combination of dyes with less scattering characteristics with respect to laser light. Even when exposed to high temperatures during melting or melting, it is desirable that the material does not easily fade and has excellent heat resistance.
- the anthraquinone dye C1 used as the (C) colorant of the present invention and having a maximum absorption wavelength in the range of 590 to 635 nm is usually a blue oil-soluble dye.
- this dye for example, the visibility is higher than that of a green anthraquinone dye, and even when a black mixed dye is combined, a subtractive color mixture can be used to combine a red dye and a yellow dye to increase coloring power. A colorant exhibiting black color can be obtained.
- anthraquinone dye C1 having a maximum absorption wavelength in the range of 590 to 635 nm it is preferable to select one having a measured value (decomposition start temperature) of a thermogravimetric analyzer TG / DTA in the presence of air of 300 ° C. or higher.
- a preferred anthraquinone dye C1 is C.I. as described in COLOR INDEX. I. Solvent Blue 97 (decomposition start temperature 320 ° C.), C.I. I. Solvent blue 104 (decomposition start temperature 320 degreeC) etc. are illustrated. One or more of them may be used.
- anthraquinone dye C1 examples include “NUBIAN (registered trademark) BLUE series” and “OPLAS (registered trademark) BLUE series” (both trade names, manufactured by Orient Chemical Industry Co., Ltd.).
- a perinone dye C2 having a maximum absorption wavelength in the range of 460 to 480 nm is used in combination with the anthraquinone dye C1.
- These are usually red oil-soluble dyes.
- Specific examples of such perinone dye C2 include C.I. I. Solvent Red 135, 162, 178, 179 etc. can be used. One or more of them may be used.
- the commercially available red perinone dye C2 include “NUBIAN (registered trademark) RED series, OPLAS (registered trademark) RED series” (both manufactured by Orient Chemical Industry Co., Ltd.) and the like.
- an anthraquinone dye C3 having good heat resistance having a maximum absorption wavelength in the range of 435 to 455 nm is used in combination.
- Anthraquinone dye C3 having a maximum absorption wavelength in the range of 435 to 455 nm is usually a yellow oil-soluble dye.
- Specific examples of the anthraquinone dye C3 having a maximum absorption wavelength in the range of 435 to 455 nm include C.I. I. Solvent Yellow 163, C.I. I. Vat Yellow 1, 2, 3, etc. can be used. One or more of them may be used.
- anthraquinone dye C3 examples include “NUBIAN (registered trademark) YELLOW series, OPLAS (registered trademark) YELLOW series” (both trade names, manufactured by Orient Chemical Industries). Can be mentioned.
- the colorant (C) used in the present invention includes an anthraquinone dye C1 having a maximum absorption wavelength in the range of 590 to 635 nm, a perinone dye C2 having a maximum absorption wavelength in the range of 460 to 480 nm, and a maximum absorption wavelength of 435 to 455 nm.
- the anthraquinone dye C3 in the range is used, but the hue of the oil-soluble dye constituting the (B) nigrosine and (C) colorant is changed depending on the compatibility with the polybutylene terephthalate homopolymer. In order to obtain a jet black molded plate, it is necessary to adjust the ratio of the oil-soluble dye constituting the colorant (C).
- the preferred ratio of C1: C2: C3 is 28-41: 24-39: 24-46.
- the colorant comprises a perinone dye C2 having a maximum absorption wavelength in the range of 460 to 480 nm and an anthraquinone dye C1 having a maximum absorption wavelength in the range of 590 to 635 nm.
- the colorant is preferably contained at a ratio of 0.61 to 1.50. In consideration of color developability and suppression of bleed-out by the resin composition of the present invention, it is more preferably 0.62 to 1.15.
- the content of the colorant (C) is 0.01 to 2 parts by weight, preferably 0.05 to 0.8 parts by weight, more preferably 100 parts by weight of the (A) thermoplastic polyester resin material. 0.1 to 0.6 parts by mass. By adjusting the content of the colorant to such a range, a laser welding resin composition having a high black coloring power can be obtained.
- the colorant may contain other dyes other than the above-mentioned C1, C2 and C3.
- other dyes include azo dyes, quinacridone dyes, dioxazine dyes, quinophthalone dyes, perylene dyes, perinone dyes ( And compounds such as isoindolinone dyes, azomethine dyes, triphenylmethane dyes, anthraquinone dyes (compounds having wavelengths different from those of C1 and C3 described above).
- thermoplastic polyester resin material (A) contained in the resin composition for laser welding of the present invention comprises a polybutylene terephthalate homopolymer (A1), a polybutylene terephthalate copolymer (A2a), a polyethylene terephthalate resin (A2b), or a polycarbonate resin. And at least one of (A2c).
- the polybutylene terephthalate homopolymer (A1) used in the thermoplastic polyester resin material (A) of the present invention is a polymer obtained by polycondensation of terephthalic acid as an acid component and 1,4-butanediol as an alcohol component. It is.
- the intrinsic viscosity of the polybutylene terephthalate homopolymer (A1) is preferably 0.5 to 2 dl / g. From the viewpoint of moldability and mechanical properties, those having an intrinsic viscosity in the range of 0.6 to 1.5 dl / g are preferred. If a material having an intrinsic viscosity lower than 0.5 dl / g is used, the obtained welding member tends to have a low mechanical strength. Moreover, in the thing higher than 2 dl / g, the fluidity
- the intrinsic viscosity is a value measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.
- the terminal carboxyl group amount of the polybutylene terephthalate homopolymer (A1) may be appropriately selected and determined, but is usually 60 eq / ton or less, preferably 50 eq / ton or less, and preferably 30 eq / ton or less. More preferably. If it exceeds 50 eq / ton, gas tends to be generated during the melt molding of the (A) thermoplastic polyester resin material.
- the lower limit value of the terminal carboxyl group amount is not particularly defined, but is usually 5 eq / ton.
- the terminal carboxyl group amount of the polybutylene terephthalate homopolymer (A1) is obtained by dissolving 0.5 g of resin in 25 mL of benzyl alcohol and titrating with 0.01 mol / l benzyl alcohol solution of sodium hydroxide. This is the required value.
- a conventionally known arbitrary method such as a method for adjusting polymerization conditions such as a raw material charge ratio during polymerization, a polymerization temperature, a pressure reduction method, a method for reacting a terminal blocking agent, etc. Just do it.
- the polybutylene terephthalate copolymer (A2a) used for the thermoplastic polyester resin material is preferably isophthalic acid, dimer acid, polytetramethylene glycol (PTMG) in addition to terephthalic acid and 1,4-butanediol. It is a polymer obtained by copolymerizing a polyalkylene glycol or the like.
- the proportion of the tetramethylene glycol component in the copolymer is preferably 3 to 40% by mass, and 5 to 30% by mass. % Is more preferable, and 10 to 25% by mass is still more preferable. By setting it as such a copolymerization ratio, it tends to be excellent in the balance between laser weldability and heat resistance, which is preferable.
- the ratio of the dimer acid component to the total carboxylic acid component is preferably 0.5 to 30 mol% as carboxylic acid groups. 1 to 20 mol% is more preferable, and 3 to 15 mol% is still more preferable. By setting it as such a copolymerization ratio, it exists in the tendency which is excellent in the balance of laser weldability, long-term heat resistance, and toughness, and is preferable.
- the proportion of the isophthalic acid component in the total carboxylic acid component is preferably 1 to 30 mol% as carboxylic acid groups. More preferred is ⁇ 20 mol%, and further more preferred is 3 to 15 mol%. By setting it as such a copolymerization ratio, it exists in the tendency which is excellent in the balance of laser weldability, heat resistance, injection moldability, and toughness, and is preferable.
- the polybutylene terephthalate copolymer (A2a) is preferably a copolymer polybutylene terephthalate copolymerized with polytetramethylene glycol or an isophthalic acid copolymerized polybutylene terephthalate.
- the intrinsic viscosity of the polybutylene terephthalate copolymer (A2a) is preferably 0.5 to 2 dl / g. In view of moldability and mechanical properties, those having an intrinsic viscosity in the range of 0.6 to 1.5 dl / g are preferred. If the intrinsic viscosity is lower than 0.5 dl / g, the resulting resin composition tends to have a low mechanical strength. Moreover, if it is higher than 2 dl / g, the fluidity of the resin composition may be deteriorated and the moldability may be deteriorated or the laser weldability may be deteriorated.
- the intrinsic viscosity is a value measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.
- the amount of terminal carboxyl groups of the polybutylene terephthalate copolymer (A2a) may be appropriately selected and determined, but is usually 60 eq / ton or less, preferably 50 eq / ton or less, and preferably 30 eq / ton or less. More preferably it is. If it exceeds 50 eq / ton, gas tends to be generated during melt molding of the resin composition.
- the lower limit value of the terminal carboxyl group amount is not particularly defined, but is usually 5 eq / ton.
- the amount of terminal carboxyl groups of the polybutylene terephthalate copolymer (A2a) is a value measured by titration using a 0.01 mol / l benzyl alcohol solution of sodium hydroxide by dissolving 0.5 g of resin in 25 mL of benzyl alcohol. is there.
- a method for adjusting the amount of terminal carboxyl groups a conventionally known arbitrary method such as a method for adjusting polymerization conditions such as a raw material charge ratio during polymerization, a polymerization temperature, a pressure reduction method, a method for reacting a terminal blocking agent, etc. Just do it.
- the content of the polybutylene terephthalate copolymer (A2a) is (A1).
- the polybutylene terephthalate copolymer (A2a) is preferably 5 to 70% by mass, more preferably 10 to 65% by mass, and still more preferably 20 to 60% by mass based on 100% by mass in total. % By mass, particularly preferably 30 to 55% by mass.
- the content of the polybutylene terephthalate copolymer (A2a) is less than 5% by mass, the laser transmittance and the laser welding strength are liable to be lowered, and when it exceeds 70% by mass, the moldability is liable to be lowered.
- the polyethylene terephthalate resin (A2b) used for the thermoplastic polyester resin material is a resin whose main constituent unit is an oxyethyleneoxyterephthaloyl unit composed of terephthalic acid and ethylene glycol for all constituent repeating units. A repeating unit having a configuration other than the ethyleneoxyterephthaloyl unit may be included.
- the polyethylene terephthalate resin is produced using terephthalic acid or a lower alkyl ester thereof and ethylene glycol as main raw materials, but other acid components and / or other glycol components may be used together as raw materials.
- Acid components other than terephthalic acid include phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3- Examples thereof include phenylenedioxydiacetic acid and structural isomers thereof, dicarboxylic acids such as malonic acid, succinic acid and adipic acid and derivatives thereof, and oxyacids such as p-hydroxybenzoic acid and glycolic acid or derivatives thereof.
- diol components other than ethylene glycol examples include 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, aliphatic glycols such as pentamethylene glycol, hexamethylene glycol, and neopentyl glycol, cyclohexane Examples include alicyclic glycols such as dimethanol, and aromatic dihydroxy compound derivatives such as bisphenol A and bisphenol S.
- the polyethylene terephthalate resin is a branched component, for example, trifunctional acid such as tricarballylic acid, trimellitic acid, trimellitic acid, etc., or tetrafunctional ester-like acid such as pyromellitic acid or glycerin, trimethylolpropane, pentane.
- An alcohol having a trifunctional or tetrafunctional ester-forming ability such as erythritol is copolymerized in an amount of 1.0 mol% or less, preferably 0.5 mol% or less, more preferably 0.3 mol% or less. There may be.
- the intrinsic viscosity of the polyethylene terephthalate resin (A2b) is preferably 0.3 to 1.5 dl / g, more preferably 0.3 to 1.2 dl / g, and particularly preferably 0.4 to 0.8 dl / g. .
- the intrinsic viscosity of the polyethylene terephthalate resin is a value measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.
- the concentration of the terminal carboxyl group of the polyethylene terephthalate resin (A2b) is preferably 3 to 60 eq / ton, more preferably 5 to 50 eq / ton, and even more preferably 8 to 40 eq / ton.
- concentration of the terminal carboxyl group of the polyethylene terephthalate resin (A2b) is preferably 3 to 60 eq / ton, more preferably 5 to 50 eq / ton, and even more preferably 8 to 40 eq / ton.
- the terminal carboxyl group concentration of the polyethylene terephthalate resin can be obtained by dissolving 0.5 g of polyethylene terephthalate resin in 25 mL of benzyl alcohol and titrating with 0.01 mol / L benzyl alcohol solution of sodium hydroxide. Value.
- a method for adjusting the amount of terminal carboxyl groups a conventionally known arbitrary method such as a method for adjusting polymerization conditions such as a raw material charge ratio during polymerization, a polymerization temperature, a pressure reduction method, a method for reacting a terminal blocking agent, etc. Just do it.
- the content of the polyethylene terephthalate resin (A2b) is that of (A1) and (A2b).
- the content is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and still more preferably 15 to 45% by mass with respect to the total of 100% by mass.
- the content of the polyethylene terephthalate homopolymer is less than 5% by mass, the laser light transmittance and the laser welding strength are liable to be lowered, and when it exceeds 50% by mass, the moldability is liable to be lowered.
- the polycarbonate resin (A2c) used for the thermoplastic polyester resin material may be branched heat obtained by reacting a dihydroxy compound or a small amount thereof with phosgene or a carbonic acid diester. It is a plastic polymer or copolymer.
- the production method of the polycarbonate resin is not particularly limited, and those produced by a conventionally known phosgene method (interfacial polymerization method) or melt method (transesterification method) can be used.
- the polycarbonate resin is preferable from the viewpoint of laser light transmittance and laser weldability.
- the raw dihydroxy compound is preferably an aromatic dihydroxy compound, such as 2,2-bis (4-hydroxyphenyl) propane (ie, bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, Examples include hydroquinone, resorcinol, 4,4-dihydroxydiphenyl, and preferably bisphenol A.
- aromatic dihydroxy compound such as 2,2-bis (4-hydroxyphenyl) propane (ie, bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene
- examples include hydroquinone, resorcinol, 4,4-dihydroxydiphenyl, and preferably bisphenol A.
- a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compound can also be used.
- polycarbonate resin (A2c) among the above, aromatic polycarbonate resins derived from 2,2-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl) propane and other
- aromatic polycarbonate copolymer derived from an aromatic dihydroxy compound is preferred. Further, it may be a copolymer such as a copolymer with a polymer or oligomer having a siloxane structure. Furthermore, you may mix and use 2 or more types of the polycarbonate resin mentioned above.
- the viscosity average molecular weight of the polycarbonate resin (A2c) is preferably from 5,000 to 30,000, more preferably from 10,000 to 28,000, and even more preferably from 14,000 to 24,000. If a material having a viscosity average molecular weight lower than 5000 is used, the obtained welding member tends to have a low mechanical strength. On the other hand, if it is higher than 30000, the fluidity of the resin composition may be deteriorated and the moldability may be deteriorated or the laser weldability may be deteriorated.
- the viscosity average molecular weight of the polycarbonate resin is a viscosity average molecular weight [Mv] converted from a solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent.
- the ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight Mw and the number average molecular weight Mn of the polycarbonate resin (A2c) measured by gel permeation chromatography (GPC) is 2 to 5. 2.5 to 4 is more preferable.
- Mw / Mn is too small, the fluidity in the molten state increases and the moldability tends to decrease.
- Mw / Mn is excessively large, the melt viscosity tends to increase and molding becomes difficult.
- the amount of terminal hydroxy groups of the polycarbonate resin (A2c) is preferably 100 ppm by mass or more, more preferably 200 ppm by mass or more, and still more preferably from the viewpoints of thermal stability, hydrolysis stability, color tone, and the like. It is 400 mass ppm or more, most preferably 500 mass ppm or more. However, it is usually 1500 mass ppm or less, preferably 1300 mass ppm or less, more preferably 1200 mass ppm or less, and most preferably 1000 mass ppm or less.
- the amount of terminal hydroxy groups of the polycarbonate resin is too small, the laser transmittance tends to be lowered, and the initial hue at the time of molding may be deteriorated.
- the amount of terminal hydroxy groups is excessively large, the residence heat stability and the moist heat resistance tend to decrease.
- the content of the polycarbonate resin (A2c) is the sum of (A1) and (A2c).
- the amount is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and still more preferably 15 to 45% by mass with respect to 100% by mass.
- the content of the polycarbonate resin is less than 5% by mass, the laser light transmittance and the laser welding strength are likely to be lowered, and when it exceeds 50% by mass, the moldability may be lowered.
- thermoplastic polyester resin material (A) can contain other thermoplastic resins other than the above (A1) and (A2a) to (A2c) as long as the effects of the present invention are not impaired.
- specific examples of the other thermoplastic resins include aromatic vinyl resins, polyacetal resins, polyphenylene oxide resins, polyphenylene sulfide resins, polysulfone resins, polyether sulfone resins, polyether imide resins, and polyether ketone resins. And polyolefin resins.
- the aromatic vinyl resin (A2d) is a polymer mainly composed of an aromatic vinyl compound.
- the aromatic vinyl compound include styrene, ⁇ -methylstyrene, paramethylstyrene, vinyltoluene, and vinylxylene. Styrene is preferred.
- a typical example of the aromatic vinyl resin is polystyrene (PS).
- PS polystyrene
- As the aromatic vinyl resin a copolymer obtained by copolymerizing an aromatic vinyl compound with another monomer can also be used.
- Typical examples include acrylonitrile-styrene copolymer (AS resin) obtained by copolymerizing styrene and acrylonitrile, and maleic anhydride-styrene copolymer (maleic anhydride modified polystyrene) obtained by copolymerizing styrene and maleic anhydride. Resin).
- AS resin acrylonitrile-styrene copolymer
- maleic anhydride-styrene copolymer maleic anhydride modified polystyrene
- a rubber-containing aromatic vinyl resin obtained by copolymerizing or blending rubber components can also be preferably used.
- the rubber component include conjugated diene hydrocarbons such as butadiene, isoprene and 1,3-pentadiene.
- butadiene rubber is preferably used.
- An acrylic rubber component can be used as the rubber component, but it is not preferable because it is poor in terms of toughness.
- the amount of the rubber component is usually 1% by mass or more and less than 50% by mass, preferably 3 to 40% by mass, more preferably 5 to 5% in all segments of the aromatic vinyl resin. 30% by mass, more preferably 5 to 20% by mass.
- rubber-containing polystyrene is preferable, butadiene rubber-containing polystyrene is more preferable, and high impact polystyrene (HIPS) is particularly preferable from the viewpoint of toughness.
- HIPS high impact polystyrene
- aromatic vinyl resin polystyrene, acrylonitrile-styrene copolymer (AS resin), butadiene rubber-containing polystyrene and maleic anhydride-modified polystyrene are preferable, and polystyrene and high impact polystyrene (HIPS) are particularly preferable.
- AS resin acrylonitrile-styrene copolymer
- HIPS high impact polystyrene
- the aromatic vinyl resin (A2d) preferably has a mass average molecular weight of 50,000 to 500,000, more preferably 100,000 to 400,000, particularly 150,000 to 300,000 as measured by GPC. If the molecular weight is less than 50,000, bleeding out is observed in the molded product, or decomposition gas is generated during molding, and it is difficult to obtain sufficient weld strength. If the molecular weight is greater than 500,000, sufficient fluidity and laser welding strength are obtained. It is difficult to improve.
- the aromatic vinyl resin (A2d) preferably has a melt flow rate (MFR) measured at 220 ° C. and 98 N of 0.1 to 50 g / 10 min. More preferably, it is 5 to 30 g / 10 minutes, and further preferably 1 to 20 g / 10 minutes. If the MFR is smaller than 0.1 g / 10 min, the compatibility with the (A1) polybutylene terephthalate resin tends to be insufficient, and the appearance of delamination may occur during injection molding. On the other hand, if the MFR is larger than 50 g / 10 minutes, the impact resistance may be greatly reduced, which is not preferable.
- MFR melt flow rate
- the MFR measured at 200 ° C. and 48 N is preferably 1 to 50 g / 10 minutes, more preferably 3 to 35 g / 10 minutes. Preferably, it is 5 to 20 g / 10 minutes.
- the MFR measured at 200 ° C. and 49 N is preferably 0.1 to 40 g / 10 minutes, and preferably 0.5 to 30 g / 10 minutes. More preferably, it is 0.8 to 20 g / 10 min.
- thermoplastic polyester resin material contains polybutylene terephthalate homopolymer (A1) and polybutylene terephthalate copolymer (A2a), and further aromatic vinyl resin (A2d), aromatic vinyl resin (A2d)
- the content of is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and still more preferably 20 to 40% by mass with respect to 100% by mass in total of these resins.
- the content of the aromatic vinyl resin is less than 10% by mass, the laser light transmittance and the laser welding strength are likely to be lowered, and when it exceeds 50% by mass, the heat resistance and the heat discoloration are easily lowered.
- thermoplastic polyester resin material contains polybutylene terephthalate homopolymer (A1) and polyethylene terephthalate copolymer (A2b), and further an aromatic vinyl resin (A2d), the aromatic vinyl resin (A2d)
- the content is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and still more preferably 20 to 40% by mass with respect to 100% by mass in total of these resins.
- the content of the aromatic vinyl resin is less than 10% by mass, the laser light transmittance and the laser welding strength are likely to be lowered, and when it exceeds 50% by mass, the heat resistance and the heat discoloration are easily lowered.
- thermoplastic polyester resin material contains the polybutylene terephthalate homopolymer (A1) and the polycarbonate resin (A2c), and further the aromatic vinyl resin (A2d), the content ratio is 100 in total of these resins. It is preferable that the polybutylene terephthalate homopolymer (A1) is 30 to 90% by mass, and the aromatic vinyl resin (A2d) and the polycarbonate resin (A2c) are at most 50% by mass, respectively.
- the more preferable content of the polybutylene terephthalate homopolymer (A1) is 40 to 40% on the basis of a total of 100% by mass of the polybutylene terephthalate homopolymer (A1), the aromatic vinyl resin (A2d) and the polycarbonate resin (A2c). It is 80% by mass, and more preferably 50 to 70% by mass. When the content is less than 30% by mass, the heat resistance tends to be lowered, and when it exceeds 90% by mass, the laser transmittance tends to be lowered.
- the content of the aromatic vinyl resin (A2d) is more preferably 1 with respect to 100% by mass in total of the polybutylene terephthalate homopolymer (A1), the aromatic vinyl resin (A2d) and the polycarbonate resin (A2c). It is ⁇ 50 mass%, more preferably 3 to 45 mass%, particularly preferably 5 to 40 mass%. If the content is less than 1% by mass, the laser weldability and toughness become poor, and if it exceeds 50% by mass, the heat resistance tends to decrease.
- the content of the polycarbonate resin (A2c) is more preferably 1 to 50 mass with respect to 100 mass% of the total of the polybutylene terephthalate homopolymer (A1), the aromatic vinyl resin (A2d) and the polycarbonate resin (A2c). %, More preferably 3 to 45% by mass, particularly preferably 5 to 40% by mass.
- the content is less than 1% by mass, the laser light transmittance and the laser weldability are liable to be lowered, and the dispersion of the aromatic vinyl resin is poor, and the surface appearance of the molded product is liable to be lowered. If it exceeds 50% by mass, transesterification with the polybutylene terephthalate homopolymer proceeds, and the residence heat stability tends to decrease.
- the total content of the aromatic vinyl resin (A2d) and the polycarbonate resin (A2c) is 100% by mass in total of the polybutylene terephthalate homopolymer (A1), the aromatic vinyl resin (A2d), and the polycarbonate resin (A2c).
- the content is preferably 10 to 50% by mass, more preferably 20 to 50% by mass, and still more preferably 25 to 45% by mass. By setting it as such content, it exists in the tendency which is excellent in the balance of heat resistance and laser beam transmittance, and is preferable.
- the content ratio of the aromatic vinyl resin (A2d) and the polycarbonate resin (A2c) is preferably 5: 1 to 1: 5 by mass ratio and 4: 1 to 1: 4. Is more preferable. By setting it as such a content ratio, it exists in the tendency which is excellent in the balance of heat resistance and laser beam transmittance, and is preferable.
- the crystallization temperature (Tc) of the obtained resin composition is preferably 190 ° C. or lower. That is, laser transmissivity can be further improved by appropriately suppressing the transesterification reaction between the polybutylene terephthalate homopolymer and the polycarbonate resin and appropriately reducing the crystallization temperature.
- the crystallization temperature (Tc) is more preferably 188 ° C. or lower, further preferably 185 ° C. or lower, particularly preferably 182 ° C. or lower, and most preferably 180 ° C. or lower.
- the minimum is 160 degreeC normally, Preferably it is 165 degreeC or more.
- the crystallization temperature (Tc) was raised from 30 to 300 ° C. at a heating rate of 20 ° C./min and held at 300 ° C. for 3 minutes using a differential scanning calorimetry (DSC) machine. Thereafter, it is defined as the peak top temperature of an exothermic peak observed when the temperature is lowered at a temperature lowering rate of 20 ° C./min.
- the laser welding resin composition of the present invention can be blended with various additives as desired.
- additives include, for example, reinforcing fillers, impact modifiers, flow modifiers, auxiliary colorants, dispersants, stabilizers, plasticizers, UV absorbers, light stabilizers, antioxidants, charging Examples include inhibitors, lubricants, mold release agents, crystal accelerators, crystal nucleating agents, flame retardants, and epoxy compounds.
- the reinforcing filler that can be contained in the resin composition of the present invention has an effect of improving the mechanical properties of the resin composition obtained by blending with the resin, and a conventional inorganic filler for plastics is used.
- a conventional inorganic filler for plastics is used.
- fibrous fillers such as glass fiber, carbon fiber, basalt fiber, wollastonite and potassium titanate fiber can be used.
- granular or amorphous fillers such as calcium carbonate, titanium oxide, feldspar minerals, clays, organic clays, glass beads, etc .; plate-like fillers such as talc; scaly forms such as glass flakes, mica and graphite A filler can also be used.
- a fibrous filler particularly glass fiber
- the glass fiber either a round sectional shape or an irregular sectional shape can be used.
- the reinforcing filler is surface-treated with a surface treatment agent such as a coupling agent.
- the glass fiber to which the surface treatment agent is attached is preferable because it is excellent in durability, heat and humidity resistance, hydrolysis resistance, and heat shock resistance.
- any conventionally known one can be used, and specific examples include silane coupling agents such as aminosilane, epoxysilane, allylsilane, and vinylsilane.
- silane coupling agents such as aminosilane, epoxysilane, allylsilane, and vinylsilane.
- aminosilane-based surface treatment agents are preferable, and specifically, for example, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, and ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane are preferable. Take as an example.
- the surface treatment agent examples include a novolac type epoxy resin surface treatment agent, a bisphenol A type epoxy resin surface treatment agent, and the like, and a treatment with a novolac type epoxy resin surface treatment agent is particularly preferable.
- the silane-based surface treatment agent and the epoxy resin-based surface treatment agent may be used singly or in combination, and it is also preferable to use both in combination.
- the glass fiber is preferably a glass fiber having an anisotropic cross-sectional shape in which the ratio of the major axis to the minor axis in the cross section is 1.5 to 10 from the viewpoints of laser weldability and heat shock resistance.
- the cross-sectional shape is preferably a rectangular or oval cross section, and has a major axis / minor axis ratio of 2.5 to 8, more preferably 3 to 6.
- the major axis is D 2
- the minor axis is D 1
- the average fiber length is L
- the aspect ratio ((L ⁇ 2) / (D 2 + D 1 )) is preferably 10 or more.
- the content of the reinforcing filler is preferably 5 to 150 parts by mass with respect to 100 parts by mass of the (A) thermoplastic polyester resin material.
- the content of the reinforcing filler is less than 5 parts by mass, sufficient strength and heat resistance are difficult to obtain, and when it exceeds 150 parts by mass, fluidity and laser weldability tend to be lowered.
- a more preferable content of the reinforcing filler is 15 to 130 parts by mass, further preferably 20 to 120 parts by mass, and particularly preferably 30 to 100 parts by mass.
- the impact modifier that can be contained in the resin composition of the present invention functions to improve the heat shock resistance of the resin composition.
- the impact resistance improver is not particularly limited as long as it has the effect of improving the impact resistance of the resin, but polyester elastomer, styrene elastomer, polyolefin elastomer, acrylic elastomer, polyamide elastomer, polyurethane elastomer. , Fluorine-based elastomers, silicone-based elastomers, acrylic core / shell type elastomers and the like are known, and polyester-based elastomers and styrene-based elastomers are preferable.
- the polyester elastomer is a thermoplastic polyester having rubber properties at room temperature, preferably a thermoplastic elastomer mainly composed of a polyester block copolymer, and has a high melting point and high crystallinity as a hard segment.
- a block copolymer having an amorphous polyester or an amorphous polyether as a soft segment is preferable.
- the content of the soft segment of the polyester elastomer is at least 20 to 95 mol% in all segments, and 50 to 50 in the case of a block copolymer of polybutylene terephthalate and polytetramethylene glycol (PBT-PTMG copolymer). 95 mol%.
- the preferred soft segment content is 50 to 90 mol%, particularly 60 to 85 mol%.
- a polyester ether block copolymer, particularly a PTMG-PBT copolymer is preferable because the decrease in transmittance is reduced.
- polyester elastomers include “Primalloy” (trade name, registered trademark (hereinafter the same)) manufactured by Mitsubishi Chemical Corporation, “Perprene” (manufactured by Toyobo), “Hytrel” (manufactured by Toray DuPont), “ “Byron” (manufactured by Toyobo Co., Ltd.), “Polyester” (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and the like are preferred.
- “Primalloy” trade name, registered trademark (hereinafter the same) manufactured by Mitsubishi Chemical Corporation
- Perprene manufactured by Toyobo
- Hytrel manufactured by Toray DuPont
- Byron manufactured by Toyobo Co., Ltd.
- Polyyester manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
- the styrene-based elastomer is preferably composed of a styrene component and an elastomer component, and the styrene component is usually contained in a proportion of 5 to 80% by mass, preferably 10 to 50% by mass, particularly 15 to 30% by mass.
- the elastomer component at this time include conjugated diene hydrocarbons such as butadiene, isoprene and 1,3-pentadiene. More specifically, a copolymer of styrene and butadiene (SBS) elastomer, styrene and Examples thereof include a copolymer (SIS) elastomer with isoprene. It is also preferable to use a resin (SEBS, SEPS) obtained by hydrogenating the above SBS elastomer or SIS elastomer.
- SEBS resin
- styrene elastomers include “Dynalon” (manufactured by JSR, trade name and registered trademark (hereinafter the same)), “Tuftec” (manufactured by Asahi Kasei Chemicals), “Hibler”, “Septon” (manufactured by Kuraray) Etc.
- a copolymer-type elastomer containing an epoxy group is also preferable because it has good reactivity with a thermoplastic polyester resin such as polybutylene terephthalate and the laser transmittance is hardly lowered.
- the type of copolymer elastomer containing an epoxy group is not limited. For example, those obtained by introducing an epoxy group into the above-described styrene elastomer, polyolefin elastomer, acrylic elastomer and the like are preferable.
- an epoxy group-containing elastomer can be obtained by epoxidizing an unsaturated double bond portion of a diene component.
- the olefin-based elastomer only needs to have a polyolefin portion in the soft phase, and ethylene propylene rubber such as EPR and EPDM can be preferably used.
- the method for introducing an epoxy group is not particularly limited, and it may be incorporated into the main chain, or a polymer containing an epoxy group may be introduced into the olefin elastomer in a block or graft form.
- a (co) polymer having an epoxy group is introduced in a graft form.
- copolymer-type elastomers containing epoxy groups include “Bond First” (trade name, registered trademark (hereinafter the same)) manufactured by Sumitomo Chemical Co., Ltd., “Rotada” (manufactured by Arkema), “Elvalloy” (Mitsui DuPont Polychemical Co., Ltd., “Paraloid” (Rohm and Haas Co., Ltd.), “Metabrene” (Mitsubishi Rayon Co., Ltd.), “Epofriend” (Daicel Chemical Industries Co., Ltd.) and the like.
- the impact modifiers may be used alone or in combination of two or more.
- the content of the impact resistance improver is 0 to 20 parts by weight, preferably 1 to 18 parts by weight, more preferably 2 to 15 parts by weight, and still more preferably 100 parts by weight of the thermoplastic polyester resin material (A). 3 to 12 parts by mass, particularly preferably 3 to 7 parts by mass. If the content of the impact resistance improver exceeds 20 parts by mass, the heat resistance rigidity tends to decrease.
- the epoxy compound that can be contained in the resin composition of the present invention functions to improve the laser weldability and heat-and-moisture resistance properties of the resin composition, and to further improve the strength and durability of the weld part of the molded product.
- the epoxy compound is not particularly limited as long as it has one or more epoxy groups in one molecule, and is usually a glycidyl compound which is a reaction product of alcohol, phenol or carboxylic acid and epichlorohydrin, or an olefinic compound. A compound obtained by epoxidizing a heavy bond may be used.
- the epoxy compound include, for example, bisphenol type epoxy compounds such as bisphenol A type epoxy compounds and bisphenol F type epoxy compounds, resorcin type epoxy compounds, novolac type epoxy compounds, alicyclic compound type diepoxy compounds, glycidyl ethers, Examples thereof include glycidyl esters and epoxidized polybutadiene.
- the alicyclic compound type epoxy compound include vinylcyclohexene dioxide and dicyclopentadiene oxide.
- glycidyl ethers include monoglycidyl ethers such as methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, phenyl glycidyl ether, butylphenyl glycidyl ether, and allyl glycidyl ether; Examples include pentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, propylene glycol diglycidyl ether, and bisphenol A diglycidyl ether.
- monoglycidyl ethers such as methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl
- glycidyl esters examples include monoglycidyl esters such as benzoic acid glycidyl ester and sorbic acid glycidyl ester; adipic acid diglycidyl ester, terephthalic acid diglycidyl ester, orthophthalic acid diglycidyl ester, and the like.
- the epoxy compound may be a copolymer having a glycidyl group-containing compound as one component.
- a copolymer of ⁇ , ⁇ -unsaturated glycidyl ester and one or more monomers selected from the group consisting of ⁇ -olefin, acrylic acid, acrylic acid ester, methacrylic acid, and methacrylic acid ester can be mentioned.
- the epoxy compound is preferably an epoxy compound having an epoxy equivalent of 100 to 500 g / eq and a number average molecular weight of 2000 or less.
- the epoxy equivalent is less than 100 g / eq, since the amount of the epoxy group is too large, the viscosity of the resin composition is increased, and the adhesiveness of the weld portion is likely to be reduced.
- the epoxy equivalent exceeds 500 g / eq, the amount of the epoxy group decreases, and thus the effect of improving the heat and moisture resistance of the resin composition tends not to be sufficiently exhibited.
- the number average molecular weight exceeds 2000, the compatibility with the (A) thermoplastic polyester resin material tends to decrease, and the mechanical strength of the molded product tends to decrease.
- the epoxy compound a bisphenol A type epoxy compound or a novolac type epoxy compound obtained from a reaction of bisphenol A or novolak with epichlorohydrin is particularly preferable.
- the content of the epoxy compound is 0 to 5 parts by mass with respect to 100 parts by mass of the (A) thermoplastic polyester resin material. If the content is more than 3 parts by mass, crosslinking may proceed and the fluidity at the time of molding may deteriorate, so 0.2 to 3 parts by mass, particularly 0.2 to 2 parts by mass is preferable.
- Examples of the flow modifier that can be contained in the resin composition of the present invention include styrene oligomers, olefin oligomers, acrylic oligomers, polyfunctional compounds, branched polymers (dendrimers (dendritic polymers), highly branched types, hyper-types). Branched and cyclic oligomers are included), and the like is preferably exemplified and plays a role of imparting fluidity and maintaining mechanical strength. In particular, when a box-shaped welded body or a welded body having a flow length of 70 mm or more is produced, the addition of a flow modifier is effective.
- a phosphorus stabilizer As the stabilizer that can be contained in the resin composition of the present invention, a phosphorus stabilizer, a sulfur stabilizer, and a phenol stabilizer are preferable. Particularly preferred is a phenol-based stabilizer.
- the resin composition contains a polyethylene terephthalate resin or a polycarbonate resin, it is preferable to use a phenol-based stabilizer and a phosphorus-based stabilizer in combination.
- the phosphorus stabilizer include phosphorous acid, phosphoric acid, phosphite ester, phosphate ester, etc. Among them, organic phosphate compounds, organic phosphite compounds, or organic phosphonite compounds are preferable.
- the organic phosphate compound is preferably the following general formula: (R 1 O) 3-n P ( ⁇ O) OH n (1)
- R 1 is an alkyl group or an aryl group, which may be the same or different.
- N represents an integer of 0 to 2). More preferably, R 1 is a long-chain alkyl acid phosphate compound having 8 to 30 carbon atoms.
- alkyl group having 8 to 30 carbon atoms include octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, hexadecyl group Group, octadecyl group, eicosyl group, triacontyl group and the like.
- Examples of the long-chain alkyl acid phosphate include octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, octadecyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid cyclophosphate, nonyl phenyl cyclo acid phosphate Acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, di Chi le acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phosphate, diphenyl acid
- the organic phosphite compound is preferably the following general formula: R 2 O—P (OR 3 ) (OR 4 ) (2) (In the formula (2), R 2 , R 3 and R 4 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and R 2 , R 3 and R 4 are At least one of which is an aryl group having 6 to 30 carbon atoms.).
- organic phosphite compound examples include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tris (tridecyl).
- the organic phosphonite compound is preferably the following general formula: R 5 -P (OR 6 ) (OR 7 ) (3) (In Formula (6), R 5 , R 6 and R 7 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and R 5 , R 6 and R 7 are At least one of which is an aryl group having 6 to 30 carbon atoms.).
- organic phosphonite compound examples include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl) -4,4′-biphenyl.
- any conventionally known sulfur atom-containing compound can be used, and among these, thioethers are preferred.
- pentaerythritol tetrakis (3-dodecylthiopropionate) is preferable
- phenol-based stabilizer examples include pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionate, thiodiethylenebis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), pentaerythritol tetrakis (3- (3,5-di-neopentyl-4-hydroxyphenyl) ) Propionate) and the like.
- pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate is preferred.
- 1 type of stabilizer may be contained and 2 or more types may be contained in arbitrary combinations and ratios.
- the content of the stabilizer is preferably 0.001 to 2 parts by mass with respect to 100 parts by mass of the (A) thermoplastic polyester resin material.
- the content of the stabilizer is more preferably 0.001 to 1.8 parts by mass, and still more preferably 0.1 to 1.5 parts by mass.
- release agent that can be contained in the resin composition of the present invention
- known release agents that are usually used for polyester resins can be used.
- polyolefin compounds, fatty acid ester compounds, and silicone compounds can be used.
- One or more mold release agents selected are preferred.
- polyolefin compound examples include compounds selected from paraffin wax and polyethylene wax. Among them, those having a mass average molecular weight measured by GPC of 700 to 10,000, more preferably 900 to 8,000 are preferable.
- a modified polyolefin compound in which a hydroxyl group, a carboxyl group, a hydroxyl group, an epoxy group or the like is introduced into the side chain is particularly preferable.
- fatty acid ester compounds examples include fatty acid esters such as glycerin fatty acid esters, sorbitan fatty acid esters, and pentaerythritol fatty acid esters, and partially saponified products thereof, among which 11 to 28 carbon atoms, preferably 17 carbon atoms.
- Fatty acid esters composed of ⁇ 21 fatty acids are preferred. Specific examples include glycerol monostearate, glycerol monobehenate, glycerol dibehenate, glycerol-12-hydroxy monostearate, sorbitan monobehenate, pentaerythritol distearate, pentaerythritol tetrastearate and the like.
- the silicone compound is preferably a modified compound from the viewpoint of compatibility with a polyester resin.
- the modified silicone oil include silicone oil in which an organic group is introduced into the side chain of polysiloxane, silicone oil in which an organic group is introduced into both ends and / or one end of polysiloxane, and the like.
- the organic group to be introduced include an epoxy group, an amino group, a carboxyl group, a carbinol group, a methacryl group, a mercapto group, and a phenol group, and preferably an epoxy group.
- a silicone oil in which an epoxy group is introduced into the side chain of polysiloxane is particularly preferable.
- the content of the release agent is preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of the (A) thermoplastic polyester resin material. If the amount is less than 0.05 parts by mass, the surface property tends to decrease due to poor mold release at the time of melt molding, while if it exceeds 2 parts by mass, the kneading workability of the resin composition decreases, Cloudiness may be seen on the surface of the molded product.
- the content of the release agent is preferably 0.07 to 1.5 parts by mass, more preferably 0.1 to 1.0 parts by mass.
- the resin composition of this invention can carry out in accordance with the conventional method of resin composition preparation.
- the components and various additives added as desired are mixed together and then melt-kneaded in a single or twin screw extruder.
- the resin composition of the present invention can also be prepared without mixing each component in advance or by mixing only a part of the components in advance and supplying them to an extruder using a feeder and melt-kneading them.
- (A) a master batch is prepared by melt-kneading a mixture of a part of the resin constituting the thermoplastic polyester resin material with a part of the other resin, and then the remaining polyester resin or other
- fibrous reinforcement fillers such as glass fiber
- the heating temperature at the time of melt kneading can be appropriately selected from the range of usually 220 to 300 ° C. If the temperature is too high, decomposition gas is likely to be generated, which may cause opacity. Therefore, it is desirable to select a screw configuration in consideration of shear heat generation. In order to suppress decomposition during kneading or molding in the subsequent process, it is desirable to use an antioxidant or a heat stabilizer.
- the manufacturing method of a molded object is not specifically limited,
- injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold were used.
- the converted absorbance a of the molded product before laser welding is preferably 0.05 to 1.0, and more preferably 0.08 to 0.9.
- the spread of the resin melt in laser welding size of the melt pool
- practically sufficient welding strength can be obtained also in butt welding.
- the width of laser welding processability is widened at the time of superposition welding and butt welding because of excellent gap weldability.
- the converted absorbance a can be adjusted depending on the alloy type of the base resin, additives such as an elastomer and a reinforcing material, and further the amount of nigrosine.
- the converted absorbance a is determined by calculating the transmittance T (%) and reflectance R (%) at a wavelength of 940 nm using an ultraviolet-visible near-infrared spectrophotometer (“UV-3100PC” manufactured by Shimadzu Corporation). And obtained by the following equation.
- UV-3100PC ultraviolet-visible near-infrared spectrophotometer
- the conversion light absorbency converted into 1 mm thickness is calculated
- Absorbance a ⁇ log ⁇ T / (100 ⁇ R) ⁇
- the incidence rate K of the molded product before laser welding is preferably in the range of 20 to 80%, more preferably 25 to 75%, and particularly preferably 30 to 70. % Range.
- the incidence rate is less than 20%, the butt welding performance is lowered and the gap welding performance is also lowered.
- the incidence rate exceeds 80% the welding performance is lowered due to the overlapping, and the gap welding performance is also lowered.
- the incident rate K is adjusted to such a range, the amount of transmitted laser light and the amount of absorbed laser light are adjusted, so that a molded body made of a laser light transmitting resin and a laser as in conventional laser welding.
- the incidence rate can be adjusted to a preferred range by controlling the crystallization temperature (Tc) to be low.
- Tc crystallization temperature
- the incidence rate varies greatly depending on the transmittance of the laser beam.
- Molding conditions can be cited as factors that change the transmittance. Examples of molding conditions include injection rate, mold temperature, resin temperature, and pressure holding. Above all, it tends to change depending on the injection rate and mold temperature. Also, the mold structure is likely to change depending on the mold surface property, gate shape, gate position, and number of gates. Furthermore, in the molded body, it varies greatly depending on the part where the transmittance is measured and the distance from the gate position at the time of molding. Therefore, the incident rate can be adjusted to a preferable range by appropriately determining these conditions.
- the crystallization temperature (Tc) is preferably 188 ° C. or lower, more preferably 185 ° C. or lower, further preferably 182 ° C. or lower, and particularly preferably 180 ° C. or lower. Moreover, the minimum is 160 degreeC normally, Preferably it is 165 degreeC or more.
- the crystallization temperature (Tc) is measured by DSC. The details are as described in the examples.
- molded using the resin composition of this invention shows the outstanding black coloring.
- it is represented by a color difference ⁇ E00 from a standard plate showing standard black.
- the color difference ⁇ E00 is obtained by the CIE2000 color difference formula.
- ⁇ E00 is an evaluation method that is closer to the sense of human eyes than ⁇ E, which is a general evaluation method. The closer the blackness of the standard plate is, the smaller the numerical value. Is suitable. Moreover, it is preferable that the value is 6.0 or less.
- the laser welding resin composition of the present invention is molded into a laser welding member having a desired shape by an injection molding method.
- the injection molding method for example, a high-speed injection molding method, an injection compression molding method, or the like can be used.
- the conditions for injection molding are not particularly limited, but the injection speed is preferably 10 to 500 mm / sec, more preferably 30 to 400 mm / sec, further preferably 50 to 300 mm / sec, and particularly preferably 80 to 200 mm / sec. preferable. Note that the faster the emission speed, the higher the transmittance, which affects the incidence rate. However, if the injection speed is too high, gas burning occurs at the flow end of the molded body, so it is preferable to take measures such as reducing the injection speed to an appropriate injection speed or increasing the size of the gas vent in the mold structure.
- the resin temperature is preferably 250 to 280 ° C, more preferably 255 to 275 ° C.
- the mold temperature is preferably 40 to 130 ° C, more preferably 50 to 100 ° C. The lower the mold temperature, the higher the transmittance, which in turn affects the incidence rate. If the mold temperature is too low, the degree of crystallinity of the molded product will be low, resulting in increased post-shrinkage and deterioration in dimensional stability. It is also preferable to adjust the mold temperature.
- the injection rate defined as the resin material capacity per unit time injected from the discharge nozzle of the injection molding machine to the mold cavity is preferably 10 to 300 cm 3 / sec, and 15 to 200 cm 3 / sec. More preferably, 25 to 100 cm 3 / sec is still more preferable, and 50 to 90 cm 3 / sec is particularly preferable.
- the injection rate in such a range, it is possible to adjust the incidence rate of the welded portion such as the non-gate side portion of the injection molded member to a preferable range, and by adjusting the gate position, welding in the member is possible. It becomes possible to further adjust the incidence rate of the part to an appropriate range.
- the volume of resin material injected in one injection is controlled by adjusting the injection volume of resin material per unit time and the time required for injection, but the material capacity of resin material per unit time is injected. Rate (unit: cm 3 / sec).
- the surface progression coefficient defined below is 100 to 1200 cm 3 / sec ⁇ cm.
- the incidence rate of the part opposite to the gate of the member can be adjusted to a preferable range, and by adjusting the gate position, the incidence rate of the welded part in the member is further adjusted to an appropriate range. Adjustment is possible.
- Surface progression coefficient a value obtained by dividing the injection rate by the average thickness of the mold cavity into which the resin material is injected.
- a preferable range of the surface progression coefficient is 200 to 1100 cm 3 / sec ⁇ cm, more preferably 250 to 1000 cm 3. / Sec ⁇ cm, more preferably 300 to 950 cm 3 / sec ⁇ cm, and particularly preferably 330 to 930 cm 3 / sec ⁇ cm.
- the shape of the laser welded molded body is arbitrary, and it may be a deformed extruded product (bar, pipe, etc.) that is used for welding by abutting the end, and a current-carrying part that requires particularly high waterproofness and airtightness, A metal-inserted molded product used for electronic parts and the like is also preferable.
- the gap is 0.1 mm or more, preferably 0.2 mm or more, more preferably 0.5 mm or more, and particularly 0.
- Laser welding is possible even when the thickness is 8 mm or more.
- the type of laser light to be irradiated is arbitrary as long as it is near-infrared laser light.
- YAG yttrium, aluminum, garnet crystal
- LD laser diode
- laser diode wavelength 808 nm, 820 nm, 840 nm, 880 nm
- 940 nm 940 nm
- the shape, size, thickness, etc. of the welded body that has been laser-welded are arbitrary. Applications of the welded body include parts for transportation equipment such as automobiles, parts for electrical and electronic equipment, parts for industrial machinery, and other consumer parts. Is preferred.
- Preferred examples of the laser welding method include butt welding and superposition welding.
- the butt welding as shown in FIG. 2, the two molded bodies 1 and 2 are butted and irradiated with the laser beam 4 while being scanned, so that a welded portion 5 is generated, whereby a laser welded body is formed.
- the superposition welding is performed by superimposing and scanning the two molded bodies 1 and 2 and irradiating the laser beam 4 while scanning to form a welded portion 5, thereby forming a laser welded body.
- the molded body obtained with the colored resin composition of the present invention is abutted or overlapped and laser-welded, so that the obtained laser-welded body has considerably improved welding strength and is required for the laser-welded body. Meet practical strength. Also, considering the laser welding conditions, it can be seen that the allowable range of the energy amount by the laser light has a much wider range, and the compact that can cope with such wide laser welding conditions has a complicated structure. It is possible to provide laser welding with high practicality for welding of molded bodies of the above, welding of molded bodies having changed thickness, and the like. Further, it is a laser welded body having a function of suppressing heat discoloration and colorant bleeding, and having little influence on electronic components.
- the absorbance and maximum absorption wavelength of the dye used above were measured by the following method, and the absorption curve is shown in FIG. [Measurement method of absorbance and maximum absorption wavelength] 0.05 g of a dye sample is weighed, dissolved in dimethylformamide (DMF), and adjusted in a 100 ml volumetric flask. Next, 2 ml of the adjustment liquid was measured with a whole pipette and diluted with a DMF in a 50 ml volumetric flask to prepare an adjustment liquid. The absorption spectrum of the obtained adjustment liquid was measured using an ultraviolet-visible spectrophotometer (trade name: UV-1100, manufactured by Shimadzu Corporation).
- Production Example 2 Production of Colorant Example 2
- the composition of Production Example 1 was changed to 0.54 parts by mass of anthraquinone dye 2 (maximum absorption wavelength 629 nm CI Solvent Blue 97), perinone dye 1 (maximum absorption wavelength 472 nm CI Solvent Red 179).
- 0.63 parts by mass and anthraquinone dye 3 instead of 0.63 parts by mass, the same procedure as in Production Example 1 was performed except that Colorant Example 2 1.8 A mass part was obtained.
- Comparative Production Example 1 Production of Comparative Colorant Example 1
- 1.50 parts by weight of anthraquinone dye 1 (maximum absorption wavelength 628 nm CI Solvent Blue 104), 0.90 parts by weight of perinone dye 1 (maximum absorption wavelength 472 nm CI Solvent Red 179) and anthraquinone dye 3 (maximum absorption) Wavelength 446 nm CI Solvent Yellow 163) 0.60 part by mass was placed in a blender and stirred for 5 hours to obtain 3.0 parts by mass of Comparative Colorant Example 1.
- Comparative Production Examples 2-3 Production of Comparative Colorant Examples 2-3
- Comparative Colorant Example 2 to Comparative Colorant Example 3 were obtained in the same manner as Comparative Production Example 1 except that the blending composition was changed to the dyes and compositions shown in Table 1.
- a molded body made of the resin composition was produced by the method described below. Thereafter, laser welding was performed using the molded body.
- the used raw materials other than a coloring agent are each component of the following Table 2.
- Example A1 Preparation of molded body example 1 50 parts by mass of polybutylene terephthalate homopolymer (A1) (Novaduran 5008), 50 parts by mass of polybutylene terephthalate copolymer (A2a) (Novaduran 5605), and a phenol-based stabilizer (stabilizer 2, Adekastab AO- 60) 0.4 parts by weight, release agent (Unistar H476) 0.7 parts by weight, nigrosine (NUBIANBLACK TH-807) 0.014 parts by weight, and Colorant Example 1 0.386 parts by weight The mixture was placed in a tumbler and mixed with stirring for 1 hour.
- the obtained mixture was put into a main hopper of a 30 mm vent type twin screw extruder (manufactured by Nippon Steel Works, “TEX30 ⁇ ”), and 43 parts by mass of glass fiber (GF) (T-187) was seventh from the hopper.
- TEX30 ⁇ glass fiber
- T-187 43 parts by mass of glass fiber (GF) (T-187) was seventh from the hopper.
- From the side feeder of the extruder kneaded under the conditions of the extruder barrel set temperatures C1 to C15 of 260 ° C., the die of 250 ° C., the screw rotation speed of 200 rpm, and the discharge rate of 40 kg / hour, extruded into a strand, and pellets of the resin composition Got.
- the obtained pellets were molded using an injection molding machine (Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C., and were black 80 mm long ⁇ 20 mm wide ⁇ 2 mm thick.
- Two molded body examples 1 (molded body example 1-1 and molded body example 1-2) were produced.
- test pieces for measurement of conversion absorbance a and incidence rate cylinder temperature 260 ° C., mold temperature of 80 ° C., injection speed 120 mm / sec, an injection rate of 51cm 3 / sec, in the conditions of surface progression factor 405cm 3 / sec ⁇ cm Molding was performed to produce a black molded plate 1K having a stepped shape of 80 mm in length, 50 mm in width, 1.5 mm in thickness and 1 mm in two steps.
- Example A the two molded bodies (in this example, molded body example 1-1 and molded body example 1-2) were used for the measurement of laser welding strength, and the stepped shaped molded plate was ( In this example, the molded plate 1K), transmittance, reflectance, converted absorbance, and color difference were used.
- Incident rate K (%) 100 ⁇ transmittance ⁇ reflectance
- the incident rate K is an incident rate with respect to a laser beam having a wavelength of 940 nm when the molded body is 1 mm thick.
- the gate part is 1.5 mm thick side
- Standard molded plates were prepared according to the following method.
- Black polybutylene terephthalate resin manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name: NOVADURAN 5010G30 BK2
- Si-50 is molded using an injection molding machine Si-50 at a cylinder temperature of 260 ° C and a mold temperature of 80 ° C.
- the welding conditions are as follows. Laser welding machine; FD-200 (50W machine) manufactured by Fine Devices Output: 50W (setting) Spot diameter: 1mm ⁇ Scanning speed: Scanning speed described in Table 3 Irradiation energy: As described in Table 3 Scanning distance: 15 mm
- a test speed of 10 mm / mm in the longitudinal direction of the welded body is obtained using a tensile tester (manufactured by Shimadzu Corporation, AG-50kNE) according to JIS K7161-1994. A tensile test was performed at min, and the welding strength was measured. The results are shown in Table 3.
- Comparative Examples A1 and A2 were the same as Example A1 except that the blending composition was changed according to Table 3. Comparative Molded Body Examples 1 and 2 of Comparative Examples A1 and A2, and respective stepped shaped molded plates Got. Table 3 shows the converted absorbance a, the incident rate K, and the color difference ⁇ E00 calculated from the transmittance and the reflectance in the same manner as in Example A1. Using the resulting molded plate, butt laser welding was performed in the same manner as in Example A1 to obtain a laser welded body. Further, a tensile test was performed to measure the welding strength, and the results are shown in Table 3.
- Example A2 Production of Molded Example 2 60 parts by mass of polybutylene terephthalate homopolymer (A1), 40 parts by mass of polyethylene terephthalate resin (A2b) (Novapet PBK1), 0.4 parts by mass of phenol-based stabilizer (stabilizer 2), 0.7 parts by weight of the mold, 0.014 parts by weight of nigrosine (NUBIAN BLACK TH-807), and 0.386 parts by weight of Colorant Example 1 were placed in a stainless steel tumbler and mixed with stirring for 1 hour.
- A1 polybutylene terephthalate homopolymer
- A2b polyethylene terephthalate resin
- stabilizer 2 phenol-based stabilizer
- 0.7 parts by weight of the mold 0.014 parts by weight of nigrosine (NUBIAN BLACK TH-807)
- nigrosine NUBIAN BLACK TH-807
- the obtained mixture is put into a main hopper of a 30 mm vent type twin screw extruder (manufactured by Nippon Steel Works, "TEX30 ⁇ "), and 43 parts by mass of glass fiber (GF) is supplied from the seventh side feeder from the hopper. Then, they were kneaded under the conditions of the extruder barrel set temperatures C1 to C15 of 260 ° C., the die of 250 ° C., the screw rotation speed of 200 rpm, and the discharge rate of 40 kg / hour, and extruded into strands to obtain resin composition pellets.
- TEX30 ⁇ glass fiber
- the obtained pellets were molded using an injection molding machine (Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C., and were black 80 mm long ⁇ 20 mm wide ⁇ 2 mm thick.
- Two molded body examples 2 (molded body example 2-1 and molded body example 2-2) were produced.
- a black molded plate 2K having a stepped shape of 80 mm in length, 50 mm in width, 1.5 mm in thickness and 1 mm was prepared as a test piece for measuring the converted absorbance a, incidence rate, and color difference.
- the converted absorbance a, the incident rate K, and the color difference ⁇ E00 were measured, and the results are shown in Table 3.
- Comparative Examples A3 to A4 were obtained in the same manner as in Example A2, except that the blending composition was changed according to Table 3. Comparative molded products 3 to 4 of Comparative Examples A3 to A4 were obtained. In the same manner as in Example A1, the converted absorbance a, the incident rate K, and the color difference ⁇ E00 were measured, and the results are shown in Table 3. Using the obtained two molded body examples, butt laser welding was performed in the same manner as in Example A2 to obtain a laser welded body. Further, a tensile test was performed to measure the welding strength, and the results are shown in Table 3.
- Example A3 Preparation of Molded Example 3 70 parts by mass of polybutylene terephthalate homopolymer (A1), 30 parts by mass of polycarbonate resin (A2c) (Iupilon H4000), 0.1 mass of phosphorus stabilizer (stabilizer 1, ADK STAB AX-71) Parts, 0.4 parts by weight of a phenol-based stabilizer (stabilizer 2), 0.7 parts by weight of a release agent, 0.014 parts by weight of nigrosine (NUBIAN BLACK TH-807), and Colorant Example 1 386 parts by mass were placed in a stainless steel tumbler and mixed with stirring for 1 hour.
- the obtained mixture is put into a main hopper of a 30 mm vent type twin screw extruder (manufactured by Nippon Steel Works, "TEX30 ⁇ "), and 43 parts by mass of glass fiber (GF) is supplied from the seventh side feeder from the hopper. Then, they were kneaded under the conditions of the extruder barrel set temperatures C1 to C15 of 260 ° C., the die of 250 ° C., the screw rotation speed of 200 rpm, and the discharge rate of 40 kg / hour, and extruded into strands to obtain resin composition pellets.
- the obtained pellets were molded using an injection molding machine (Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 260 ° C.
- Comparative Examples A5 to A6 Comparative molded bodies 5 to 6 of Comparative Examples A5 to A6 were obtained in the same manner as Example A3, except that the blending composition was changed according to Table 3.
- the converted absorbance a, the incident rate K, and the color difference ⁇ E00 were measured, and the results are shown in Table 3.
- butt laser welding was performed in the same manner as in Example A3 to obtain a laser welded body. Further, a tensile test was performed to measure the welding strength, and the results are shown in Table 3.
- Examples A1 to A3 using the composition of the present invention are all excellent in laser welding strength, small in color difference ⁇ E00, and excellent in black coloration.
- Example B1 Production of Molded Body Example 4 Nigrosin (NUBIAN BLACK TH) for a total of 600 parts by mass of 294 parts by mass of polybutylene terephthalate homopolymer (A1), 126 parts by mass of polycarbonate resin (A2c) and 180 parts by mass of glass fiber (GF) -807) 0.06 parts by weight, and 1.80 parts by weight of Colorant Example 1 were used.
- other than glass fibers were placed in a stainless steel tumbler and mixed with stirring for 1 hour.
- the obtained mixture is put into a main hopper of a 30 mm vent type twin screw extruder (manufactured by Nippon Steel Works, “TEX30 ⁇ ”), glass fiber is supplied from the seventh side feeder from the hopper, and the extruder barrel is set. Kneading was carried out under the conditions of temperatures C1 to C15 of 260 ° C., die of 250 ° C., screw rotation speed of 200 rpm, discharge rate of 40 kg / hour, and extruded into strands to obtain resin composition pellets.
- the obtained pellets were molded by an ordinary method using an injection molding machine Si-50 at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. to obtain a black molded body example 4 (80 mm long ⁇ 20 mm wide ⁇ 2 mm thick). Two molded body examples 4-1 and 4-2) were produced.
- a stepped shape having two steps of 80 mm in length, 50 mm in width, 1.5 mm in thickness and 1 mm in the same conditions of a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C.
- a black molded plate 4K was produced.
- the transmittance, reflectance, incident rate K, and converted absorbance a were as follows. Transmittance: 64.3%, Reflectance: 9.2%, Incident rate K: 26.5%, Equivalent absorbance: 0.14
- Examples C1 to C5 Each component described in Table 1 and Table 2 and nigrosine (NUBIAN BLACK TH-807) were blended in the amounts shown in Table 5 (both parts by mass), and this was blended with a 30 mm vent type twin screw extruder (Nippon Steel Works).
- the glass fiber is supplied from the seventh side feeder from the hopper, the extruder barrel set temperature C1 to C15 is 260 ° C., the die is 250 ° C., the screw speed is 200 rpm, The mixture was kneaded at a discharge rate of 40 kg / hour and extruded into a strand to obtain resin composition pellets.
- the crystallization temperature (Tc) of the resin composition was increased from 30 to 300 ° C. at a temperature increase rate of 20 ° C./min using a differential scanning calorimetry (DSC) machine (“Pyris Diamond” manufactured by PerkinElmer). After being held at 300 ° C. for 3 minutes, it was measured as the peak top temperature (unit: ° C.) of the exothermic peak observed when the temperature was lowered at a temperature lowering rate of 20 ° C./min. The lower the crystallization temperature (Tc), the slower the solidification, so the laser welding strength is considered to be higher.
- DSC differential scanning calorimetry
- the resin composition pellets obtained above were dried at 120 ° C. for 5 hours, and then using an injection molding machine (NEX80-9E, manufactured by Nissei Plastic Industry Co., Ltd.) at a cylinder temperature of 255 ° C. and a mold temperature of 65 ° C.
- An ASTM No. 4 dumbbell piece having a thickness of 0 mm and an ASTM No. 4 dumbbell piece having a thickness of 1.5 mm were produced under the conditions of an injection speed of 100 mm / sec, an injection rate of 66 cm 3 / sec, and a surface progression coefficient of 880 cm 3 / sec ⁇ cm.
- the cylinder temperature is 260 ° C.
- the mold temperature is 80 ° C.
- the step is 80 mm long, 50 mm wide, 1.5 mm thick and 1 mm in height.
- a 1 mm dumbbell piece is used for measurement of transmittance, reflectance, converted absorbance, and color tone
- a 1.5 mm dumbbell piece and a stepped plate are used for measurement of laser welding strength, respectively. did.
- Incident rate K (%) 100 ⁇ transmittance ⁇ reflectance
- the incident rate K is an incident rate with respect to a laser beam having a wavelength of 940 nm when the molded body is 1 mm thick.
- ASTM No. 4 dumbbell (1 mm) it was derived from the measurement results of the transmittance and reflectance of the portion on the side opposite to the gate (the portion on the opposite side of the gate into which the resin was injected).
- the welding conditions are as follows. Device used: FD2230 manufactured by Fine Devices Laser wavelength: 940 nm Laser spot diameter: ⁇ 2.1mm Distance between laser head and test piece: 75mm Overlay pressure on the compact: 2MPa Laser scanning speed: 10mm / sec Laser scanning distance: 16mm The laser output was varied as described in Table 5. The welded body was measured for weld strength (unit: N) under the conditions of span interval: 160 mm and tensile speed: 5 mm / min using an Instron 5544 universal testing machine. In addition, the weldability is not only high in welding strength, but also maintaining high welding strength under any conditions means that the laser welding conditions are wide and excellent in laser welding properties. It is evaluated.
- Laser weldability evaluation-1 overlap welding of plate-shaped test pieces: As shown in FIG. 3, the two plates with the same composition obtained above were overlapped with a 1.5 mm-thick portion to evaluate laser weldability (welding strength test).
- Laser weldability evaluation-2 overlap welding of dumbbell pieces: Two anti-gate side end portions of No. 4 dumbbell pieces (1.5 mm thick) having the same composition obtained above were overlapped as shown in FIG. 3 to evaluate laser weldability (welding strength test).
- Crevice welding strength Using two dumbbells 11 and 12 of ASTM4 of the same composition obtained above and having the same thickness, dumbbell 11 and dumbbell 12 end on the opposite gate side are overlapped vertically as shown in FIG.
- the metal plate spacers 15 and 15 ′ sandwiched between the overlapping portions 14 are placed on a glass base (not shown), a glass plate 16 is placed on the dumbbells 11 and 12, and 2 MPa from above. While applying pressure, welding was performed by irradiating the laser beam 17 with a laser output of 80 W and a laser scanning speed of 10 mm / sec.
- the gap between the metal spacers 15 and 15 ′ is changed from 0 mm to 0.8 mm shown in Table 5, and under the same conditions as described above, a load is applied in the pulling direction of the arrow a in the figure, The load (unit: N) at the time of destruction was determined.
- Examples D1 to D7, Comparative Examples D1 to D5 [Manufacture of laser welded body for butt welding]
- Each component described in Table 1 and Table 2 and nigrosine (NUBIAN BLACK TH-807) were blended in the amounts shown in Table 6 (both parts by mass), and this was mixed with a 30 mm vent type twin screw extruder (Nippon Steel Works).
- the glass fiber is supplied from the seventh side feeder from the hopper, the extruder barrel set temperature C1 to C15 is 260 ° C., the die is 250 ° C., the screw speed is 200 rpm,
- the mixture was kneaded at a discharge rate of 40 kg / hour and extruded into a strand to obtain resin composition pellets.
- the crystallization temperature (Tc) of the resin composition was increased from 30 to 300 ° C. at a temperature increase rate of 20 ° C./min using a differential scanning calorimetry (DSC) machine (“Pyris Diamond” manufactured by PerkinElmer). After being held at 300 ° C. for 3 minutes, it was measured as the peak top temperature (unit: ° C.) of the exothermic peak observed when the temperature was lowered at a temperature lowering rate of 20 ° C./min. It is considered that the lower the crystallization temperature (Tc), the slower the solidification, and the higher the laser welding strength and the weld strength.
- DSC differential scanning calorimetry
- the resin composition pellets obtained above were dried at 120 ° C. for 5 hours, and then using an injection molding machine (NEX80-9E, manufactured by Nissei Plastic Industry Co., Ltd.) at a cylinder temperature of 255 ° C. and a mold temperature of 65 ° C.
- ASTM No. 4 dumbbell pieces having a thickness of 0 mm and a thickness of 2.0 mm were manufactured under the conditions of an injection speed of 100 mm / sec, an injection rate of 66 cm 3 / sec, and a surface progression coefficient of 880 cm 3 / sec ⁇ cm.
- Incident rate K (%) 100 ⁇ transmittance ⁇ reflectance
- the incident rate K is an incident rate with respect to a laser beam having a wavelength of 940 nm when the molded body is 1 mm thick.
- ASTM No. 4 dumbbell (1 mm) it was derived from the measurement results of the transmittance and reflectance of the portion on the side opposite to the gate (the portion on the opposite side of the gate into which the resin was injected).
- the one sandwiching the spacers 15 and 15 ′ is placed on a glass base (not shown), the glass plate 16 is placed on the dumbbells 11 and 12, and a pressure of 0.4 MPa is applied from the side, Welding is performed by irradiating the laser beam 17 under the conditions of a laser output of 200 W, a laser scanning speed of 20 mm / sec, and a laser scanning distance of 16 mm. It was.
- the gap interval formed by the metal spacers 15 and 15 ′ was changed to 0 mm to 0.8 mm shown in Table 6, and using a 5544 universal testing machine manufactured by Instron, span interval was 160 mm, tensile speed was Under the condition of 5 mm / min, a load (unit: N) for breaking by applying a load in the pulling direction indicated by the arrow a in the figure was determined.
- the weldability is not only high in welding strength, but also maintaining high welding strength under any conditions means that the laser welding conditions are wide and excellent in laser welding properties. It is evaluated.
- Example E1 to E9 Comparative Example E1
- Each component and nigrosine (NUBIAN BLACK TH-807) listed in Table 1 and Table 2 were blended in the amounts shown in Table 7 (both parts by mass), and this was mixed with a 30 mm vent type twin screw extruder (Nippon Steel Works).
- the glass fiber is fed from the seventh side feeder from the hopper, the extruder barrel set temperatures C1 to C7 are 260 ° C., C8 to C15 are 220 ° C., and the die is 250
- the mixture was kneaded at a temperature of 220 ° C., a screw rotation speed of 220 rpm, and a discharge rate of 40 kg / hour and extruded into a strand shape to obtain a resin composition pellet.
- the crystallization temperature (Tc) of the resin composition was measured in the same manner as described above. Also, after drying the resin composition pellets obtained above at 120 ° C. for 5 hours, using an injection molding machine (manufactured by Toyo Machine Metal Co., Ltd., Si-50) at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. Production of two stepped plates of length 80 mm ⁇ width 50 mm ⁇ thickness 1.5 mm and 1 mm under conditions of an injection speed of 120 mm / sec, an injection rate of 51 cm 3 / sec, and a surface progression coefficient of 405 cm 3 / sec ⁇ cm did.
- an injection molding machine manufactured by Toyo Machine Metal Co., Ltd., Si-50
- the laser welded part of the 1 mm thick part of the two stepped plate obtained above was transmitted at a wavelength of 940 nm using an ultraviolet visible near infrared spectrophotometer (“UV-3100PC” manufactured by Shimadzu Corporation). The rate (unit:%) was determined.
- UV-3100PC ultraviolet visible near infrared spectrophotometer
- Incident rate K (%) 100 ⁇ transmittance ⁇ reflectance
- the incident rate K is an incident rate with respect to a laser beam having a wavelength of 940 nm when the molded body is 1 mm thick. In the case of a molded body of two-step plate, it was derived from the measurement results of transmittance and reflectance of a 1 mm-thick portion on the opposite gate side (a portion on the opposite side of the gate into which the resin was injected).
- Laser weldability (lap welding of plate specimens): The two stepped plates having the same composition obtained above were overlapped with a 1.5 mm thick portion as shown in FIG. 3 and laser welded.
- the obtained laser welded body is a load that breaks by applying a load in the tensile direction under the conditions of span interval: 160 mm and tensile speed of 5 mm / min using an Instron 5544 universal testing machine. : N).
- the welding conditions are as follows. Device used: FD2230 manufactured by Fine Devices Laser wavelength: 940 nm Laser spot diameter: ⁇ 2.1mm Distance between laser head and test piece: 75mm Overlay pressure on the compact: 2MPa Laser scanning speed: 10 mm / s Laser scanning distance: 16mm
- the laser output was varied as described in Table 7.
- Laser weldability overlap welding of plate specimens, gap welding strength:
- the two plates with the same composition obtained above are overlapped with a 1.5 mm thick portion, and welded with a metal piece spacer sandwiched between the overlapped portions in the same manner as in FIG. was changed with the gap interval shown in Table 7 between 0 mm and 0.3 mm, the following laser welding conditions and laser output of 80 W, laser scanning speed of 10 mm / s, and laser welding were performed.
- a load (unit: N) was determined by applying a load in the pulling direction under the conditions of span interval: 160 mm and pulling speed: 5 mm / min, using a 5544 universal testing machine manufactured by the company.
- the weldability is not only high in welding strength, but also maintaining high welding strength under any conditions means that the laser welding conditions are wide and excellent in laser welding properties. It is evaluated.
- the welding conditions are as follows. Device used: FD2230 manufactured by Fine Devices Laser wavelength: 940 nm Laser spot diameter: ⁇ 2.1mm Distance between laser head and test piece: 75mm Overlay pressure on the compact: 2MPa Laser scanning distance: 16mm
- Color difference measurement was performed on a 1.0 mm thick part of the two-stage plate obtained above using “CM-3600d” (light source: D65, field of view: 10 °, method: SCE, target mask 8 mm) manufactured by Konica Minolta, ⁇ E00 and ⁇ E with respect to the standard plate were determined.
- Color after heat treatment The plate with the two steps obtained above is left in a 140 ° C. hot air oven for 12 hours, and the color difference of the 1.0 mm thick portion of the plate after heat treatment is measured in the same manner as described above to obtain ⁇ E of the color tone before and after the heat treatment. It was. Further, the hue after the heat treatment was determined as ⁇ E00 with respect to the standard plate.
- the resin composition for laser welding of the present invention has extremely excellent laser welding processability in addition to high colorability and heat resistance. Therefore, since the resin composition of the present invention can be suitably and widely applied to automobile parts, electrical / electronic equipment parts, and other materials, industrial applicability is very high.
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Abstract
Description
近年、特に自動車用部品は軽量化が進んでおり、従来金属を使用していた部品の樹脂化や、樹脂製品の小型化等により、高いレベルの耐熱性を求められる場合が多くなっている。そのためガラス繊維等の充填材を配合した強化熱可塑性樹脂が多く使われ、中でもポリブチレンテレフタレート等の熱可塑性ポリエステル樹脂は機械的強度や成形性に優れ、自動車用電子部品ケースやモーター部品筐体等に広く使用されている。
しかしながらポリカーボネート樹脂やポリスチレン系樹脂等に比べて、ポリエステル樹脂はレーザー光透過性が比較的低く、また、成形品に反りが出やすいこと等から、溶着強度が不十分な場合が多かった。
成形品に反りが生じる場合は、溶着時に反りを矯正するように押し付け力を加える方法も採られるが、成形品の形状によっては効率的に押し付け力を加えることが難しい場合も多く、また、溶着後に押し付け力を取り除いた溶着体に残留応力が残るため、高い溶着強度が得にくい問題がある。
しかしながら、これらの手法では、成形品の反り変形等によって生じる溶着部材間の隙間等のため、十分な溶着性が得られない場合があった。
また、熱可塑性樹脂にニグロシン等のレーザー透過吸収剤を添加して、溶着性を向上させる方法(特許文献5)も提案されているが、レーザー溶着に適したポリエステル樹脂組成物については記載されていない。
本発明は、以下のレーザー溶着用樹脂組成物、レーザー溶着用成形体およびレーザー溶着体に関する。
(A)ポリブチレンテレフタレートホモポリマーと、
ポリブチレンテレフタレートコポリマー、ポリエチレンテレフタレート樹脂又はポリカーボネート樹脂の少なくとも1種とを含む熱可塑性ポリエステル系樹脂材料100質量部に対し、
(B)ニグロシン0.0005~0.5質量部及び、
(C)最大吸収波長が590~635nmの範囲であるアントラキノン染料C1と、最大吸収波長が460~480nmの範囲であるペリノン染料C2と、最大吸収波長が435~455nmの範囲であるアントラキノン染料C3を、C1、C2及びC3の合計100質量部に対する質量比でC1:C2:C3=24~41:24~39:22~46で少なくとも含む、着色剤0.01~2質量部を含有することを特徴とするレーザー溶着用樹脂組成物。
[3](A)熱可塑性ポリエステル系樹脂材料が、ポリブチレンテレフタレートホモポリマー及びポリブチレンテレフタレートコポリマーを含み、ポリブチレンテレフタレートコポリマーの含有量が、両者の合計100質量%に対して、5~70質量%である上記[1]又は[2]に記載のレーザー溶着用樹脂組成物。
[4](A)熱可塑性ポリエステル系樹脂材料が、ポリブチレンテレフタレートホモポリマー及びポリエチレンテレフタレート樹脂を含み、ポリエチレンテレフタレート樹脂の含有量が、両者の合計100質量%に対して、5~50質量%である上記[1]又は[2]に記載のレーザー溶着用樹脂組成物。
[5](A)熱可塑性ポリエステル系樹脂材料が、ポリブチレンテレフタレートホモポリマー及びポリカーボネート樹脂を含み、ポリカーボネート樹脂の含有量が、ポリブチレンテレフタレートホモポリマー及びポリカーボネート樹脂の合計100質量%に対して、5~50質量%である上記[1]又は[2]に記載のレーザー溶着用樹脂組成物。
[7]前記樹脂組成物からなる1mm厚の成形板の940nmのレーザー光に対する入射率Kが、20~80%である上記[1]~[6]のいずれかに記載のレーザー溶着用樹脂組成物。
但し、入射率K(%)=100-透過率-反射率とする。
[9]上記[8]に記載の成形体のレーザー溶着体。
[10]溶着体が、少なくともその溶着部の一部において、溶着する際の成形体の隙間が0.1mm以上である上記[9]に記載のレーザー溶着体。
[11]成形体同士を突き合わせ溶着した上記[9]又は[10]に記載のレーザー溶着体。
[12]成形体同士を重ね合わせ溶着した上記[9]又は[10]に記載のレーザー溶着体。
レーザー光による溶着に用いる樹脂組成物であって、
(A)ポリブチレンテレフタレートホモポリマーと、
ポリブチレンテレフタレートコポリマー、ポリエチレンテレフタレート樹脂又はポリカーボネート樹脂の少なくとも1種とを含む熱可塑性ポリエステル系樹脂材料100質量部に対し、
(B)ニグロシン0.0005~0.5質量部及び、
(C)最大吸収波長が590~635nmの範囲であるアントラキノン染料C1と、最大吸収波長が460~480nmの範囲であるペリノン染料C2と、最大吸収波長が435~455nmの範囲であるアントラキノン染料C3を、C1、C2及びC3の合計100質量部に対する質量比でC1:C2:C3=24~41:24~39:22~46で少なくとも含む、着色剤0.01~2質量部を含有することを特徴とする。
本発明のレーザー溶着用樹脂組成物は、(B)ニグロシンを含有する。
ニグロシンは、レーザー光吸収性を有する染料として働き、800nm~1200nmのレーザー光の範囲に、緩やかな吸収を有している。
ニグロシンは、C.I.Solvent Black 5やC.I.Solvent Black 7として、Color Indexに記載されているような、黒色のアジン系縮合混合物である。これは、例えば、アニリン、アニリン塩酸塩及びニトロベンゼンを、塩化鉄の存在下、反応温度160~190℃で酸化及び脱水縮合することにより合成できる。ニグロシンの市販品としては、例えば、「NUBIAN(登録商標) BLACK シリーズ」(商品名、オリヱント化学工業社製)等が挙げられる。
なお、上記含有量は、後記するような(A)熱可塑性ポリエステル系樹脂材料がポリカーボネート樹脂及び/又は芳香族ビニル樹脂を併せて含有する場合には、これら樹脂の合計100質量部に対する量である。
レーザー溶着用樹脂組成物の入射率Kを20~80%、更に好ましくは25~75%、特に好ましくは、30~70%とすることができる。また、ニグロシンを配合することで、黒色着色力の向上と、成形体の表面外観や平滑性の向上が可能となり、レーザー溶着性が向上する。
なお、入射率K(単位:%)は、以下の式で定義される。
入射率K(%)=100-透過率-反射率
入射率Kは、成形体の1mm厚時の波長940nmのレーザー光に対する入射率である。
ASTM4号ダンベル(1mm)の成形体の場合、反ゲート側の部位(樹脂を注入したゲートの反対側にある部位)の透過率と反射率の測定結果から導き出される。なお、その成形体は、シリンダー温度255℃、金型温度65℃で、射出速度100mm/sec、後記する射出率(injection rate)66cm3/sec、後記する面進行係数(surface progression factor)880cm3/sec・cmの条件で、製造される。
2段プレート(縦80mm×横50mm×厚さ1.5mmと1mm、ゲート部は1.5mm厚側)の場合、反ゲート側である厚さ1mmの部位の透過率と反射率の測定結果から導き出される。なお、その成形体は、シリンダー温度260℃、金型温度80℃で、射出速度120mm/sec、射出率51cm3/sec、面進行係数405cm3/sec・cmの条件で、製造される。
また、レーザー溶着用樹脂組成物は、本発明を実施できる有効範囲でレーザー光に対するその他の吸収性染料またはレーザー光吸収剤を含んでいてもよい。
本発明のレーザー溶着用樹脂組成物に用いる(C)着色剤は、最大吸収波長が590~635nmの範囲であるアントラキノン染料C1と、最大吸収波長が460~480nmの範囲であるペリノン染料C2と、最大吸収波長が435~455nmの範囲であるアントラキノン染料C3を、C1、C2及びC3の合計100質量部に対する質量比でC1:C2:C3=24~41:24~39:22~46で少なくとも含むものである。
なお、最大吸収波長は、ジメチルホルムアミド(DMF)に溶解させた溶液を紫外可視分光光度計を用いて測定した吸収スペクトルにおいて、最大吸収を示した波長として定義される。
本発明の(C)着色剤として用いる、最大吸収波長が590~635nmの範囲であるアントラキノン染料C1は、通常青色の油溶性染料である。本発明において、この染料を用いることにより、例えば、緑色アントラキノン染料より、視認性が高く、黒色混合染料を組み合わせる場合にも、減法混色で、赤色染料、黄色染料を組み合わせることにより、着色力の高い黒色を示す着色剤を得ることができる。
好ましいアントラキノン染料C1は、COLOR INDEXに記載されているようなC.I.ソルベントブルー97(分解開始温度320℃)、C.I.ソルベントブルー104(分解開始温度320℃)等が例示される。それらは、1種または2種以上使用されてもよい。但し、配合量が多くなると高温雰囲気下で成形体からブリードしやすくなり、耐熱変色特性が悪化する傾向がある。
市販品されているアントラキノン染料C1としては、例えば、「NUBIAN(登録商標) BLUE シリーズ」、「OPLAS(登録商標) BLUE シリーズ」(いずれも商品名、オリヱント化学工業社製)等が挙げられる。
赤色ペリノン染料C2の市販品としては、例えば、「NUBIAN(登録商標) RED シリーズ、OPLAS(登録商標) RED シリーズ」(いずれも商品名でオリヱント化学工業社製)等が挙げられる。
最大吸収波長が435~455nmの範囲のアントラキノン染料C3の具体例は、C.I.ソルベント イエロー 163、C.I.バット イエロー 1、2、3等を使用することができる。それらは、1種または2種以上使用されてもよい。但し、配合量が多くなると高温雰囲気下で成形体からブリードしやすくなり、耐熱変色特性が悪化する傾向がある。
このようなアントラキノン染料C3としての黄色アントラキノン染料の市販品としては、例えば、「NUBIAN(登録商標) YELLOW シリーズ、OPLAS(登録商標) YELLOW シリーズ」(いずれも商品名、オリヱント化学工業社製)等が挙げられる。
本発明のレーザー溶着用樹脂組成物が含有する(A)熱可塑性ポリエステル系樹脂材料は、ポリブチレンテレフタレートホモポリマー(A1)と、ポリブチレンテレフタレートコポリマー(A2a)、ポリエチレンテレフタレート樹脂(A2b)又はポリカーボネート樹脂(A2c)の少なくとも1種とを含む。
本発明の(A)熱可塑性ポリエステル系樹脂材料に使用されるポリブチレンテレフタレートホモポリマー(A1)は、酸成分としてテレフタル酸を、アルコール成分として1,4-ブタンジオールを重縮合させて得られるポリマーである。
なお、固有粘度は、テトラクロロエタンとフェノールとの1:1(質量比)の混合溶媒中、30℃で測定される値である。
(A)熱可塑性ポリエステル系樹脂材料に用いられるポリブチレンテレフタレートコポリマー(A2a)は、テレフタル酸と、1,4-ブタンジオールに加えて、好ましくはイソフタル酸、ダイマー酸、ポリテトラメチレングリコール(PTMG)等のポリアルキレングリコール等が共重合されたポリマーである。
なお、固有粘度は、テトラクロロエタンとフェノールとの1:1(質量比)の混合溶媒中、30℃で測定する値である。
(A)熱可塑性ポリエステル系樹脂材料に用いられるポリエチレンテレフタレート樹脂(A2b)は、全構成繰り返し単位に対するテレフタル酸及びエチレングリコールからなるオキシエチレンオキシテレフタロイル単位を主たる構成単位とする樹脂であり、オキシエチレンオキシテレフタロイル単位以外の構成の繰り返し単位を含んでいてもよい。ポリエチレンテレフタレート樹脂は、テレフタル酸又はその低級アルキルエステルとエチレングリコールとを主たる原料として製造されるが、他の酸成分及び/又は他のグリコール成分を併せて原料として用いてもよい。
また、エチレングリコール以外のジオール成分としては、1,2-プロパンジオール、1,3-プロパンジオール、1,4-ブタンジオール、ペンタメチレングリコール、ヘキサメチレングリコール、ネオペンチルグリコール等の脂肪族グリコール、シクロヘキサンジメタノール等の脂環式グリコール、ビスフェノールA、ビスフェノールS等の芳香族ジヒドロキシ化合物誘導体等が挙げられる。
なお、ポリエチレンテレフタレート樹脂の固有粘度は、テトラクロロエタンとフェノールとの1:1(質量比)の混合溶媒中、30℃で測定する値である。
なお、ポリエチレンテレフタレート樹脂の末端カルボキシル基濃度は、ベンジルアルコール25mLにポリエチレンテレフタレート樹脂0.5gを溶解し、水酸化ナトリウムの0.01モル/Lベンジルアルコール溶液を使用して滴定することにより、求められる値である。
末端カルボキシル基量を調整する方法としては、重合時の原料仕込み比、重合温度、減圧方法などの重合条件を調整する方法や、末端封鎖剤を反応させる方法等、従来公知の任意の方法により行えばよい。
(A)熱可塑性ポリエステル系樹脂材料に用いられるポリカーボネート樹脂(A2c)は、ジヒドロキシ化合物又はこれと少量のポリヒドロキシ化合物を、ホスゲン又は炭酸ジエステルと反応させることによって得られる、分岐していてもよい熱可塑性重合体又は共重合体である。ポリカーボネート樹脂の製造方法は、特に限定されるものではなく、従来公知のホスゲン法(界面重合法)や溶融法(エステル交換法)により製造したものを使用することができるが、溶融重合法で製造したポリカーボネート樹脂が、レーザー光透過性、レーザー溶着性の点から好ましい。
なお、ポリカーボネート樹脂の粘度平均分子量は、溶媒としてメチレンクロライドを用い、温度25℃で測定された溶液粘度より換算される粘度平均分子量[Mv]である。
また、(A)熱可塑性ポリエステル系樹脂材料は、上記した(A1)、(A2a)~(A2c)以外のその他の熱可塑性樹脂を、本発明の効果を損なわない範囲で含有することができる。その他の熱可塑性樹脂としては、具体的には、例えば、芳香族ビニル系樹脂、ポリアセタール樹脂、ポリフェニレンオキサイド樹脂、ポリフェニレンサルファイド樹脂、ポリサルフォン樹脂、ポリエーテルサルフォン樹脂、ポリエーテルイミド樹脂、ポリエーテルケトン樹脂、ポリオレフィン樹脂等が挙げられる。
また、芳香族ビニル系樹脂としては、芳香族ビニル化合物に他の単量体を共重合させた共重合体も用いることができる。代表的なものとしては、スチレンとアクリロニトリルを共重合させたアクリロニトリル-スチレン共重合体(AS樹脂)、スチレンと無水マレイン酸を共重合させた無水マレイン酸-スチレン共重合体(無水マレイン酸変性ポリスチレン樹脂)が挙げられる。
ゴム成分を共重合又はブレンドする場合、ゴム成分の量は、芳香族ビニル系樹脂全セグメント中の通常1質量%以上50質量%未満であり、好ましくは3~40質量%、より好ましくは5~30質量%、更に好ましくは5~20質量%である。
ゴム成分含有芳香族ビニル系樹脂としては、ゴム含有ポリスチレンが好ましく、ブタジエンゴム含有ポリスチレンがより好ましく、靱性の点から、ハイインパクトポリスチレン(HIPS)が特に好ましい。
また、芳香族ビニル系樹脂(A2d)がポリスチレンである場合は、200℃、48Nで測定されたMFRが1~50g/10分であることが好ましく、3~35g/10分であることがより好ましく、5~20g/10分であることが更に好ましい。
芳香族ビニル系樹脂(A2d)がブタジエンゴム含有ポリスチレンである場合は、200℃、49Nで測定されたMFRが0.1~40g/10分であることが好ましく、0.5~30g/10分であることがより好ましく、0.8~20g/10分であることが更に好ましい。
また、ポリブチレンテレフタレートホモポリマー(A1)のより好ましい含有量は、ポリブチレンテレフタレートホモポリマー(A1)、芳香族ビニル系樹脂(A2d)及びポリカーボネート樹脂(A2c)の合計100質量%基準で、40~80質量%であり、更には50~70質量%が好ましい。含有量が30質量%未満であると耐熱性が低下しやすく、90質量%を超えるとレーザー透過性が低下しやすい。
なお、結晶化温度(Tc)は、示差走査熱量測定(DSC)機を用いて、窒素雰囲気下、30~300℃まで昇温速度20℃/minで昇温し、300℃で3分保持した後、降温速度20℃/minにて降温した際に観測される発熱ピークのピークトップ温度として定義される。
本発明のレーザー溶着用樹脂組成物は、所望に応じ、種々の添加剤を配合することも可能である。このような添加剤としては、例えば、強化充填材、耐衝撃改良剤、流動改質剤、助色剤、分散剤、安定剤、可塑剤、紫外線吸収剤、光安定剤、酸化防止剤、帯電防止剤、潤滑剤、離型剤、結晶促進剤、結晶核剤、難燃剤、及びエポキシ化合物等が挙げられる。
強化充填材は、カップリング剤等の表面処理剤によって、表面処理されたものを用いることがより好ましい。表面処理剤が付着したガラス繊維は、耐久性、耐湿熱性、耐加水分解性、耐ヒートショック性に優れるので好ましい。
シラン系表面処理剤とエポキシ樹脂系表面処理剤は、それぞれ単独で用いても複数種で用いてもよく、両者を併用することも好ましい。
また、上記のSBSエラストマーやSISエラストマーに水素添加して水素化した樹脂(SEBS、SEPS)を用いることも好ましい。
エポキシ基を含有する共重合型エラストマー自体の種類は問わない。例えば、上記したスチレン系エラストマー、ポリオレフィン系エラストマー、アクリル系エラストマー等にエポキシ基を導入したものが好ましく挙げられる。例えば、ハードセグメントとしてポリスチレン、ソフトセグメントとしてブタジエンを共重合したスチレン-ブタジエン共重合体の場合、ジエン成分の不飽和二重結合部分をエポキシ化することでエポキシ基含有エラストマーが得られる。
また、オレフィン系エラストマーは軟質相にポリオレフィン部があればよく、EPR、EPDM等のエチレンプロピレンゴム等が好ましく使用できる。
エポキシ基を導入する方法は特に制限はなく、主鎖中に組み入れてもよく、また、エポキシ基を含有するポリマーをブロックもしくはグラフト形態でオレフィン系エラストマーに導入してもよい。好ましくはエポキシ基を有する(共)重合体をグラフト形態で導入するのがよい。
エポキシ化合物としては、一分子中に一個以上のエポキシ基を有するものであればよく、通常はアルコール、フェノール類またはカルボン酸等とエピクロロヒドリンとの反応物であるグリシジル化合物や、オレフィン性二重結合をエポキシ化した化合物を用いればよい。
エポキシ化合物の好ましい具体例としては、例えば、ビスフェノールA型エポキシ化合物、ビスフェノールF型エポキシ化合物等のビスフェノール型エポキシ化合物、レゾルシン型エポキシ化合物、ノボラック型エポキシ化合物、脂環化合物型ジエポキシ化合物、グリシジルエーテル類、グリシジルエステル類、エポキシ化ポリブタジエン等が挙げられる。
脂環化合物型エポキシ化合物としては、ビニルシクロヘキセンジオキシド、ジシクロペンタジエンオキシド等が挙げられる。
また、グリシジルエステル類としては、安息香酸グリシジルエステル、ソルビン酸グリシジルエステル等のモノグリシジルエステル類;アジピン酸ジグリシジルエステル、テレフタル酸ジグリシジルエステル、オルトフタル酸ジグリシジルエステル等が挙げられる。
エポキシ化合物としては、ビスフェノールAやノボラックとエピクロロヒドリンとの反応から得られる、ビスフェノールA型エポキシ化合物やノボラック型エポキシ化合物が特に好ましい。
特に好ましくはフェノール系安定剤であり、樹脂組成物中にポリエチレンテレフタレート樹脂又はポリカーボネート樹脂を含有する場合には、フェノール系安定剤とリン系安定剤を併用して用いるのが好ましい。
リン系安定剤としては、亜リン酸、リン酸、亜リン酸エステル、リン酸エステル等が挙げられ、中でも有機ホスフェート化合物、有機ホスファイト化合物または有機ホスホナイト化合物が好ましい。
(R1O)3-nP(=O)OHn ・・・(1)
(式(1)中、R1は、アルキル基またはアリール基であり、それぞれ同一であっても異なっていてもよい。nは0~2の整数を示す。)で表される化合物である。より好ましくは、R1が炭素数8~30の長鎖アルキルアシッドホスフェート化合物が挙げられる。炭素数8~30のアルキル基の具体例としては、オクチル基、2-エチルヘキシル基、イソオクチル基、ノニル基、イソノニル基、デシル基、イソデシル基、ドデシル基、トリデシル基、イソトリデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、エイコシル基、トリアコンチル基等が挙げられる。
R2O-P(OR3)(OR4) ・・・(2)
(式(2)中、R2、R3及びR4は、それぞれ水素原子、炭素数1~30のアルキル基または炭素数6~30のアリール基であり、R2、R3及びR4のうちの少なくとも1つは炭素数6~30のアリール基である。)で表される化合物が挙げられる。
R5-P(OR6)(OR7) ・・・(3)
(式(6)中、R5、R6及びR7は、それぞれ水素原子、炭素数1~30のアルキル基または炭素数6~30のアリール基であり、R5、R6及びR7のうちの少なくとも1つは炭素数6~30のアリール基である。)で表される化合物が挙げられる。
なお、ガラス繊維等の繊維状の強化充填材を用いる場合には、押出機のシリンダー途中のサイドフィーダーから供給することも好ましい。
成形体の製造方法は、特に限定されず、ポリエステル樹脂組成物について一般に採用されている成形法を任意に採用できる。その例を挙げると、射出成形法、超高速射出成形法、射出圧縮成形法、二色成形法、ガスアシスト等の中空成形法、断熱金型を使用した成形法、急速加熱金型を使用した成形法、発泡成形(超臨界流体も含む)、インサート成形、IMC(インモールドコーティング成形)成形法、押出成形法、シート成形法、熱成形法、回転成形法、積層成形法、プレス成形法、ブロー成形法等が挙げられ、中でも射出成形が好ましい。
換算吸光度aは、ベース樹脂のアロイ種やエラストマー、強化材等の添加剤配合、さらにはニグロシンの量によって調整することが可能である。また成形体作製時には、金型の表面度合いやゲートからの距離、さらには射出率、面進行係数、金型温度といった成形条件を調整することによっても、調整することが可能である。
換算吸光度aは、紫外可視近赤外分光光度計(島津製作所社製「UV-3100PC」)を用いて、波長940nmにおける透過率T(%)と反射率R(%)を求め、その値を用いて、以下の式によって求める。尚、厚みが1mmでない成形板を用いて測定する場合には、1mm厚みに換算した換算吸光度は、測定部の肉厚t(mm)を用いて、a/tとして求める。
吸光度a=-log{T/(100-R)}
入射率が20%未満の場合には、突き合わせ溶着性能が低下し、かつ隙間溶着性能も低下する。また逆に、入射率が80%を超える場合には、重ね合わせて溶着性能が低下し、かつ隙間溶着性能も低下する。
そして、入射率Kをこのような範囲にすることによりレーザー光の透過量とレーザー光の吸収量を調整しているので、従来のレーザー溶着のようにレーザー光透過性樹脂からなる成形体とレーザー光吸収性樹脂からなる成形体の2種を用いる必要はなく、1種類の樹脂材料のみでレーザー溶着が可能なポリエステル系レーザー溶着用成形体を提供することが可能となる。特に、同種の樹脂材料からなる溶着体同士を溶着させる場合に、本発明の効果は顕著である。
尚、入射率は、レーザー光の透過率によっても大きく変化する。透過率を変化させる要因として成形条件が挙げられるが、その成形条件としては、射出率、金型温度、樹脂温度、保圧等がある。中でも、射出率と金型温度によって変化しやすい。また、金型構造においては、金型表面性やゲート形状、ゲートの位置、ゲートの数によっても変化しやすい。更に、成形体においては、透過率を測定する部位と、成形時のゲート位置からの距離によっても大きく変化する。従って、これらの条件を適宜決めることによって、入射率を好ましい範囲に調整することができる。
色差ΔE00は、CIE2000色差式で求められる。一般的な評価法であるΔEよりも、ΔE00は、人間の目の感覚に近い評価方法であり、標準プレートの黒色度に近いほど、数値が小さくなるため、黒色度の差を評価するのに適している。また、その値は6.0以下であるのが好ましい。
射出成形の条件としては、特に制限はないが、射出速度は、10~500mm/secが好ましく、30~400mm/secがより好ましく、50~300mm/secが更に好ましく、80~200mm/secが特に好ましい。
尚、射出速度が速いほど、透過率が高くなり、入射率に影響する。但し、射出速度が速すぎると、成形体の流動末端部にガス焼けが生じるため適切な射出速度へ下げるか、金型構造においてガスベントのサイズを大きくする等の対策が講じるのが好ましい。
金型温度は、低い方が透過率が高くなり、ひいては入射率にも影響する。金型温度が低すぎると、成形体の結晶化度が低くなるため、後収縮が大きくなり、寸法安定性が悪化することにもなるため、適切な透過率及び入射率になるように、金型温度を調整することも好ましい。
面進行係数:前記射出率を、樹脂材料が射出される金型キャビティの平均厚みで除した値
好ましい面進行係数の範囲は200~1100cm3/sec・cmであり、より好ましくは250~1000cm3/sec・cm、更に好ましくは300~950cm3/sec・cm、特に好ましくは330~930cm3/sec・cmである。
本発明のレーザー溶着用樹脂組成物からなる成形体を用いると、従来は必要であったレーザー光透過性樹脂からなる成形体とレーザー光吸収性樹脂からなる成形体の2種を用いる必要がなくなる。また、レーザー光の透過深さが大きく、そのため大きい溶融深さを確保することができるので、重ね合わせ溶着は勿論、今まで出来なかったレーザー溶着用成形体の端部同士の突き合わせ溶着でも、十分高い溶着強度を達成することができる。また、成形体が、成形時のヒケや反りにより接合用部に仮に隙間が生じた場合にも、隙間が0.1mm以上、好ましくは0.2mm以上、更には0.5mm以上、特には0.8mm以上ある場合であっても、レーザー溶着が可能である。
照射するレーザー光の種類は、近赤外レーザー光であれば任意であり、YAG(イットリウム・アルミニウム・ガーネット結晶)レーザー(波長1064nm)、LD(レーザーダイオード)レーザー(波長808nm、820nm、840nm、880nm、940nm)等を好ましく用いることができる。
突き合わせ溶着は、図2に示すように、2枚の成形体1と2を突き合わせ、走査しながら、レーザー光4を照射し、溶着部5が生成することにより、レーザー溶着体ができる。
アントラキノン染料1(最大吸収波長628nm C.I.ソルベント ブルー104)0.66質量部、ペリノン染料1(最大吸収波長472nm C.I.ソルベント レッド179)0.58質量部及びアントラキノン染料3(最大吸収波長446nm C.I.ソルベント イエロー163)0.56質量部を配合機に入れて、5時間攪拌して、着色剤例1 1.8質量部を得た。
[吸光度及び最大吸収波長の測定方法]
染料サンプル 0.05gを計量し、ジメチルホルムアミド(DMF)にて溶解させ、100mlメスフラスコにて調整を行う。次にその調整液2mlをホールピペットで計り取り、DMFにて50mlメスフラスコでメスアップし、調整液を作製した。
得られた調整液を、紫外可視分光光度計(島津製作所社製の商品名:UV-1100)を用いて、吸収スペクトルを測定した。
製造例2は、製造例1の配合組成を、アントラキノン染料2(最大吸収波長629nm C.I.ソルベント ブルー97)0.54質量部、ペリノン染料1(最大吸収波長472nm C.I.ソルベント レッド179)0.63質量部及びアントラキノン染料3(最大吸収波長446nm C.I.ソルベント イエロー163)0.63質量部に代えて、それ以外は製造例1と同様にして、着色剤例2 1.8質量部を得た。
製造例3~9は、製造例1の配合組成を表1に記載した組成に変更した以外は、製造例1と同様にして、着色剤例3~着色剤例9を得た。
アントラキノン染料1(最大吸収波長628nm C.I.ソルベント ブルー104)1.50質量部、ペリノン染料1(最大吸収波長472nm C.I.ソルベント レッド179)0.90質量部及びアントラキノン染料3(最大吸収波長446nm C.I.ソルベント イエロー163)0.60質量部を配合機に入れて、5時間攪拌して、比較着色剤例1 3.0質量部を得た。
比較製造例2~3は、配合組成を、表1に記載の染料と組成に変更した以外は、比較製造例1と同様にして、比較着色剤例2~比較着色剤例3を得た。
上記で製造したいずれかの着色剤例を用いて、以下に記載の方法で樹脂組成物からなる成形体を作製した。その後、その成形体を用いてレーザー溶着を行った。
なお、着色剤以外の使用した原料は、以下の表2に記載の各成分である。
成形体例1の作製
ポリブチレンテレフタレートホモポリマー(A1)(ノバデュラン5008)50質量部と、ポリブチレンテレフタレートコポリマー(A2a)(ノバデュラン5605)50質量部と、フェノール系安定剤(安定剤2、アデカスタブAO-60)0.4質量部と、離型剤(ユニスターH476)0.7質量部と、ニグロシン(NUBIANBLACK TH-807)0.014質量部、及び着色剤例1 0.386質量部を、ステンレス製タンブラーに入れ、1時間攪拌混合した。得られた混合物を、30mmのベントタイプ2軸押出機(日本製鋼所社製、「TEX30α」)のメインホッパーに投入し、ガラス繊維(GF)(T-187)43質量部はホッパーから7番目のサイドフィーダーより供給し、押出機バレル設定温度C1~C15を260℃、ダイを250℃、スクリュー回転数200rpm、吐出量40kg/時間の条件で混練してストランド状に押し出し、樹脂組成物のペレットを得た。得られたペレットを、射出成形機(東洋機械金属社製、Si-50)を用いて、シリンダー温度260℃、金型温度80℃で成形して、縦80mm×横20mm×厚さ2mmの黒色の成形体例1(成形体例1-1、成形体例1-2)を2枚作製した。
更に換算吸光度aと入射率の測定用試験片として、シリンダー温度260℃、金型温度80℃、射出速度120mm/sec、射出率51cm3/sec、面進行係数405cm3/sec・cmの条件で成形して、縦80mm×横50mm×厚さ1.5mmと1mmの2段の段付き形状の黒色の成形板1Kを作製した。
尚、実施例Aにおいては、2枚作成した成形体は(本実施例では、成形体例1-1及び成形体例1-2)、レーザー溶着強度の測定に、また段付き形状の成形板は(本実施例では成形板1K)、透過率、反射率及び換算吸光度、並びに、色差の測定に用いた。
2段の段付き成形板の反ゲート側である1mm厚の部位において、紫外可視近赤外分光光度計(島津製作所社製「UV-3100PC」)を用いて、波長940nmにおける透過率T(%)と反射率R(%)を求めた。
更に吸光度aを、a=-log{T/(100-R)}の式によって求めた。
[入射率の求め方]
入射率K(単位:%)は、以下の式で求めた。
入射率K(%)=100-透過率-反射率
入射率Kは、成形体の1mm厚時の波長940nmのレーザー光に対する入射率である。2段プレート(縦80mm×横50mm×厚さ1.5mmと1mm、ゲート部は1.5mm厚側)の場合、反ゲート側である1mm厚の部位の透過率と反射率の測定結果から導き出した。
(色差測定用標準成形板の作製)
標準成形板は下記の方法に従って調製した。
黒色ポリブチレンテレフタレート樹脂(三菱エンジニアリングプラスチックス社製、商品名:ノバデュラン5010G30 BK2)を、射出成形機Si-50を用いて、シリンダー温度260℃、金型温度80℃にて成形して、縦80mm×横50mm×厚さ1.5mmと1mmの2段形状の色差測定用標準成形板STD・BKを1枚作製した。この標準成形板は、L*=16.05、a*=-0.24、b*=-1.70であった。
前記で得られた成形板1Kと標準成形板とを、分光色差計(スガ試験機社製 商品名 SC-T)を用いて、測定光源 D65/10° 測色径 30mmφ 測定箇所 1mm厚部の裏面を測色し、標準成形板と成形板1Kの色差を求め、標準成形板を標準にして、成形板1KのΔE00を求めた。その結果を以下の表3に示した。
2枚の成形体例1(成形体例1-1・成形体例1-2)を、図3のように突き合わされたまま当接させ、突き合わされた成形体1と2の界面に沿って、出力50Wのダイオード・レーザー[波長:940nm 連続的](社製)によるレーザービーム4を、走査速度を表3に記載の走査速度(mm/sec)にて、15mm走査させて、照射すると、一体化したレーザー溶着体が得られた。
レーザー溶着機;ファインディバイス社製 FD-200(50W機)
出力 ;50W(設定)
スポット径 ;1mmφ
走査速度 ;表3に記載の走査速度
照射エネルギー:表3に記載の通り
走査距離 ;15mm
比較例A1~A2は、配合組成を、表3に従い変更した以外は、実施例A1と同様にして、比較例A1~A2の比較成形体例1~2、並びに、それぞれの段付き形状の成形板を得た。実施例A1と同様にして、透過率と反射率から算出した、換算吸光度aと入射率Kと色差のΔE00を表3に示した。
得られた成形板を用い、実施例A1と同様に突き合わせのレーザー溶着を行い、レーザー溶着体を得た。更に引張試験を行って、溶着強度を測定し、その結果を表3に示した。
成形体例2の作製
ポリブチレンテレフタレートホモポリマー(A1)60質量部と、ポリエチレンテレフタレート樹脂(A2b)(ノバペットPBK1)40質量部と、フェノール系安定剤(安定剤2)0.4質量部と、離型剤0.7質量部と、ニグロシン(NUBIAN BLACK TH-807)0.014質量部、及び着色剤例1 0.386質量部を、ステンレス製タンブラーに入れ、1時間攪拌混合した。得られた混合物を、30mmのベントタイプ2軸押出機(日本製鋼所社製、「TEX30α」)のメインホッパーに投入し、ガラス繊維(GF)43質量部はホッパーから7番目のサイドフィーダーより供給し、押出機バレル設定温度C1~C15を260℃、ダイを250℃、スクリュー回転数200rpm、吐出量40kg/時間の条件で混練してストランド状に押し出し、樹脂組成物のペレットを得た。
更に、換算吸光度a、入射率及び色差の測定用試験片として、縦80mm×横50mm×厚さ1.5mmと1mmの2段の段付き形状の黒色の成形板2Kを作製した。
実施例A1と同様にして、換算吸光度a、入射率K、及び色差ΔE00を測定し、その結果を表3に示した。
2枚の成形体例2(成形体例2-1・成形体例2-2)を用い、実施例A1と同様に、突き合わせのレーザー溶着を行い、レーザー溶着体を得た。更に引張試験を行って、溶着強度を測定し、その結果を表3に示した。
比較例A3~A4は、配合組成を、表3に従い変更した以外は、実施例A2と同様にして、比較例A3~A4の比較成形体3~4を得た。実施例A1と同様にして、換算吸光度a、入射率K、及び色差ΔE00を測定し、その結果を表3に示した。
得られた2枚の成形体例を用い、実施例A2と同様に突き合わせのレーザー溶着を行い、レーザー溶着体を得た。更に引張試験を行って、溶着強度を測定し、その結果を表3に示した。
成形体例3の作製
ポリブチレンテレフタレートホモポリマー(A1)70質量部と、ポリカーボネート樹脂(A2c)(ユーピロンH4000)30質量部と、リン系安定剤(安定剤1、アデカスタブAX-71)0.1質量部と、フェノール系安定剤(安定剤2)0.4質量部と、離型剤0.7質量部と、ニグロシン(NUBIAN BLACK TH-807)0.014質量部、及び着色剤例1 0.386質量部を、ステンレス製タンブラーに入れ、1時間攪拌混合した。得られた混合物を、30mmのベントタイプ2軸押出機(日本製鋼所社製、「TEX30α」)のメインホッパーに投入し、ガラス繊維(GF)43質量部はホッパーから7番目のサイドフィーダーより供給し、押出機バレル設定温度C1~C15を260℃、ダイを250℃、スクリュー回転数200rpm、吐出量40kg/時間の条件で混練してストランド状に押し出し、樹脂組成物のペレットを得た。得られたペレットを、射出成形機(東洋機械金属社製、Si-50)を用いて、シリンダー温度260℃、金型温度80℃で成形して、縦80mm×横20mm×厚さ2mmの黒色の成形体例3(成形体例3-1、成形体例3-2)を2枚作製した。更に換算吸光度a、入射率及び色差の測定用試験片として、縦80mm×横50mm×厚さ1.5mmと1mmの2段の段付き形状の黒色の成形板3Kを作製した。
実施例A1と同様にして、換算吸光度a、入射率K、及び色差ΔE00を測定し、その結果を表3に示した。
2枚の成形体例3(成形体例3-1・成形体例3-2)を用い、実施例A1と同様に、突き合わせのレーザー溶着を行い、レーザー溶着体を得た。更に引張試験を行って、溶着強度を測定し、その結果を表3に示した。
比較例A5~A6は、配合組成を、表3に従い変更した以外は、実施例A3と同様にして、比較例A5~A6の比較成形体5~6を得た。実施例A1と同様にして、換算吸光度a、入射率K、及び色差ΔE00を測定し、その結果を表3に示した。
得られた2枚の成形体例を用い、実施例A3と同様に突き合わせのレーザー溶着を行い、レーザー溶着体を得た。更に引張試験を行って、溶着強度を測定し、その結果を表3に示した。
成形体例4の作製
ポリブチレンテレフタレートホモポリマー(A1)294質量部と、ポリカーボネート樹脂(A2c)126質量部及び、ガラス繊維(GF)180質量部からなる合計600質量部に対し、ニグロシン(NUBIAN BLACK TH-807)0.06質量部、及び着色剤例1 1.80質量部を使用した。上記原料の中、ガラス繊維以外をステンレス製タンブラーに入れ、1時間攪拌混合した。得られた混合物を、30mmのベントタイプ2軸押出機(日本製鋼所社製、「TEX30α」)のメインホッパーに投入し、ガラス繊維はホッパーから7番目のサイドフィーダーより供給し、押出機バレル設定温度C1~C15を260℃、ダイを250℃、スクリュー回転数200rpm、吐出量40kg/時間の条件で混練してストランド状に押し出し、樹脂組成物のペレットを得た。得られたペレットを、射出成形機Si-50を用い、シリンダー温度260℃、金型温度80℃で通常の方法により成形して、縦80mm×横20mm×厚さ2mmの黒色の成形体例4(成形体例4-1、成形体例4-2)を2枚作製した。
透過率:64.3%、反射率:9.2%、入射率K:26.5%、換算吸光度:0.14
2枚の成形体例4(成形体例4-1・成形体例4-2)を、図2のように突き合わされたまま当接させ、突き合わされた成形体1と2の界面に沿って、出力50Wのダイオード・レーザー[波長:940nm 連続的](ファインディバイス社製)によるレーザービーム4を、走査速度を表4に記載の走査速度(mm/sec)に変えて、15mm走査させて、照射すると、一体化したレーザー溶着体が得られた。更に引張試験を行って、溶着強度を測定し、その結果を表4に示した。
表1及び表2に記載した各成分及びニグロシン(NUBIAN BLACK TH-807)を表5に記載の量(いずれも質量部)でブレンドし、これを30mmのベントタイプ2軸押出機(日本製鋼所社製、「TEX30α」)のメインホッパーに投入し、ガラス繊維はホッパーから7番目のサイドフィーダーより供給し、押出機バレル設定温度C1~C15を260℃、ダイを250℃、スクリュー回転数200rpm、吐出量40kg/時間の条件で混練してストランド状に押し出し、樹脂組成物のペレットを得た。
結晶化温度(Tc)が低い方が固化が遅くなるので、レーザー溶着強度は高くなるものと考えられる。
尚、実施例Cにおいては、1mmのダンベル片は、透過率、反射率、換算吸光度、及び、色調の測定に、また1.5mmのダンベル片及び段付きプレートはそれぞれレーザー溶着強度の測定に使用した。
1mm厚のASTM4号ダンベルの反ゲート側の溶着用部において、紫外可視近赤外分光光度計(島津製作所社製「UV-3100PC」)を用いて、波長940nmにおける透過率T(%)と反射率R(%)を求めた。
更に吸光度aを、a=-log{T/(100-R)}の式によって求めた。
[入射率の求め方]
入射率K(単位:%)は、以下の式で求めた。
入射率K(%)=100-透過率-反射率
入射率Kは、成形体の1mm厚時の波長940nmのレーザー光に対する入射率である。ASTM4号ダンベル(1mm)の成形体の場合、反ゲート側の部位(樹脂を注入したゲートの反対側にある部位)の透過率と反射率の測定結果から導き出した。
溶着条件は以下の通りである。
使用装置:ファインディバイス社製FD2230
レーザー波長:940nm
レーザースポット径:Φ2.1mm
レーザーヘッドと試験片間の距離:75mm
成形体への重ね合わせ加圧力:2MPa
レーザー走査スピード:10mm/sec
レーザー走査距離:16mm
レーザー出力は、表5に記載の通り可変させた。
また溶着体は、インストロン社製5544の万能型試験機を用いて、スパン間:160mm、引張速度:5mm/minの条件下にて溶着強度(単位:N)を求めた。
なお、溶着性は溶着強度が高いことだけでなく、どのような条件下においても高い溶着強度を保持していることが、レーザー溶着条件幅が広いことを意味し、レーザー溶着性に優れていると評価される。
上記で得た同じ組成からなる2段付きプレート2枚を、図3のように、1.5mm厚の部分を重ね合わせて、レーザー溶着性(溶着強度試験)を評価した。
レーザー溶着性評価-2(ダンベル片の重ね合わせ溶着):
上記で得た同じ組成からなる4号ダンベル片(1.5mm厚)2枚の反ゲート側端部を、図3のように重ね合わせて、レーザー溶着性(溶着強度試験)を評価した。
上記で得た同じ組成からなる1.5mm厚のASTM4号の2つのダンベル11、12を使用し、ダンベル11とダンベル12の反ゲート側の端部を、図5に示すように上下に重ね合わせ、その重ね合わせ部14に金属片スペーサー15,15’を挟んだものを、ガラス製土台(図示せず)の上に載せ、ダンベル11、12上にガラスプレート16を載せて、その上から2MPaで加圧しながら、レーザービーム17をレーザー出力80W、レーザー走査スピード10mm/sec下にて照射させて溶着を行った。その際、金属スペーサー15,15’で作る隙間間隔を、表5に記載の0mm~0.8mmに変化させ、また上記同様の条件で、図中の矢印aの引っ張り方向に荷重をかけて、破壊した時の荷重(単位:N)を求めた。
上記で得られた組成からなるASTM4号ダンベル(1.0mm厚)の反ゲート側の端部をコニカミノルタ社製「CM-3600d」(光源:D65、視野:10°、方式:SCE、ターゲットマスク8mm)を用いて色差測定を行い、前記した色差測定用標準成形板STD・BKに対するΔE00及びΔEを求めた。
結果を以下の表5に記載した。
[突き合わせ溶着用レーザー溶着体の製造]
表1及び表2に記載した各成分及びニグロシン(NUBIAN BLACK TH-807)を表6に記載の量(いずれも質量部)でブレンドし、これを30mmのベントタイプ2軸押出機(日本製鋼所社製、「TEX30α」)のメインホッパーに投入し、ガラス繊維はホッパーから7番目のサイドフィーダーより供給し、押出機バレル設定温度C1~C15を260℃、ダイを250℃、スクリュー回転数200rpm、吐出量40kg/時間の条件で混練してストランド状に押し出し、樹脂組成物のペレットを得た。
結晶化温度(Tc)が低い方が固化が遅くなるので、レーザー溶着強度、ウエルド強度も高くなるものと考えられる。
ASTM4号ダンベルの反ゲート側の溶着用部において、紫外可視近赤外分光光度計(島津製作所社製「UV-3100PC」)を用いて、波長940nmにおける透過率T(%)と反射率R(%)を求めた。更に吸光度aを、a=-log{T/(100-R)}の式によって求め、1mm厚みに換算した換算吸光度は、測定部の肉厚t(mm)を用いて、a/tとして求めた。
[入射率の求め方]
入射率K(単位:%)は、以下の式で求めた。
入射率K(%)=100-透過率-反射率
入射率Kは、成形体の1mm厚時の波長940nmのレーザー光に対する入射率である。ASTM4号ダンベル(1mm)の成形体の場合、反ゲート側の部位(樹脂を注入したゲートの反対側にある部位)の透過率と反射率の測定結果から導き出した。
上記で得た同じ組成からなる2mm厚のASTM4号の2つのダンベル11、12を使用し、ファインディバイス社製レーザー溶着装置(レーザー波長:940nm、レーザースポット径:Φ2.1mm、レーザーヘッドと試験片間の距離:79.7mm)を用いて、図4に示すように、ダンベル11とダンベル12の樹脂注入ゲートとは反対側(反ゲート側)の端部同士を突き合わせ、その突き合わせ部13に金属片スペーサー15,15’を挟んだものを、ガラス製土台(図示せず)の上に載せ、ダンベル11、12上にガラスプレート16を載せて、横から0.4MPaの加圧をかけながら、レーザービーム17をレーザー出力200W、レーザー走査速度20mm/sec、レーザー走査距離:16mmの条件にて照射させて溶着を行った。その際、金属スペーサー15,15’で作る隙間間隔を、表6に記載の0mm~0.8mmに変化させ、またインストロン社製5544の万能型試験機を用いて、スパン間160mm、引張速度5mm/minの条件で、図中の矢印aの引っ張り方向に荷重をかけて破壊する荷重(単位:N)を求めた。
なお、溶着性は溶着強度が高いことだけでなく、どのような条件下においても高い溶着強度を保持していることが、レーザー溶着条件幅が広いことを意味し、レーザー溶着性に優れていると評価される。
前記したASTM4号ダンベルを成形したのと同様にして、厚さ1.6mmのUL94(アンダーライターズラボラトリーズのサブジェクト94)燃焼試験片を、試験片の両側長手方向からの2点ゲートで樹脂を射出して、試験片中央部にウエルドラインが形成された厚さ1.6mmのUL94燃焼試験片を射出成形し、これをスパン間40mm、試験速度2mm/minの条件にて、ウエルド曲げ強度(単位:MPa)を測定した。
結果を以下の表6に記載した。
表1及び表2に記載した各成分及びニグロシン(NUBIAN BLACK TH-807)を表7に記載の量(いずれも質量部)でブレンドし、これを30mmのベントタイプ2軸押出機(日本製鋼所社製、「TEX30α」)のメインホッパーに投入し、ガラス繊維はホッパーから7番目のサイドフィーダーより供給し、押出機バレル設定温度C1~C7を260℃、C8~C15を220℃、ダイを250℃、スクリュー回転数220rpm、吐出量40kg/時間の条件で混練してストランド状に押し出し、樹脂組成物のペレットを得た。
また、上記で得られた樹脂組成物ペレットを120℃で5時間乾燥した後、射出成形機(東洋機械金属社製、Si-50)を用いて、シリンダー温度260℃、金型温度80℃で縦80mm×横50mm×厚さ1.5mmと1mmの2段の段付き形状のプレートを射出速度120mm/sec、射出率51cm3/sec、面進行係数405cm3/sec・cmの条件で、作製した。
段付き2段プレートの1mm厚部分において、紫外可視近赤外分光光度計(島津製作所社製「UV-3100PC」)を用いて、波長940nmにおける透過率T(%)と反射率R(%)を求めた。更に吸光度aを、a=-log{T/(100-R)}の式によって求めた。
[入射率の求め方]
入射率K(単位:%)は、以下の式で求めた。
入射率K(%)=100-透過率-反射率
入射率Kは、成形体の1mm厚時の波長940nmのレーザー光に対する入射率である。2段の段付きプレートの成形体の場合、反ゲート側の1mm厚の部位(樹脂を注入したゲートの反対側にある部位)の透過率と反射率の測定結果から導き出した。
上記で得た同じ組成からなる2段付きプレート2枚を1.5mm厚の部分を、図3のように重ね合わせて、レーザー溶着した。
得られたレーザー溶着体は、インストロン社製5544の万能型試験機を用いて、スパン間:160mm、引張速度5mm/minの条件下にて、引っ張り方向に荷重をかけて破壊する荷重(単位:N)を求めた。
溶着条件は以下の通りである。
使用装置:ファインディバイス社製FD2230
レーザー波長:940nm
レーザースポット径:Φ2.1mm
レーザーヘッドと試験片間の距離:75mm
成形体への重ね合わせ加圧力:2MPa
レーザー走査速度:10mm/s
レーザー走査距離:16mm
レーザー出力は、表7に記載の通り可変させた。
上記で得た同じ組成からなる2段付きプレート2枚を1.5mm厚の部分を重ね合わせて、図5と同様にして、その重ね合わせ部に金属片スペーサーを挟んで溶着を行い、隙間間隔を0mm~0.3mmの表7に記載の隙間間隔で変化させ、下記のレーザー溶着条件とレーザー出力80Wとし、レーザー走査速度10mm/sにて、レーザー溶着し、得られた溶着体をインストロン社製5544の万能型試験機を用いて、スパン間:160mm、引張速度:5mm/minの条件下にて引っ張り方向に荷重をかけて破壊する荷重(単位:N)を求めた。
なお、溶着性は溶着強度が高いことだけでなく、どのような条件下においても高い溶着強度を保持していることが、レーザー溶着条件幅が広いことを意味し、レーザー溶着性に優れていると評価される。
溶着条件は以下の通りである。
使用装置:ファインディバイス社製FD2230
レーザー波長:940nm
レーザースポット径:Φ2.1mm
レーザーヘッドと試験片間の距離:75mm
成形体への重ね合わせ加圧力:2MPa
レーザー走査距離:16mm
上記で得た2段付きプレートの1.0mm厚部をコニカミノルタ社製「CM-3600d」(光源:D65、視野:10°、方式:SCE、ターゲットマスク8mm)を用いて色差測定を行い、標準プレートに対するΔE00、ΔEを求めた。
熱処理後の色調:
上記で得た2段付きプレートを140℃熱風オーブン下に12時間放置し、上記と同様に熱処理後のプレートの1.0mm厚の部分の色差測定を行い、熱処理前後での色調のΔEを求めた。
また、熱処理後の色相を標準プレートに対するΔE00として求めた。
ポリブチレンテレフタレート樹脂(三菱エンジニアリングプラスチックス社製、商品名:ノバデュラン5010R5 NA(自然色))を、射出成形機NEX80-9Eを用いて、シリンダー温度260℃、金型温度80℃にて成形された縦100mm×横100mm×厚さ3mmのポリブチレンテレフタレート(自然色)プレートを成形し、これを上記で得た2段付きプレートと重ね合わせてクリップで固定し、140℃熱風オーブン下に3時間放置し、ポリブチレンテレフタレート(自然色)プレートへの染料移行状態を、目視にて、以下の評価結果に仕分けした。
○:染料の移行が少ない
△:染料の移行がやや多い
×:染料の移行が著しい
結果を以下の表7に記載した。
Claims (12)
- レーザー光による溶着に用いる樹脂組成物であって、
(A)ポリブチレンテレフタレートホモポリマーと、
ポリブチレンテレフタレートコポリマー、ポリエチレンテレフタレート樹脂又はポリカーボネート樹脂の少なくとも1種とを含む熱可塑性ポリエステル系樹脂材料100質量部に対し、
(B)ニグロシン0.0005~0.5質量部及び、
(C)最大吸収波長が590~635nmの範囲であるアントラキノン染料C1と、最大吸収波長が460~480nmの範囲であるペリノン染料C2と、最大吸収波長が435~455nmの範囲であるアントラキノン染料C3を、C1、C2及びC3の合計100質量部に対する質量比でC1:C2:C3=24~41:24~39:22~46で少なくとも含む、着色剤0.01~2質量部を含有することを特徴とするレーザー溶着用樹脂組成物。 - (C)着色剤が、460~480nmの範囲であるペリノン染料C2及び最大吸収波長が590~635nmの範囲であるアントラキノン染料C1を、両者の質量比C2/C1=0.61~1.50の割合で含有する着色剤である請求項1に記載のレーザー溶着用樹脂組成物。
- (A)熱可塑性ポリエステル系樹脂材料が、ポリブチレンテレフタレートホモポリマー及びポリブチレンテレフタレートコポリマーを含み、ポリブチレンテレフタレートコポリマーの含有量が、両者の合計100質量%に対して、5~70質量%である請求項1又は2に記載のレーザー溶着用樹脂組成物。
- (A)熱可塑性ポリエステル系樹脂材料が、ポリブチレンテレフタレートホモポリマー及びポリエチレンテレフタレート樹脂を含み、ポリエチレンテレフタレート樹脂の含有量が、両者の合計100質量%に対して、5~50質量%である請求項1又は2に記載のレーザー溶着用樹脂組成物。
- (A)熱可塑性ポリエステル系樹脂材料が、ポリブチレンテレフタレートホモポリマー及びポリカーボネート樹脂を含み、ポリカーボネート樹脂の含有量が、ポリブチレンテレフタレートホモポリマー及びポリカーボネート樹脂の合計100質量%に対して、5~50質量%である請求項1又は2に記載のレーザー溶着用樹脂組成物。
- 前記樹脂組成物からなる1mm厚の成形板の940nmのレーザー光に対する換算吸光度aが、0.05~1である請求項1~5のいずれか1項に記載のレーザー溶着用樹脂組成物。
- 前記樹脂組成物からなる1mm厚の成形板の940nmのレーザー光に対する入射率Kが、20~80%である請求項1~6のいずれか1項に記載のレーザー溶着用樹脂組成物。
但し、入射率K(%)=100-透過率-反射率とする。 - 請求項1~7のいずれか1項に記載のレーザー溶着用樹脂組成物からなるレーザー溶着用成形体。
- 請求項8に記載の成形体のレーザー溶着体。
- 溶着体が、少なくともその溶着部の一部において、溶着する際の成形体の隙間が0.1mm以上である請求項9に記載のレーザー溶着体。
- 成形体同士を突き合わせ溶着した請求項9又は10に記載のレーザー溶着体。
- 成形体同士を重ね合わせ溶着した請求項9又は10に記載のレーザー溶着体。
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WO2019088058A1 (ja) * | 2017-10-31 | 2019-05-09 | 三菱エンジニアリングプラスチックス株式会社 | レーザー溶着体の製造方法 |
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JP7122490B1 (ja) * | 2020-10-22 | 2022-08-19 | 三菱エンジニアリングプラスチックス株式会社 | 樹脂組成物、成形品、樹脂組成物の使用、キット、レーザー溶着品、および、レーザー溶着品の製造方法 |
WO2023223775A1 (ja) * | 2022-05-17 | 2023-11-23 | ポリプラスチックス株式会社 | レーザー光透過性樹脂組成物、成形品及び複合成形品 |
Also Published As
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US10781308B2 (en) | 2020-09-22 |
EP3421540A4 (en) | 2019-07-24 |
EP3421540B1 (en) | 2020-05-13 |
US20190016883A1 (en) | 2019-01-17 |
CN108699322A (zh) | 2018-10-23 |
EP3421540A1 (en) | 2019-01-02 |
CN108699322B (zh) | 2020-07-10 |
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