CN102850730B - Laser-transmitting resin molded article, and composite molded article comprising the same - Google Patents

Laser-transmitting resin molded article, and composite molded article comprising the same Download PDF

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Publication number
CN102850730B
CN102850730B CN201210040854.3A CN201210040854A CN102850730B CN 102850730 B CN102850730 B CN 102850730B CN 201210040854 A CN201210040854 A CN 201210040854A CN 102850730 B CN102850730 B CN 102850730B
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CN
China
Prior art keywords
resin
laser
transmitting
molding
brominated
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Expired - Fee Related
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CN201210040854.3A
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Chinese (zh)
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CN102850730A (en
Inventor
春原淳
平川阳一
坂田耕一
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WinTech Polymer Ltd
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WinTech Polymer Ltd
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • 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
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    • B29C65/16—Laser beams
    • B29C65/1603—Laser beams characterised by the type of electromagnetic radiation
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • 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
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C65/82—Testing the joint
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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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    • B29C65/82—Testing the joint
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    • B29C65/8215—Tensile tests
    • 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
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    • 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
    • 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
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    • 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
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  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Electromagnetism (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Toxicology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Disclosed is a laser-transmitting resin molded article which comprises a polyester resin as a base material and has both of a laser-weldable property (a laser-transmitting property) and flame retardancy at high levels. The molded article is formed from a resin composition comprising a polyester resin (A) (e.g., a PBT resin), at least one bromine-containing compound (B) selected from a brominated (meth)acrylate resin, a brominated styrene resin, a brominated polycarbonate resin and a brominated epoxy resin, and an antimony oxide (C) having an average particle diameter of 2 to 10 [mu]m. The molded article has an excellent laser-transmitting property and excellent flame retardancy, and may have a laser beam transmissivity of 20% or more as measured at a thickness of 1 mm and a flame retardancy evaluation rating of V-0 as measured in accordance with UL94 standard at a thickness of 0.8 mm. The resin composition may further comprise a filler, a fluorine-containing resin, a polycarbonate resin, a phosphorus compound and/or a crystallization nucleating agent.

Description

Laser-transmitting resin molding and composite formed article thereof
The application is to be dividing an application of May 27, application number in 2008 are 2008800186427, denomination of invention is " laser-transmitting resin molding and composite formed article thereof " patent application the applying date.
Technical field
What the present invention relates to that laser-transmitting is high and excellent in flame retardance, by laser welding, with the transmissive side parts of the laser welding (with) resin combination, formed can be used as the molding for laser welding of the transmissive side parts of laser (laser-transmitting side molding) and the composite formed article that uses this molding.
Background technology
Polyester based resin such as polybutylene terephthalate (PBT) be resin owing to thering is the various characteristicses such as excellent thermotolerance, chemical-resistant, electrical characteristic, mechanical characteristics and shaping processability, can be used for many purposes.As concrete purposes, can list the junctor class of carrying in various automobile electricals dress parts (various control units, various sensor, spark coil etc.), automobile and electric products, switch block, relay1 block, coil component, transformer part, lamp part etc.These parts have conductive part mostly, in these parts, in recent years, because the impact of the faults such as extremely overheated, short circuit causes that danger on fire increases, and is seeking to improve flame retardant resistance.
With regard to improving PBT, be that the flame retardant resistance of the polyester based resins such as resin is studied in the past.The flame-retardant polyester resin composition of the certain aromatic polyester, brominated epoxy compound, bromination polyacrylic ester and the ANTIMONY TRIOXIDE SB 203 99.8 PCT that contain specified proportion for example, is disclosed in TOHKEMY 2000-256545 communique (patent documentation 1).In the document, record, about ANTIMONY TRIOXIDE SB 203 99.8 PCT, preferably use those of purity more than 98%, particle diameter 0.1～5 μ m, those of purity more than 99%, particle diameter 0.5～3 μ m are particularly preferred.To show the method for flame retardant resistance be known in combination by bromine compounds and antimony compounds like this.Wherein, in Japanese kokai publication sho 61-66746 communique (patent documentation 2), record, in polybutylene terephthalate, be used as aromatic series bromine compounds (bromine 5～10 substitution compounds of phenyl ether of fire retardant, the low molecular weight brominated compounds such as bromine 5～10 substitution compounds of the aromatic nucleus hydrogen such as ethylene diphenyl ether, aromatic copolycarbonate, the bromide of the monomer of epoxy compounds and their polymkeric substance, the bromide of polystyrene oligomer, cyanogen bromide urea ester compound etc.) and above (preferably more than 2 μ m as the median size 1 μ m of flame retardant, especially ANTIMONY TRIOXIDE SB 203 99.8 PCT 5～7 μ m), can improve the melting heat stability of flame retardance poly butylene terephthalate composition.
In addition, in these documents about the laser-transmitting of flame-retardant polyester resin composition and laser welding all without any record.
On the other hand, above-mentioned parts (molding) mostly the joint by a plurality of parts (or part) etc. make or engage with miscellaneous part after forming parts.And the joint of each part or parts utilizes that tackiness agent, screw are fixed, snap engagement (snap-fit), various welding process (hot plate welding, ultrasonic welding, vibration welded, laser welding etc.) etc.Yet, while using tackiness agent, there is the operation problem consuming time and that generation is loaded to environment till tackiness agent extremely solidifies.In addition, fixing for screw, the man-hour of link and cost increase.In the middle of welding process, hot plate welding, ultrasonic welding, vibration welded are because heat, vibration etc. likely damage goods.In contrast, with the method for joining of laser welding, do not have because follow the heat of welding or vibrate and damage goods, and welding operation is also very simple and easy.Therefore, the recently application of laser welding method is more extensive, as the welding process of various resin components, attracts attention.
Yet, the PBT of take be the resin polyester based resin that is representative because the transmissivity of laser is low, there is the problem that is difficult to welding, this has been proposed to various schemes.For example, TOHKEMY 2003-136601 communique (patent documentation 3) discloses a kind of plastic components, it is the radioparent plastic components with the Application Areas that is applicable to laser welding, aforementioned plastic components comprises the composition that contains polyester, under the wavelength of 800～1200nm, it is more than 10% using the transmissivity of every 1mm thickness of the molding mensuration of being made by foregoing.In the document, record, in order to improve flame retardant resistance, can add fire retardant and flame retardant.In addition, in TOHKEMY 2001-26656 communique (patent documentation 4), a kind of method that manufactures body is disclosed, comprise by molding (A) and other molding (B) are carried out to welding processing and make it integrated, described molding (A) by be selected from fusing point be the PBT based copolymer of 170～220 ℃, polyethylene terephthalate based copolymer that fusing point is 200～250 ℃ and fusing point be 210～260 ℃ Polyethylene Naphthalate based copolymer at least one polyester based copolymer (a) form.In the document, record, in not damaging the scope of invention effect, can add the fire retardants such as halogenide, phosphorus compound, flame retardant etc.Yet, in the fire-retardant polyester based resin composition of recording in these documents, lack the transmissivity to laser, be difficult to carry out fully laser welding.
In addition, in Japanese Unexamined Patent Application Publication 2006-509893 communique (patent documentation 5), a kind of polyester and resin composition is disclosed, its be flame retardant resistance can laser welding polyester and resin composition, the phosphonium flame retardant of the thermoplastic polyester that comprises (A) 10～90 % by weight, (B) 1～35 % by weight, the phenol polymer of (C) 1～25 % by weight and (D) thermoplastic acrylic copolymer of 1～25 % by weight.Although the resin combination in the document can have sufficient flame retardant resistance in laser-transmitting and the desired practicality of polyester and resin composition concurrently, but owing to take phenol polymer as essential composition, therefore the problem existing is, molding variable color is dark brown, in addition, heat deflection temperature (HDT) is reduced, damaged sufficient color harmony thermal property in the desired practicality of polyester and resin composition.
Like this, in the prior art, can have laser welding and high flame retardant resistance concurrently, it is difficult further having desired other characteristics of high-caliber these characteristics and polyester and resin composition concurrently.
Patent documentation 1: TOHKEMY 2000-256545 communique (claims, paragraph [0028])
Patent documentation 2: Japanese kokai publication sho 61-66746 communique (claims, hurdle, 18 row～page 3 upper left, hurdle, page 2 bottom right 9 row, hurdle, page 3 upper left 17～19 row)
Patent documentation 3: TOHKEMY 2003-136601 communique (claims, paragraph [0018])
Patent documentation 4: TOHKEMY 2001-26656 communique (claims, paragraph [0027])
Patent documentation 5: Japanese Unexamined Patent Application Publication 2006-509893 communique (claims)
Summary of the invention
the problem that invention will solve
Therefore, the object of the invention is to, the composite formed article that laser-transmitting resin molding is provided and uses this molding, although it be take polyester based resin (especially the polyaromatic such as polybutylene terephthalate acid alkylene ester (polyalkylene arylate) is resin) and, for basic, can have high-caliber laser welding (laser-transmitting) and flame retardant resistance concurrently.
Another object of the present invention is, provides and can have high-caliber laser welding and flame retardant resistance concurrently, and have the laser-transmitting resin molding of excellent color harmony thermostability and the composite formed article that uses this molding.
Another object of the present invention is, provides and has excellent laser-transmitting, the laser-transmitting resin molding of the flame retardant resistance that also can remain high when very thin of being simultaneously shaped and the composite formed article that uses this molding.
A further object of the present invention is, provides by laser welding the molding with high flame retardant resistance is engaged to the composite formed article forming with resin forming product that can absorbing laser.
for the scheme of dealing with problems
The inventor etc. conduct in-depth research in order to realize aforementioned problems, found that, while forming laser-transmitting parts with the polyester resin composition that specific bromine based compound (or bromide fire retardant) and the sb oxide with specified particle diameter are combined, although take polyester based resin (especially the polyaromatic such as polybutylene terephthalate acid alkylene ester is resin) for basic, but do not damage laser-transmitting, can have high-caliber laser welding and flame retardant resistance concurrently, thereby complete the present invention.
, laser-transmitting resin molding of the present invention (or laser-transmitting side molding) is to contact with laser absorption resin forming product that can absorbing laser, the laser-transmitting resin molding that makes laser-transmitting and engage with aforementioned laser absorbent resin molding, wherein this laser-transmitting resin molding (is referred to as the transmissive side parts resin combination in laser welding sometimes by resin combination, laser welding (transmissive side parts are used) flame retardant resin composition etc.) form, this resin combination comprises polyester based resin (A) and is selected from bromination (methyl) acrylic resin, brominated styrene is resin, brominated polycarbonate is at least one the bromine based compound (B) (or bromide fire retardant (B)) in resin and brominated epoxy resin and the sb oxide (C) with greater particle size (median size approximately 2～10 μ m).
This molding has excellent laser-transmitting, and for example, when thickness 1mm (or molding of thickness 1mm), laser-transmitting rate can be for more than 20%.
In aforementioned molding (or resin combination), aforementioned polyester based resin (A) can be that polyaromatic acid alkylene ester is resin (polyaromatic acid C 2-4alkylene ester is resin etc., and especially polybutylene terephthalate is resin).
Aforementioned sb oxide (C) can be especially at least one being selected from ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide and sodium antimonate (sodium antimonate).
In aforementioned molding (or resin combination), with respect to 100 weight part polyester based resins (A), the ratio of bromine based compound (B) can be approximately 10～50 weight parts, with respect to 100 weight part polyester based resins (A), the ratio of sb oxide (C) can be approximately 5～30 weight parts.
Aforementioned molding (or resin combination) can further contain polycarbonate-based resin (D) and phosphorus series compound (E).Aforementioned molding (or resin combination) can further contain crystallization promoter (F).Aforementioned molding (or resin combination) can further contain packing material.In addition, aforementioned molding (or resin combination) can further contain fluorine resin.
Molding of the present invention (or resin combination) has excellent flame retardant resistance, and when thickness 0.8mm (or molding of thickness 0.8mm), the flame retardant resistance evaluation based on UL 94 standards can be V-0 conventionally.
The present invention also comprises by laser welding aforementioned laser transmitting resin molding is engaged to the composite formed article forming with laser absorption resin forming product that can absorbing laser.This composite formed article can be: laser-transmitting resin molding at least has the resin forming product that makes position laser-transmitting, that thickness is 0.1～1.0mm, and the composite formed article engaging with laser absorption resin forming product at this position.Aforementioned composite formed article for example can pass through the contact surface to laser-transmitting resin molding and laser absorption resin forming product, and the direction irradiating laser of laser absorption resin forming product from aforementioned laser-transmitting resin molding side direction is manufactured.
invention effect
In laser-transmitting resin molding of the present invention, due to the sb oxide of polyester based resin (polybutylene terephthalate is resin etc.), specific bromine based compound (bromide fire retardant) and specified particle diameter is combined, although the polyester based resin (especially polybutylene terephthalate is that the polyaromatic acid alkylene esters such as resin are resin) of therefore take is basis, can have high-caliber laser welding (laser-transmitting) and flame retardant resistance concurrently.Therefore, although keep the excellent properties (mechanical characteristics, thermotolerance, chemical-resistant etc.) of polyester based resin, do not damage laser-transmitting, can have high-caliber laser welding and flame retardant resistance concurrently.In addition, laser-transmitting resin molding of the present invention, owing to can being substantially devoid of phenol polymer etc., therefore, has high-caliber laser welding and flame retardant resistance concurrently, and has excellent color harmony thermostability.Further, laser-transmitting resin molding of the present invention has excellent laser-transmitting, even and be shaped very thinly, also can maintain high flame retardant resistance.Therefore, can obtain by the molding (especially thin molding) with high flame retardant resistance and resin forming product that can absorbing laser are engaged to the composite formed article forming by laser welding.
Accompanying drawing explanation
Fig. 1 is for the schematic side view of the laser welding of embodiment and comparative example is described.
Fig. 2 is for the diagrammatic top view of the laser welding of embodiment and comparative example is described.
Embodiment
Laser-transmitting resin molding of the present invention (or laser-transmitting side molding) is to contact with laser absorption resin forming product that can absorbing laser, the laser-transmitting resin molding that makes laser-transmitting and engage with aforementioned laser absorbent resin molding, and form with specific polyester resin composition.And, in the present invention, also comprise the specific polyester resin composition (transmissive side in laser welding is resin combination, laser welding (transmissive side parts are used) flame retardant resin composition for parts) that this laser welding is used.
Aforementioned resin (be sometimes referred to as resin combination for laser welding, flame retardant resin composition, polyester resin composition, transmissive side resin combination, resin combination etc. for parts for laser welding) comprises polyester based resin (A), specific bromine based compound (B) and specific sb oxide (C).
(polyester based resin (A))
As the polyester based resin of base resin, be equal polyester or the copolyesters that the polycondensation of polycondensation, hydroxycarboxylic acid or lactone by dicarboxylic acid composition and diol component or polycondensation of these compositions etc. obtain.
As dicarboxylic acid composition, such as listing aliphatic dicarboxylic acid (C such as hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, dimeracid 4-40dicarboxylic acid, preferably C 4-14dicarboxylic acid), ester ring type dicarboxylic acid is (such as C such as six hydrogen terephthalic acids 8-12dicarboxylic acid), aromatic dicarboxylic acid (for example terephthalic acid, phthalic acid, m-phthalic acid; The naphthalene dicarboxylic acids such as 2,6-naphthalene dicarboxylic acids; 4,4'-diphenyldicarboxylic acids, 4,4 '-diphenyl ether dicarboxylic acid, 4,4 '-ditan dicarboxylic acid, 4, the C such as 4 '-diphenylketone dicarboxylic acid 8-16dicarboxylic acid) or their reactive derivatives [for example, the lower alkyl esters (C of terephthalic acid, phthalic acid or the m-phthalic acid such as dimethyl terephthalate (DMT), dimethyl phthalate, dimethyl isophthalate (DMI) 1-4alkyl esters etc.), acyl chlorides, acid anhydrides etc. can form the derivative of ester] etc.In addition, as required, except dicarboxylic acid composition, can be used together the polycarboxylic acids such as trimellitic acid, pyromellitic acid and become to grade.
As diol component, such as listing aliphatic diol (C such as ethylene glycol, trimethylene, propylene glycol, BDO, neopentyl glycol, hexylene glycol, ethohexadiol, decanediol 2-12alkane diol, preferably C 2-10alkane diol), polyalkylene glycol [has a plurality of oxidation C 2-4the glycol of alkylidene unit, such as Diethylene Glycol～TEG, dipropylene glycol～tetra-propylene glycol, polytetramethylene glycol etc.], alicyclic diol (for example, 1,4-cyclohexane diol, 1,4-cyclohexanedimethanol, Hydrogenated Bisphenol A etc.), aromatic diol [for example, the C such as quinhydrones, Resorcinol, naphthalene glycol 6-14aromatic diol; Xenol; Bisphenols; Xylyl alcohol etc.] etc.
As bisphenols, can list two (4-hydroxyphenyl) methane (Bisphenol F), 1, two (4-hydroxyphenyl) ethane (dihydroxyphenyl propane D), 1 of 1-, two (4-hydroxyphenyl) propane, 2 of 1-, two (4-hydroxyphenyl) propane (dihydroxyphenyl propane), 2 of 2-, two (the 4-hydroxy-3-methyl phenyl) propane, 2 of 2-, two (4-hydroxyphenyl) butane, 2 of 2-, two (hydroxyaryl) C such as two (4-hydroxyphenyl) hexanes of 2- 1-6alkane; Two (hydroxyaryl) C such as two (4-hydroxyphenyl) hexanaphthenes of 1,1- 4-10naphthenic hydrocarbon; Two (4-hydroxyphenyl) ether; 4,4 '-dihydroxy-diphenyl sulfone; 4,4 '-dihydroxyl diphenylsulfide; 4,4 '-dihydroxyl diphenylketone and their alkylene oxide adducts.As alkylene oxide adducts, can list the C of bisphenols 2-3alkylene oxide adducts, for example, 2,2-is two-[4-(2-hydroxyl-oxethyl) phenyl] propane, diethoxy dihydroxyphenyl propane (EBPA), 2, and 2-is two-[4-(2-hydroxyl propoxy-) phenyl] propane, dipropoxy dihydroxyphenyl propane etc.In alkylene oxide adducts, the epoxy alkane (C such as oxyethane, propylene oxide 2-3epoxy alkane) addition mole number is approximately 1～10 mole with respect to each hydroxyl, is preferably approximately 1～5 mole.
In addition, as required, except diol component, can be used together the polyhydroxy reactants such as glycerine, TriMethylolPropane(TMP), trimethylolethane, tetramethylolmethane.
Hydroxycarboxylic acid comprises hydroxycarboxylic acids such as Para Hydroxy Benzoic Acid, hydroxynaphthoic acid, hydroxyl phenylacetic acid, oxyacetic acid, hydroxycaproic acid or their derivative etc.Lactone comprises the C such as propiolactone, butyrolactone, valerolactone, caprolactone (for example, 6-caprolactone etc.) 3-12lactone etc.
Polyester based resin can separately or be used in combination of two or more.In the middle of polyester based resin, from laser welding, consider, low-crystalline or amorphism aromatic polyester resin are preferred.
It is resin that preferred polyester based resin comprises saturated polyester, especially aromatic series saturated polyester is resin, conventionally mostly using polybutylene terephthalate (PBT) is resin (PBT (homopolymer) or PBT based copolymer etc.), poly-naphthalic acid fourth diester (PBN) is resin (PBN (homopolymer) or PBN based copolymer etc.), polyethylene terephthalate (PET) is resin (PET (homopolymer) or PET based copolymer), Polyethylene Naphthalate (PEN) is that the polyaromatic such as resin (PEN (homopolymer) or PEN based copolymer etc.) acid alkylene ester is resin (polyaromatic acid C for example 2-6alkylene ester is resin, preferably polyaromatic acid C 2-4alkylene ester is resin, more preferably poly terephthalic acid C 2-4alkylene ester).
This polyaromatic acid alkylene ester is that resin comprises such as polyaromatic acid alkylene ester (homopolymer), polyaromatic acid alkylene ester based copolymer etc.
As the co-polymerized monomer using in polyaromatic acid alkylene ester based copolymer (especially polyalkylene terephthalates based copolymer), can list the glycols [C that the alkylidene unit different from alkylidene unit (such as ethylidene, tetramethylene etc.) in polyaromatic acid alkylene ester based polymer is corresponding 2-6aklylene glycol (for example, the straight or branched aklylene glycols such as ethylene glycol, trimethylene, 1,2-PD, hexylene glycol etc.), has the poly-C of the alkylidene oxide unit of repeat number approximately 2～4 2-4aklylene glycol (Diethylene Glycol etc.), bisphenols (bisphenols or its alkylene oxide adducts etc.) etc.], omega-dicarboxylic acids [for example, C 6-12aliphatic dicarboxylic acid (hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid etc.), the asymmetric aromatic dicarboxylic acid that carboxyl replaces on the asymmetric position of aromatic hydrocarbon ring, 1,4-cyclohexanedimethanol etc.], hydroxycarboxylic acid (above illustrative compound etc.), lactone (caprolactone etc. are illustrative compound above) etc.In the middle of these compounds, aromatics is preferred such as the alkylene oxide adducts of bisphenols (especially dihydroxyphenyl propane) and asymmetric aromatic dicarboxylic acid [phthalic acid, m-phthalic acid and reactive derivatives thereof (lower alkyl esters of dimethyl isophthalate (DMI) etc.) etc.] etc.
With respect to polyester based resin (especially polyaromatic acid alkylene ester is resin) (or total amount of monomer), the ratio of co-polymerized monomer (modification amount) is for example 30mol% following (for example 0～30mol%), for example can in the scope of about 0.01～30mol%, select, conventionally can be about 1～30mol%, be preferably approximately 3～25mol%, more preferably about 5～20mol% (for example 5～15mol%).
Especially preferred polyester based resin is that PBT is resin (PBT, modified PBT (PBT based copolymer).PBT is that resin can be used singly or in combination of two or more.In addition, from improving the viewpoint of flame retardant resistance, mechanical properties, consider, PBT is that resin can be resin (PET such as PET (homopolymer), modified PET (PET based copolymer) is resin etc.) and use with other polyaromatic acid alkylene esters.
From the viewpoint of laser welding, consider, PBT is that the fusing point of resin is for example approximately 190 ℃ above (for example approximately 190～270 ℃), is preferably approximately 200～260 ℃, more preferably approximately 210～250 ℃.
In addition, PBT is that the limiting viscosity (IV) of resin for example can be selected from the approximately scope of 0.5～1.3dL/g, from the viewpoint of plasticity and/or mechanical characteristics, is preferably approximately 0.6～1.2dL/g, more preferably about 0.65～1.1dL/g.When limiting viscosity is too low, physical strength likely reduces, and when limiting viscosity is too high, mobility even plasticity likely reduces.In addition, limiting viscosity (IV) for example can be measured in orthomonochlorphenol under the condition of 35 ℃ of temperature.
Polyester based resin can be used commercially available product, also can such as transesterify, direct esterification etc., prepare by conventional method.For example, PBT be resin can by by above-mentioned conventional method, allow terephthalic acid or its reactive derivatives and BDO and as required can copolymerization monomer carry out copolymerization and prepare.
(bromine based compound (B))
In the present invention, as the fire retardant with sb oxide (C) combination, use specific bromide fire retardant, , use is selected from brominated (methyl) acrylic resin (or bromination (methyl) acrylic resin, such as poly-(methyl) benzyl acrylate of bromination, be resin (such as poly-(methyl) benzyl acrylate of the brominations such as poly-(methyl) vinylformic acid pentabromo-benzyl ester), the homopolymer of (methyl) vinylformic acid benzyl halide esters such as poly-(methyl) vinylformic acid pentachloro-benzyl ester or multipolymer etc.) etc. poly-(methyl) acrylate of bromination), [or brominated styrene is resin to brominated phenylethylene resin series, for example, the bromide of the phenylethylene resin series such as brominated styrene (or the bromide that phenylethylene resin series is carried out to bromination processing), brominated styrene is the homopolymer of monomer or multipolymer etc., such as brominated polystyrene etc.], (or brominated polycarbonate is resin to brominated polycarbonate-based resin, for example, the brominated bisphenol type polycarbonate resins such as brominated bisphenol A type polycarbonate resin), and brominated epoxy is that [or brominated epoxy is resin to resin, such as brominated epoxy resins such as brominated bisphenol type epoxy resin (brominated bisphenol a type epoxy resin etc.), the bromize phenoxy resins such as brominated bisphenol type phenoxy resin (brominated bisphenol A type phenoxy resin etc.) etc.] at least one bromine based compound (B).
By this specific bromine based compound and the sb oxide with specified particle diameter described later are combined, can give high flame retardant resistance and laser-transmitting for aforementioned resin (or laser-transmitting resin molding) simultaneously.
In bromine based compound, overall with respect to bromine based compound, the ratio of bromine atoms (part by weight) can for example, be selected conventionally in the scope of more than 30 % by weight (approximately 35～90 % by weight), be preferably 40 % by weight above (for example approximately 45～90 % by weight), more preferably 50 % by weight above (for example approximately 55～85 % by weight).
Below describe bromine based compound in detail.
Brominated (methyl) acrylic resin comprises poly-(methyl) acrylate of bromination (or brominated poly-(methyl) acrylate or poly-bromination (methyl) acrylate), and especially poly-(methyl) benzyl acrylate of bromination is resin etc.Bromination polyacrylic ester is that resin can be the compound for example representing by following formula.
[Chemical formula 1]
(in formula, m represents more than 2 integers, and R represents alkyl, and X represents hydrogen atom or halogen atom, and at least one X is bromine atoms.)
Poly-(methyl) acrylic ester resin of representative bromination comprise poly-(methyl) benzyl acrylate of bromination be resin [for example, for example, with (methyl) vinylformic acid cylite ester ((methyl) vinylformic acid pentabromo-benzyl ester, (methyl) vinylformic acid tetrabromo benzyl ester, (methyl) vinylformic acid three bromobenzyl esters) be the resin of polymerization composition, for example homopolymer or the multipolymer of (methyl) vinylformic acid cylite ester, the multipolymer of (methyl) vinylformic acid cylite ester and co-polymerized monomer etc.] etc.
At poly-(methyl) benzyl acrylate of bromination, be in resin, as co-polymerized monomer, can list vinyl monomer (especially not by the ethene base system monomer of bromination), for example (methyl) vinylformic acid; (methyl) esters of acrylic acid of (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) benzyl acrylate and so on; The styrenic monomers such as vinylbenzene; The vinyl cyanide base system monomers such as (methyl) vinyl cyanide; The unsaturated carboxylic acid such as fumaric acid, toxilic acid or its acid anhydrides; The vinyl esters of carboxylic acids classes such as vinyl acetate etc.In addition, as co-polymerized monomer, can also use bridging property vinyl monomer, such as poly-(methyl) acrylate (such as dimethylbenzene two (methyl) acrylate, tetrabromo dimethylbenzene two (methyl) acrylate etc.), diene monomer (such as divinyl, isoprene etc.), Vinylstyrene etc.These co-polymerized monomers can be used singly or in combination of two or more.
In addition, in the multipolymer of (methyl) vinylformic acid cylite ester and co-polymerized monomer, with respect to whole formation monomers, the ratio of (methyl) vinylformic acid cylite ester can be above for 50mol% (for example approximately 55～99.5mol%), be preferably 60mol% above (for example approximately 65～99mol%), more preferably 70mol% above (for example approximately 75～98mol%).
The number-average molecular weight of brominated (methyl) acrylic resin (especially bromination poly-(methyl) benzyl acrylate be resin) is for example approximately 1000～300000, is preferably approximately 3000～200000, more preferably approximately 5000～150000.
In addition, brominated phenylethylene resin series (or brominated styrene is resin) can be for example the resin representing by following formula.
[Chemical formula 2]
(in formula, j represents more than 2 integers, and m represents 1～4 integer.)
Representative brominated phenylethylene resin series (or brominated styrene is resin) comprises that to take brominated styrene be the resin that monomer (brominated styrenes such as Dowspray 9, phenylstilbene bromide) is polymerization composition, such as brominated styrene, be homopolymer or the multipolymer (brominated Polystyrene etc.) of monomer, brominated styrene is the multipolymer of monomer and co-polymerized monomer etc.Co-polymerized monomer comprises above illustrative co-polymerized monomer etc.Co-polymerized monomer can separately or be used in combination of two or more.
In addition, at brominated styrene, be in the multipolymer of monomer and co-polymerized monomer, with respect to whole formation monomers, brominated styrene is that the ratio of monomer can be above for 50mol% (for example approximately 55～99.5mol%), be preferably 60mol% above (for example approximately 65～99mol%), more preferably 70mol% above (for example approximately 75～98mol%).
The number-average molecular weight of brominated phenylethylene resin series can be for example approximately 1000～300000, is preferably approximately 3000～200000, more preferably approximately 5000～150000.
Brominated polycarbonate-based resin (brominated polycarbonate is that resin, poly-bromination carbonic ether are resin) can be for example the resin representing by following formula.
[chemical formula 3]
(in formula, R and R ' represent respectively hydrogen atom or alkyl, X represent alkyl, carbonyl, ether ,-S-or-SO 2-, k and m represent respectively 1～4 integer, n represents more than 2 integers.)
In the R and R ' of above-mentioned formula, as alkyl, such as the alkyl such as alkyl (methyl, ethyl, propyl group, sec.-propyl etc.) that can list carbon number 1～10.In addition, in X, as alkyl, can list the C of divalence 1-10alkyl (the C such as methylene radical, ethylidene, 2-propylidene 1-4alkyl) etc.
Representative brominated polycarbonate-based resin comprises that (or brominated bisphenol class, such as two (hydroxyphenyl) C of the brominations such as tetrabromo-bisphenol with brominated bisphenols 1-10alkane etc.) be the polycarbonate-based resin of polymerization (basis) composition (or diol component), such as brominated bisphenol type polycarbonate resins such as brominated bisphenol A type polycarbonate resin (such as tetrabromobisphenol A carbonic ester polymkeric substance or oligopolymer) etc.In addition, the diol component of brominated polycarbonate-based resin can be separately or by two or more combinations, also can comprise not by the diol component of bromination (such as two (hydroxyphenyl) C of dihydroxyphenyl propane etc. 1-10alkane).
The number-average molecular weight of brominated polycarbonate-based resin can be for example approximately 1000～40000, is preferably approximately 2000～30000.
Brominated epoxy resin (brominated epoxy resin) can be for example the resin representing by following formula.
[chemical formula 4]
[in formula, X represents bromine atoms, and i and j represent 1～4 integer, and n represents more than 0 integer, T 1and T 2can be identical or different, represent glycidyl or-CH 2cH (OH) CH 2oPh (in formula, Ph represents to have substituent halogenated phenyl).]
Representative brominated epoxy resin (brominated epoxy resin) comprises that (or brominated bisphenol class, such as two (hydroxyphenyl) C of the brominations such as tetrabromo-bisphenol with brominated bisphenols 1-10alkane etc.) be the epoxy resin of polymerization composition (or diol component), for example, such as the brominated bisphenol type epoxy resin such as brominated bisphenol a type epoxy resin (reaction product of tetrabromo-bisphenol and Epicholorohydrin).In addition, the diol component of brominated epoxy resin can be used separately or by two or more combinations, also can comprise not by the diol component of bromination (such as two (hydroxyphenyl) C such as dihydroxyphenyl propanes 1-10alkane).In addition, the end of brominated epoxy resin and the T of aforementioned formula 2situation similarly can carry out termination process.Especially, the epoxy resin (or the epoxy resin that contains tetrabromo-bisphenol and diglycidylether) that the tetrabromo-bisphenol of take is polymerization (basis) composition is when use level is too much, the foreign matter of the blackspot shape in molding increases, infringement mechanical characteristics and/or electrical characteristic, when laser welding, produce extremely overheated, likely damage weldability, therefore preferably carry out termination process.
The number-average molecular weight of brominated epoxy resin can be for example approximately 1000～40000, is preferably approximately 2000～30000, more preferably approximately 3000～20000.
In these brominated resins, from having the viewpoint of the stability of excellent laser welding, especially preferred use is selected from poly-(methyl) acrylic ester resin (especially bromination polypropylene acid benzyl ester is that the bromination polyacrylic ester such as resin are resin) of bromination and brominated styrene is at least one in resin (brominated Polystyrene etc.).
In aforementioned resin (or laser-transmitting resin molding), with respect to 100 weight part polyester based resins (A), the ratio of bromine based compound (B) is for example approximately 5～70 weight parts, be preferably approximately 8～60 weight parts, more preferably approximately 10～50 weight parts (for example 15～40 weight parts).When using bromine based compound (B) with aforementioned proportion, easily effectively show high flame retardant resistance and maintain the intrinsic excellent specific property of polyester based resin (mechanical characteristics, electrical characteristic, shaping processability).
(sb oxide (C))
As sb oxide, for example can list weisspiessglanz [ANTIMONY TRIOXIDE SB 203 99.8 PCT (or antimonous oxide, Sb 2o 3deng), antimony pentaoxide (or antimony peroxide, xNa 2oSb 2o 5yH 2o (x=0～1, y=0～4) etc.) etc.], stibnate [metaantimmonic acid metal-salt (such as an alkali metal salts such as sodium antimonates, the alkaline earth salts such as metaantimmonic acid magnesium etc.), ammonium antimonate etc.] etc.
In the middle of these sb oxides, weisspiessglanz (especially ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide), sodium antimonate (sodium antimonate) are preferred.Sb oxide can be used separately or be used in combination of two or more.
In addition, as required, sb oxide can carry out surface treatment with surface treatment agents such as epoxy compounds, silane compound, isocyanate compound and/or titanate compounds.
In the present invention, as sb oxide, use the sb oxide with specified particle diameter.The median size of sb oxide can be selected in scopes more than 2 μ m, for example, be approximately 2～10 μ m, is preferably approximately 2.5～9 μ m (for example 3～8 μ m).In addition, median size is such as obtaining as median particle diameter by laser diffraction/diffuse transmission type particle size distribution device etc.In addition, while using conventional bromide fire retardant and sb oxide, the laser-transmitting of resin combination or laser-transmitting resin molding reduces, and can not carry out laser welding.Yet, in the present invention, by by the sb oxide of this specified particle diameter and specific aforementioned bromine based compound use, can give high-caliber high flame retardant and laser-transmitting for polyester based resin (the especially aromatic polyester resin such as PBT).In addition, if the particle diameter of sb oxide is excessive, while applying mechanical stress, easily form the starting point of destroying, produce fragility, reduce in addition flame retardant resistance.In addition, if the particle diameter of sb oxide is too small, be possiblely, infringement laser-transmitting, polyester based resin (A) itself is decomposed, or promote reacting of polyester based resin (A) and halogen-containing resin system fire retardant (B), damage shape stability.
In resin combination of the present invention, with respect to 100 weight part polyester based resins (A), the ratio of sb oxide (C) can be for example approximately 3～40 weight parts, is preferably approximately 5～30 weight parts, more preferably approximately 10～50 weight parts.In addition, when use level is very few, can not show sufficient flame retardant resistance; And when use level is too much, likely damage the intrinsic mechanical characteristics of polyester based resin, shaping processing characteristics, or because sharp scattering of light and screening effect reduce laser-transmitting.
In addition, in aforementioned resin (or laser-transmitting resin molding), the ratio of bromine based compound (B) and sb oxide (C) is for the former/the latter's (weight ratio)=approximately 95/5～30/70, be preferably approximately 90/10～40/60, more preferably approximately 80/20～50/50.
(polycarbonate-based resin (D))
Resin combination of the present invention can comprise polycarbonate-based resin.
Polycarbonate-based resin is normally by the dihydroxy compound resin obtained with reacting of the carbonic ethers such as phosgene or diphenyl carbonate.Dihydroxy compound can be alicyclic compound etc., but is preferably aromatics (especially bisphenol cpd).
As bisphenol cpd, can list [for example, two (hydroxyaryl) C such as dihydroxyphenyl propane of the bisphenols shown in aforementioned polyester based resin item 1-6alkane; Two (hydroxyaryl) C 4-10naphthenic hydrocarbon; 4,4 '-dihydroxy diphenyl ether; 4,4 '-dihydroxy-diphenyl sulfone; 4,4 '-dihydroxyl diphenylsulfide; 4,4 '-dihydroxyl diphenylketone etc.].Preferred polycarbonate-based resin comprises bisphenol A polycarbonate.
In addition, polycarbonate-based resin is easily compatible with polyester based resin (especially polybutylene terephthalate is resin), has the high effect of improving laser-transmitting.In addition, when using polycarbonate-based resin, can effectively improve the warpage of molding.With respect to 100 weight part polyester based resins (A), the preferred use level of polycarbonate-based resin can be for example approximately 5～100 weight parts, is preferably approximately 10～70 weight parts, more preferably approximately 10～50 weight parts.When the use level of polycarbonate-based resin is too much, likely polyester based resin (for example PBT is resin) loses crystallinity, and chemical-resistant, thermotolerance reduce.
(phosphorus series compound (E))
For stable crystalline, laser-transmitting, in aforementioned resin (or laser-transmitting resin molding), can further add phosphorus series compound (or P contained compound).The preferred embodiment of phosphorus series compound can list phosphorous acid esters { list～tri-(side chain C such as three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, two (2-tert-butyl-phenyl) phenyl phosphites for example 3-6alkyl-phenyl) phosphorous acid ester; Two (2,6-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,4-di-tert-butyl-phenyl) (the side chain C of pentaerythritol diphosphites, four (2,4-di-tert-butyl-phenyl)-4, the 4 '-aliphatic polyols such as bis-phenylene diphosphites 3-6alkyl-aryl) phosphorous acid ester etc. }, phosphiinic acid ester (four (2,4-di-tert-butyl-phenyl)-4,4 '-bis-phenylene two phosphinates etc.) etc., phosphoric acid ester [for example, the triphenyl based compounds such as three (2,4-di-tert-butyl-phenyl) phosphoric acid ester], phosphoric acid salt (the phosphate metal salt such as the salt such as the phosphoric acid alkali metal such as monocalcium phosphate, biphosphate sodium-hydrate or alkaline earth salt (or its hydrate)).In the middle of these phosphorus series compounds, (the side chain C of aliphatic polyol 3-6alkyl-aryl) phosphorous acid ester, phosphate metal salt etc. are preferred.
With respect to 100 weight part polyester based resins (A), the use level of phosphorus series compound is for example 0.01～3 weight part, is preferably 0.03～2 weight part, more preferably 0.05～1.0 weight part.When use level is few, can not contribute to the stable of crystallinity, laser-transmitting, and when use level is too much, likely ooze out, the insulativity reduction of molding, have around in the situation of metal, likely there is the detrimentally affect of metallic corrosion, short circuit.
(crystallization promoter (F))
Equally for stable crystalline, laser-transmitting, in aforementioned resin (or laser-transmitting molding), can within the scope of laser-transmitting, add crystallization promoter not damaging.As crystallization promoter, such as being the organic nucleating agents such as rosin, but can use aptly inorganic nucleator, such as metal oxide (silica, aluminum oxide, zirconium white, titanium oxide, ferric oxide, zinc oxide etc.), metal carbonate (calcium carbonate, magnesiumcarbonate, barium carbonate etc.), silicate (Calucium Silicate powder, pure aluminium silicate, talcum etc.), metallic carbide (silicon carbide etc.), metal nitride (silicon nitride, boron nitride, tantalum nitride etc.) etc.These crystallization promoters can separately or be used in combination of two or more.Crystallization promoter can be granular or tabular.
In addition, the median size of crystallization promoter (inorganic nucleator etc.) is for example approximately 0.01～10 μ m, is preferably approximately 0.02～5 μ m.In addition, median size for example obtains as median particle diameter by the particle size distribution device of laser diffraction/diffuse transmission type.With respect to 100 weight part polyester based resins, the ratio of crystallization promoter is for example 0.001～10 weight part, is preferably 0.01～7 weight part.
Aforementioned resin (or laser-transmitting molding) can also comprise packing material (or supporting material), as long as the transmissivity of laser is not being applied in dysgenic scope.
This packing material (or weighting agent) comprises fibrous packing material [inorganic fibre (glass fibre for example for example, silica fibre, sapphire whisker, silica-alumina fiber, aluminum silicate fiber, Zirconium oxide fibre, potassium titanate fiber, whisker (silicon carbide, aluminum oxide, the whiskers such as boron nitride), wollastonite etc.), organic fiber (for example aliphatics or aromatic polyamide, aromatic polyester, fluoro-resin, the acrylic resins such as polyacrylonitrile, the fiber that artificial silk etc. form, carbon fiber etc.) etc.], tabular packing material [talcum for example, mica, glass flake etc.], granular packing material [glass beads for example, glass powder, milled fibre (such as milled glass fibre etc.), clay, organized clay, kaolin, potassium titanate, calcium carbonate, titanium oxide, feldspar is mineral, graphite etc.] etc.
The median size of fibrous packing material (fiber diameter) can be for example approximately 1～50 μ m (being preferably 3～30 μ m), and mean length (average fiber length) can be for example approximately 100 μ m～3mm (being preferably 300 μ m～1mm).In addition, median size tabular or granular packing material can be for example approximately 0.1～100 μ m, is preferably approximately 0.1～50 μ m.These packing materials can be used singly or in combination of two or more.
In the middle of these packing materials, the packing material of transmissive laser is preferred.This packing material can be selected according to sharp light wavelength, and especially, glassiness packing material or supporting material (glass fibre, glass flake, glass beads etc.) are preferred.
In addition, cross-sectional shape to glass fibre does not have specific limited, can list circle, ellipse (or Long Circle, also comprise the indicatrix ellipses such as eyebrow shape), semicircle, fan-shaped (circular arc), polygon (trilateral, square (rectangle, trapezoidal etc.) etc.) or their analogous shape etc.
As required, packing material or strengthening agent can be processed by conventional collecting agent or surface treatment agent.As collecting agent or surface treatment agent, such as listing the functionality compounds such as epoxy based compound, isocyanic ester based compound, silane based compound, titanic acid ester based compound etc.In addition, packing material can be processed with above-mentioned collecting agent or surface treatment agent in advance before mixing with other compositions (composition (A), (B) and (C) etc.), also can when packing material is mixed with other compositions, by interpolation collecting agent or surface treatment agent, process.With respect to 100 weight part packing materials (glass fibre etc.), the ratio of collecting agent or surface treatment agent is for example approximately 0～10 weight part (for example 0.01～10 weight part), is preferably approximately 0.05～5 weight part.
With respect to 100 weight part polyester based resins, the ratio of packing material for example can be selected in the scope of approximately 0～200 weight part, is preferably approximately 5～150 weight parts, more preferably approximately 10～100 weight parts (for example 15～65 weight parts).When the ratio of packing material is too much, according to the kind of packing material, likely damages laser-transmitting and can not obtain sufficient heat seal strength.
Resin combination of the present invention can further contain fluorine resin.This fluorine resin comprises homopolymer or the multipolymer of fluorochemical monomer, such as the homopolymer of fluorochemical monomer (tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, R 1216, perfluoroalkyl vinyl ether etc.) or multipolymer of multipolymer, aforementioned fluorochemical monomer and other co-polymerized monomers (acrylic monomers such as ethylene series monomer, (methyl) acrylate such as ethene, propylene etc.) etc.
As this fluorine resin, can exemplify the homopolymer such as tetrafluoroethylene, polychlorotrifluoroethylene, poly(vinylidene fluoride) particularly; The multipolymers such as tetrafluoraoethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoro-ethylene copolymer.Fluorine resin can separately or be used in combination of two or more.As preferred fluorine resin, can list the homopolymer of tetrafluoroethylene or the multipolymer of multipolymer, tetrafluoroethylene and (methyl) acrylate etc.
Fluorine resin can have antidrip effect (that is, preventing the effect under the drop of resin of the melting along with burning).In addition, carry out radioactive rays processing or 200 ℃ of above heat treated fluorine resins because antidrip effect is inferior, therefore can use the fluorine resin that does not carry out this processing.
With respect to 100 weight part polyester based resins (A), the ratio of fluorine resin is approximately 0～3 weight part (for example 0.01～3 weight part), is preferably approximately 0.05～2 weight part, more preferably approximately 0.1～1.5 weight part.Wherein, when aforementioned ratio is too much, possible, the viscosity of resin combination raises, and plasticity reduces, and produces white dot in molding, infringement outward appearance, and local laser-transmitting rate reduces, laser welding strength decreased.
Depend on the needs, in not damaging the scope of effect of the present invention, according to purposes etc., in aforementioned resin (or laser-transmitting resin molding), can add various additives, stablizer (antioxidant for example, UV light absorber, photostabilizer, thermo-stabilizer etc.), other fire retardants (sulfur-bearing fire retardant for example, Silicone-containing Flame Retardant, alcohol flame retardant, nitrogenated flame retardant, phosphorus flame retardant etc.), flame retardant, lubricant, releasing agent, static inhibitor, tinting material (organic or inorganic dyestuff and pigment etc.), softening agent, dispersion agent, other thermoplastic resins (such as amorphism or low-crystalline resin etc.) etc.Especially, recently, fire-retardantization of the non-halogen flame retardant based on except the halogen flame retardants such as bromide fire retardant also proposed, such as can be used together the phosphorus flame retardant shown in Japanese kokai publication hei 5-70671 communique, Japanese kokai publication hei 8-73720 communique etc.
As aforementioned antioxidant, can list conventional antioxidant, such as sterically hindered phenol, be that antioxidant, bulky amine are that antioxidant, quinhydrones are antioxidant etc.Antioxidant can separately or be used in combination of two or more.In the middle of antioxidant, sterically hindered phenol is that antioxidant is preferred, for example, as antioxidant, sterically hindered phenol is that [for example [3-(3 for glycerine three for antioxidant, 5-di-tert-butyl-hydroxy phenyl) propionic ester], two～tetra-[3-(3,5-, bis--side chain C of the aliphatic polyol such as tetramethylolmethane four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester] 3-6alkyl-4-hydroxyphenyl) propionic ester] etc. can be separately or with other antioxidants and use.
With respect to 100 weight part polyester based resins (A), the ratio of antioxidant is for example approximately 0.005～3 weight part, is preferably approximately 0.01～1.5 weight part (for example 0.02～1 weight part), more preferably approximately 0.05～0.5 weight part.In addition, when antioxidant ratio is too much, likely the dispersiveness in resin reduces, and antioxidant oozes out on molding surface, and the outward appearance of molding is along with oozing out likely variation.
As releasing agent, such as using higher fatty acid (C such as stearic acid, montanic acid, oleic acid 10-30saturated or unsaturated fatty acidss etc.), with the ester (also comprising partial ester) of polyvalent alcohol aliphatic polyols such as (etc.) such as ethylene glycol, polyoxyethylene glycol etc. (gathering) aklylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, anhydro sorbitols, wax is [such as paraffin, Microcrystalline Wax, polyolefin wax (the poly-C such as polyethylene wax, Poly Propylene Wax 2-4the olefin copolymer waxes such as ethylene series wax (preferred low molecular weight polyethylene wax etc.), ethylene copolymer wax etc.) etc.] etc.Object lesson as aforementioned ester, can list (gathering) alkylidene diol fatty acid ester (monoesters or diester, Unister E 275 for example, polyethylene glycol monolaurate etc.), glycerol fatty acid ester (monoesters～tri-ester, Zerol for example, glycerol tripalmitate etc.), trimethylolpropane fatty acid ester (monoesters～tri-ester, such as TriMethylolPropane(TMP) monopalmitate etc.), pentaerythritol fatty ester (monoesters～tetra-ester, pentaerythritol stearate etc.), fatty acid esters of sorbitan (monoesters～tetra-ester, such as Arlacel-60 etc.) etc.Releasing agent can separately or be used in combination of two or more.
With respect to 100 weight part polyester based resins (A), the ratio of releasing agent is for example approximately 0.005～3 weight part, is preferably approximately 0.01～1.5 weight part.Wherein, when the ratio of releasing agent is too much, likely the dispersiveness in resin reduces, and releasing agent oozes out on molding surface, and the outward appearance of molding is along with oozing out likely variation.
In addition, in significantly not damaging the radioparent scope of the laser for welding, aforementioned resin can also contain tinting material (such as tinting material of recording in TOHKEMY 2000-309694 communique, TOHKEMY 2001-71384 communique etc.).As tinting material, can list laser is non-absorbent tinting material (inorganic or organic dye and pigment), such as yellow dyes and pigment (pigment dyestuffs such as mineral dye, diarylide yellow such as cadmium yellow), orange dye and pigment (organic yellow etc.), red pigment (pigment dyestuffs such as mineral dye, C lake red CAN'T such as red inorganic pigment), blue pigments (pigment dyestuffs such as mineral dye, phthalocyanine blue such as cobalt blue), green colouring material and pigment (pigment dyestuffs such as mineral dye, phthalocyanine green such as chrome green), purple dye and pigment etc.This tinting material can be used separately, also multiple colorant combination can be used to be adjusted into required tone.For example, the utilization mixing (multiple dyestuff and pigment are as combination of combination, yellow dyes and the pigment of yellow dyes and pigment and purple dye and pigment and orchil and pigment and blue dyes and pigment etc.) of losing lustre, can be coloured to aforementioned resin Achromatic color (grey, black).
Consumption to this tinting material does not have specific limited, with respect to 100 weight part polyester based resins (A), for example, can be approximately 0.001～5 weight part, is preferably approximately 0.005～3 weight part, more preferably approximately 0.01～2 weight part.
Aforementioned resin (or laser-transmitting resin molding) has excellent flame retardant resistance, the molding forming with resin combination is when thickness 0.8mm, and the flame retardant resistance evaluation based on UL94 standard (Subject 94 of Underwriters Laboratories) is generally V-0.And, aforementioned resin (or laser-transmitting resin molding) is even if be shaped the very thin high flame retardant resistance that also has, even if the thickness of aforementioned molding is below about 0.8mm, be for example about 0.3～0.8mm, be preferably approximately 0.4～0.75mm, the flame retardant resistance evaluation based on UL94 standard also can reach V-0.
Aforementioned resin can be bulk material mixture or molten mixture (pellet etc.).This resin combination can polyester based resin (A), bromine based compound (B) and sb oxide (C) (with other compositions as required in addition) be mixed by the method with conventional or prepared by mixing (melting mixing).Especially, aforementioned resin is owing to having excellent plasticity, and the molten mixture (melting mixing thing) that therefore can be effective as each composition [polyester based resin (A), bromine based compound (B) and sb oxide (C) (with other compositions as required)] obtains.Molten mixture can be prepared each composition melting mixing by the method with conventional.For example, aforementioned resin can be prepared by following method: (1) mixes each composition, mixing with forcing machine (single screw rod or twin screw extruder), extrude, and prepares pellet, the method further forming as required; (2) preparation forms different pellets (masterbatch) for the time being, mixes the described pellet of (dilution) specified amount for being shaped, and obtains the method for the molding (pellet etc.) of composition requirement; (3) one or more of each composition are directly added to method of forming mill etc.In addition, the molding such as pellet can prepared remix crispness component (glass is supporting material) after the composition melting mixing except crispness component (glass is supporting material etc.), and can be from the side material inlet feed of forcing machine.In addition, in order to coordinate equably each composition, can, by a part of micronization of resinous principle (polyester based resin etc.), then gained powder be mixed with other compositions.In addition, resin combination of the present invention can be for example, with the form former state of mixture (bulk material or molten mixture) for the manufacture of molding.
Aforementioned resin (or laser-transmitting resin molding), although formed by polyester based resin, has high light transmissivity to laser, is suitable for laser welding.For example, for the molding of thickness 1.0mm, the laser-transmitting rate of aforementioned resin (or laser-transmitting resin molding) is for example more than approximately 20% (for example approximately 20～100%), be preferably more than approximately 25% (for example 25～80%), more preferably more than approximately 30% (for example 30～50%), is generally approximately 20～40% (for example 20～30%).In addition, aforementioned resin (or laser-transmitting resin molding) for example, for example, can have the laser-transmitting rate of above-mentioned scope for the optical maser wavelength for laser welding (any wavelength in aftermentioned laser wavelength range (wavelength 940nm)).
Like this, although the base resin of resin combination of the present invention is polyester based resin (PBT is resin etc.), but there is high-caliber flame retardant resistance and laser-transmitting, therefore can be used as laser welding resin combination, can be used for forming the transmissive side parts in foregoing laser welding.In addition, resin combination also has the character such as excellent plasticity, physical strength, thermotolerance, chemical-resistant.
Therefore, the resin combination that resin combination of the present invention can be used as laser welding aptly, specifically, the resin combination for parts of the transmissive side in laser welding (resin combination of be sometimes referred to as laser-transmitting resin resin combination for molding, be used to form the resin combination of laser-transmitting resin molding, the transmissive side parts in laser welding being used etc.).In addition, aforementioned laser transmitting resin molding (being sometimes referred to as laser-transmitting molding, laser-transmitting side resin forming product, laser-transmitting side molding, laser-transmitting resin parts, laser-transmitting parts etc.) is to contact with laser absorption resin forming product that can absorbing laser as previously mentioned, make laser-transmitting, the molding engaging with aforementioned resin molding, and be the molding forming by aforementioned resin.
[molding]
Laser-transmitting resin molding of the present invention is formed by aforementioned resin (that is, the transmissive side parts resin combination in laser welding), can be used for forming the transmissive side parts of laser welding.
This molding (laser-transmitting resin molding) is as mentioned above by aforementioned resin (or each composition) melting mixing, by common methods such as extrusion molding, injection molded, compression molding, blow molding, vacuum forming, spinning-shaping, gas injection shapings, be shaped, but conventionally by injection molded, be shaped.Molding can be especially the molding (injection molding product) being shaped by injection molded.The condition of injection molded can suitably be selected according to the kind of polyester based resin, for example approximately 200～300 ℃, preferably at approximately 250～280 ℃ by resin combination melting mixing, prepare as required pellet, for example, by injection molding machine injection molded under the condition of approximately 200～300 ℃ of barrel zone temperatures (250～280 ℃).In addition, die temperature can for example, be selected in the scope of approximately 40～100 ℃ (40～90 ℃), from maintaining the viewpoint of laser-transmitting, die temperature can be approximately 40～95 ℃ (for example 45～90 ℃), be preferably approximately 40～80 ℃ (for example 45～80 ℃), be especially preferably approximately 50～85 ℃ (for example 46～80 ℃).
Shape to molding does not have specific limited, in order to be engaged and to use with compounding ingredient (other resin forming products) by laser welding, normally at least has the shape (for example tabular) of contact surface (plane etc.).In addition, molding of the present invention at least has (the position of laser welding, position that makes laser-transmitting, laser welding position), the thickness at this position (thickness of the direction of laser-transmitting) is for example about 0.1～1.5mm, be preferably approximately 0.2～1.0mm, more preferably about 0.5～0.8mm.Molding for example can have this laser welding position in aforementioned contact surface region.
The present invention also comprises the composite formed article (or composite molded product or compound forming component or combined shaping resin component) forming with aforementioned laser transmissivity molding.This composite formed article is, by laser welding, the aforementioned laser transmitting resin molding (or first molding) being formed by aforementioned resin is engaged to the molding forming with the laser absorption resin forming product (being sometimes referred to as laser absorption side resin forming product, laser absorption side molding, laser absorption side resin component, laser absorption side component, the second molding, adherend etc.) of compounding ingredient, and two molding are mutually integrated.In addition, the first resin forming product at least has the position (laser welding position) of laser-transmitting as previously mentioned, and in composite formed article, this laser-transmitting position (or laser welding position) engages with the second resin forming product.The first resin forming product and the second resin forming product are conventionally ground integrated by being engaged to small part.
To forming the resin of aforementioned the second resin forming product, there is no specific limited, can list various thermoplastic resins, such as ethylene series resin, vinyl resin, phenylethylene resin series, acrylic resin, polyester based resin, polyamide-based resin, polycarbonate-based resin etc.In the middle of these resins, can using and form the base resin identical type of aforementioned the first resin forming product (aforementioned resin) or the resin of same system, is that resin, PET are that the polyester based resins such as resin (aromatic polyester resin) or its composition form the second resin forming product such as PB T.In order further to improve the flame retardant resistance of composite formed article, the second resin forming product can be fire-retardant with fire retardant etc.In addition, the first resin forming product and the second resin forming product the two can form with aforementioned flame retardant resin composition.In addition, in the present invention, the first resin forming product is owing to having excellent flame retardant resistance, even if do not utilize fire retardant etc. to carry out fire-retardant finish to the second resin forming product, also can provide practical sufficient flame retardant resistance for composite formed article.
The second resin forming product can contain the absorption agent of laser or tinting material.Aforementioned tinting material can be selected according to sharp light wavelength, can list mineral dye [white pigments such as the orange pigmentss such as the red pigments such as black pigment, red iron oxide, molybdate orange, titanium oxide such as carbon black (such as acetylene black, dim, thermal black (Thermal Black), furnace treated black (furnace black), thermally oxidized black (Channel Black), section's qin carbon black (Ketjen black) etc.) etc.], pigment dyestuff (yellow ultramarine, orange pigments, red pigment, blue pigments, veridian etc.) etc.These absorption agents can separately or be used in combination of two or more.As absorption agent, conventionally can use black pigment or dyestuff, especially carbon black.The median size of carbon black can be about 10～1000nm conventionally, is preferably approximately 10～100nm.With respect to whole the second resin forming products, the ratio of tinting material is approximately 0.1～10 % by weight, is preferably approximately 0.5～5 % by weight (for example 1～3 % by weight).In addition, between the first and second resin forming products, can clamp the resin sheet (PBT series resin sheet etc.) of laser absorbents such as containing carbon black or tinting material, or coating laser absorbent, two moldinies are closely sealed, then by laser radiation, engage.In addition, about the details of the aforementioned resin sheet that contains tinting material, such as can be with reference to No. 1829720 communique of Japanese Patent etc.
This composite formed article can be by engaging the first resin forming product to prepare with the second resin forming product.That is, composite formed article can be by preparing laser radiation on the contact surface (or interface) of laser-transmitting resin molding and laser absorption resin forming product.Specifically, by the first molding is contacted (especially with the second molding, at least make laser-transmitting position or junction surface carry out face contact), irradiating laser, with the interface of melting the first molding and the second molding at least in part, and under the state that makes junction surface closely sealed (fusion) cooling joint.In this composite formed article, if use molding of the present invention, by fusion, can obtain high bond strength, can keep equal height to fuse intensity with the non-fusion parts that there is no fusion by irradiating laser.
The irradiation of laser is carried out towards the direction of the second molding from the first resin forming product side (transmitting member side) conventionally.And, by this laser radiation, the heating of the interface of the second molding that makes to contain absorption agent or tinting material, thus the first molding and the second molding are fused.In addition, as required, utilize lens system, laser is gathered on the interface of the first molding and the second molding, contact interface is fused.In the present invention, due to transmissive side parts, the first resin forming product is that aforementioned resin by aforementioned laser transmissivity excellence forms, and therefore can carry out laser welding effectively with the second resin forming product, can give composite formed article with high flame retardant resistance.
Kind to laser does not have specific limited, for example, can use wavelength for about 600～2000nm, is preferably approximately 700～1500nm, more preferably the about laser of 800～1200nm (for example 800～1100nm).
As the laser source that can be used for the laser welding of molding, such as utilizing pigment laser, gas laser (excimer laser, argon laser, krypton laser, helium-neon laser etc.), Solid State Laser (YAG laser etc.), semiconductor laser etc.As laser, conventionally utilize pulse laser.
In addition, the laser scanning speed of laser welding (speed that laser irradiating position moves on sample) is not had to specific limited, can at random select.In order to prevent that welding is bad and to improve heat seal strength, aforementioned laser sweep velocity is for example preferably approximately 0～150mm/ second, about 1～100mm/ second more preferably, more preferably about 2～50mm/ second.
Aforementioned molding, owing to having excellent laser welding, therefore can easily engage with the resin forming product of compounding ingredient by laser welding conventionally.In addition, as required, can be by laser welding and other burning-on methods (such as vibration welded method, ultrasonic welding method, hot plate burning-on method etc.) combination.
utilizability in industry
Laser welding of the present invention has excellent laser-transmitting and high flame retardant resistance with flame retardant resin composition and molding (transmissive side parts) thereof, therefore go for various uses, such as Electrical and Electronic parts, office automation (OA) equipment unit, household electrical appliance parts, machine structural parts, structural partsof automobiles etc.Molding and composite formed article are especially suitable for automobile electric parts (various control units, spark coil parts etc.), engine parts, various sensor element, connector component, switch block, relay1 block, coil component, transformer part, lamp part etc.
Embodiment
According to embodiment, illustrate in greater detail the present invention below, yet, the invention is not restricted to these embodiment.
In addition, in embodiment and comparative example, use following composition.
Polyester based resin (A):
(A1) polybutylene terephthalate (limiting viscosity=0.69dL/g, Win Tech Polymer Ltd. manufactures)
(A2) modification polybutylene terephthalate is (in terephthalic acid and 1, in the reaction of 4-butyleneglycol, replace a part of terephthalic acid (12.5mol%), use 12.5mol% dimethyl isophthalate (DMI) as the prepared modification polybutylene terephthalate of copolymer composition, limiting viscosity=0.76dL/g)
(A3) (multipolymer of polybutylene terephthalate and polycaprolactone, TEIJIN FIBERS LIMITED manufactures polybutylene terephthalate-polycaprolactone elastomerics, Q4110).
Bromine based compound (B):
(B1): bromination polyacrylic ester (poly-(vinylformic acid pentabromo-benzyl ester), デ ッ De シ mono-Block ロ ミ Application グ ルYi プ company manufactures, FR 1025)
(B2): brominated Polystyrene (manufacture, PyroChek68PB) by ァ Le ベ マ mono-Le (strain)
(B3): brominated polycarbonate (brominated bisphenol A type polycarbonate, Supreme Being people changes into (strain) and manufactures, Fire Guard FG-7500)
(B4): brominated epoxy resin (brominated bisphenol a type epoxy resin, manufacture, SRT5000) by this pharmaceutical industries of slope (strain)
(B5): ethylenebis (tetrabromo phthalimide) (SAYTEX BT-93, ァ Le ベ マ mono-Le (strain) is manufactured).
Sb oxide (C):
(C1) antimony pentaoxide (median size 3.8 μ m, daily output chemical industry (strain) is manufactured, サ Application ェ Port ッ Network NA-1030)
(C2) ANTIMONY TRIOXIDE SB 203 99.8 PCT (median size 6.3 μ m, manufacture, PATOX-L) by Japanese concentrate (strain)
(C3) ANTIMONY TRIOXIDE SB 203 99.8 PCT (median size 1.2 μ m, manufacture, PATOX-M) by Japanese concentrate (strain)
In addition, ((strain) hole field makes manufacturing to the particle diameter of sb oxide use laser diffraction/diffuse transmission type particle size distribution device, and LA-920), the distilled water of usining is measured as dispersion medium, and gained median particle diameter is as particle diameter.
Polycarbonate resin (D):
(D1) polycarbonate resin (ェ of Mitsubishi Application ジ ニ ァ リ Application グ プ ラ ス チ ッ Network ス (strain) manufactures, ュ mono-ピ ロ Application S-3000).
Phosphorus series compound (E):
(E1) SODIUM PHOSPHATE, MONOBASIC (rice mountain chemical industry (strain) is manufactured, SODIUM PHOSPHATE, MONOBASIC)
(E2) four (2,4-di-tert-butyl-phenyl)-4,4 '-bis-phenylene two phosphinates (Network ラ リ ァ Application ト ジ ャ パ Application (strain) is manufactured, Sandostab P-EPQ)
Crystallization promoter (F):
(F1) boron nitride (water island alloy iron (strain), boron nitride FS-1)
(F2) talcum (woods changes into (strain) and manufactures, TALCAN PAWDER PL-NN)
Packing material (G):
(G1) glass fibre (diameter 13 μ m, NEG (strain) is manufactured, ECS 03T-187)
(G2) glass fibre (diameter 10 μ m, NEG (strain) is manufactured, ECS 03T-187H)
(G3) glass flake (manufacture, REFG-108) by NHTechno (strain).
Fluorine resin (H):
(H1) tetrafluoroethylene (Asahi Glass (strain) is manufactured, Aflon PTFE C D076)
(H2) tetrafluoroethylene-vinylformic acid core-shell polymer (Mitsubishi Rayon Co., Ltd. manufactures, METABLEN A-3800)
(embodiment 1～19 and comparative example 1～12)
(1) preparation of pellet
In the ratio shown in table 1～3, each composition [bromine based compound (B), sb oxide (C) and/or polycarbonate-based resin (D), phosphorus series compound (E), Nucleating Agent (F)] is coordinated with the polyester based resin shown in table 1～3 (A), with V-type mixing machine, mix equably.Use the twin screw extruder of 30mm φ by the packing material (G) of ratio shown in gained mixture and table 1, fluorine resin (H) melting mixing at the cylinder temperature of 260 ℃, the wire rod spraying from die head is cooling cut-out, acquisition pellet.In addition, to contain 0.3 weight part phenol be antioxidant (チ バ (strain) manufacture, " Irganox 1010 ") and 0.5 weight part releasing agent (Network ラ リ ァ Application ト (strain) manufactures, " Wax E ") to this pellet.
(2) making of molding and laser welding
The pellet that uses above-mentioned (1) to obtain, by injection molding machine (manufactures of (strain) Toshiba), shaping resin molding A (long 8cm * wide 1cm * thick 1.0mm) under the condition of 260 ℃ of barrel zone temperatures and 80 ℃ of die temperatures.In addition, as the resin forming product for resin forming product A welding (adherend) B, except using carbon black (Win Tech Polymer Ltd.'s manufacture for black colorant of the aforementioned pellet of 100 weight part and 3 weight parts, trade(brand)name " 2020B ") in addition, similarly make painted resin forming product B with resin forming product A.In addition, resin forming product B plays a part the heating element based on laser.
(3) judgement of weldability (mensuration of intensity)
As depicted in figs. 1 and 2, under the state contacting in resin forming product A (3) mode overlapping with a part with resin forming product B (4), with quartz glass plate (5) and metal sheet (6), grip, the laser welding machine (MODULAS C type) of manufacturing with ラ ィ ス タYi company, laser with wavelength 940nm, from light source (1) by laser (2) with live width W (2mm) optically focused to the contact surface of resin forming product A and resin forming product B, from resin forming product A (3) side, within the scope of the Laser output of 10～50W, irradiating laser under the condition of 5W step-length and sweep velocity 10mm/ second, carry out welding experiment.For the molding after welding experiment, use tensile testing machine (ORIENTEC CO., LTD. manufactures, RT C-1325), with 5mm/ minute, by the resin forming product A of laser welding and resin forming product B tensile shear, shearing resistance surpassed 300N and is judged as " welding ".In addition, with face of weld vertical direction on cut off, with carbonization and the foamed state of stereoscopic microscope observing face of weld, be determined with without excessively welding.From above result judgement welding, Non-carbonized and foamed state are chosen as " 3 ", and the in sight but welding of foamed state is also identified and is chosen as " 2 ", and carbonization is remarkable, laser-transmitting is insufficient is chosen as " 1 ", more than 2 is judged as laser welding good.
Result is shown in table 1～3.In addition, in table 1～3, flame retardant resistance and laser beam transmissivity mensuration as described below and evaluation.
(A) flame retardant resistance (flammability test (UL-94))
According to the method for the Subject of Underwriters Laboratories 94 (UL94), use 5 test films (thickness: the characteristic of dripping when 0.8mm) test flame retardant resistance and resin burn of the resin combination making of embodiment and comparative example.The grade (being expressed as notV) that flame retardant resistance is categorized as V-0, V-1, V-2 and does not correspond to these V grades according to the evaluation method of recording in UL 94.
(B) laser beam transmissivity
Use spectrophotometer (Japanese light splitting (strain) is manufactured, and V570, with integrating sphere) to measure the light transmittance of the resin forming product A under wavelength 940nm.
As can be seen from Table 1 and Table 2, in using the embodiment of specific bromine based compound and specific sb oxide, because the transmissivity of laser is high, therefore obtained high heat seal strength, welding is judged to be 3 or 2.In addition, the result of flame retardant resistance is also excellent.In contrast, in using the comparative example of halogen contained compound in addition and sb oxide, even if flame retardant resistance is high, can not welding, or allow to engage by laser welding, flame retardant resistance is also low-down.

Claims (9)

1. a laser-transmitting resin molding, described laser-transmitting resin molding can contact with laser absorption resin forming product that can absorbing laser, make laser-transmitting and engage with described laser absorption resin forming product, wherein this laser-transmitting resin molding is formed by resin combination, and this resin combination comprises polyester based resin (A) and is the bromine based compound (B) of bromination (methyl) acrylic resin and the sb oxide (C) with 2～10 μ m median sizes.
2. laser-transmitting resin molding according to claim 1, its laser-transmitting rate when thickness 1mm is more than 20%.
3. laser-transmitting resin molding according to claim 1 and 2, wherein said sb oxide (C) is at least one being selected from ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide and sodium antimonate.
4. laser-transmitting resin molding according to claim 1 and 2, wherein, with respect to 100 weight part polyester based resins (A), the ratio of bromine based compound (B) is 10～50 weight parts, and the ratio of sb oxide (C) is 5～30 weight parts.
5. laser-transmitting resin molding according to claim 1 and 2, it further contains polycarbonate-based resin (D) and phosphorus series compound (E).
6. laser-transmitting resin molding according to claim 1 and 2, it further contains crystallization promoter (F).
7. laser-transmitting resin molding according to claim 1 and 2, it is when thickness 0.8mm, and the flame retardant resistance based on UL94 standard is evaluated as V-0.
8. a composite formed article, it is engaged the laser-transmitting resin molding described in any one of claim 1～7 to form with laser absorption resin forming product that can absorbing laser by laser welding.
9. composite formed article according to claim 8, wherein, described laser-transmitting resin molding is at least to have the resin forming product that makes position laser-transmitting, that thickness is 0.1～1.0mm, and engages with laser absorption resin forming product at this position.
CN201210040854.3A 2007-06-13 2008-05-27 Laser-transmitting resin molded article, and composite molded article comprising the same Expired - Fee Related CN102850730B (en)

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Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5577755B2 (en) * 2010-03-04 2014-08-27 東レ株式会社 Polyester resin composition
CN101875783B (en) * 2010-07-14 2012-09-26 深圳市科聚新材料有限公司 Reinforced polytetramethyleneadiamide material and preparation method thereof
WO2012043599A1 (en) * 2010-09-29 2012-04-05 ウィンテックポリマー株式会社 Polybutylene terephthalate resin film
JP5650496B2 (en) * 2010-10-28 2015-01-07 ウィンテックポリマー株式会社 Integrated molded body
JP5927762B2 (en) * 2011-02-22 2016-06-01 東洋製罐株式会社 Laser welded sealed package and manufacturing method thereof
BR112013021242B1 (en) * 2011-03-07 2021-04-20 Basf Se uses of thermoplastic molding compositions, and transparent laser molded parts, process for producing welded molded parts, and welded molded part
MY161695A (en) * 2011-03-08 2017-05-15 Basf Se Laser-transparent polyesters having carboxylic acid salts
WO2012119967A1 (en) * 2011-03-08 2012-09-13 Basf Se Laser-transparent polyester comprising inorganic salts
JP6039372B2 (en) * 2012-11-09 2016-12-07 三菱エンジニアリングプラスチックス株式会社 Polybutylene terephthalate resin composition
JP5632567B1 (en) * 2013-02-12 2014-11-26 ポリプラスチックス株式会社 Grooved resin molded product
JP2016155939A (en) * 2015-02-25 2016-09-01 三菱エンジニアリングプラスチックス株式会社 Resin composition for laser welding and welding body thereof
EP3248757B1 (en) 2015-01-22 2021-03-03 Mitsubishi Engineering-Plastics Corporation Use of a laser welding member
JP7073636B2 (en) 2017-06-16 2022-05-24 オムロン株式会社 Method of curing adhesive composition and method of manufacturing adhesive structure
JP7339480B2 (en) * 2018-04-02 2023-09-06 グローバルポリアセタール株式会社 Polyamide resin composition and molded article
JP7265979B2 (en) * 2019-12-17 2023-04-27 ポリプラスチックス株式会社 Molded products for laser welding, agents for suppressing variations in laser transmittance of molded products for laser welding
CN112521729B (en) * 2020-11-12 2023-04-18 上海金发科技发展有限公司 High-fluidity black flame-retardant reinforced polyethylene glycol terephthalate composition and preparation method thereof
JP2022182215A (en) * 2021-05-28 2022-12-08 ポリプラスチックス株式会社 Laser transmissive resin composition and molded article thereof
CN114561089A (en) * 2022-02-24 2022-05-31 金发科技股份有限公司 PBT/PET alloy and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1690121A (en) * 2003-12-02 2005-11-02 东丽株式会社 Colored resin composition for laser welding and composite molding product using the same

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0662837B2 (en) * 1984-09-10 1994-08-17 ポリプラスチックス株式会社 Flame-retardant polybutylene terephthalate composition
DE19960104A1 (en) * 1999-12-14 2001-06-21 Bayer Ag Laser-weldable thermoplastic molding compounds
CN1497014A (en) * 2002-10-10 2004-05-19 胜技高分子株式会社 Polyester type resin composition
US20040186208A1 (en) * 2002-12-17 2004-09-23 Hiroyuki Sumi Flame resistant, laser weldable polyester resin composition
US20050167025A1 (en) * 2004-01-06 2005-08-04 Toshikazu Kobayashi Process for laser welding polyester compositions
PT1967549E (en) * 2005-12-26 2012-04-11 Wintech Polymer Ltd Use of a flame-retardant resin composition for transmission side member in laser welding
JP2008133341A (en) * 2006-11-28 2008-06-12 Mitsubishi Engineering Plastics Corp Black polyester resin composition for laser welding and molded product using the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1690121A (en) * 2003-12-02 2005-11-02 东丽株式会社 Colored resin composition for laser welding and composite molding product using the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JP特许昭61-66746A 1986.04.05

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