CN102850730A - 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
CN102850730A
CN102850730A CN2012100408543A CN201210040854A CN102850730A CN 102850730 A CN102850730 A CN 102850730A CN 2012100408543 A CN2012100408543 A CN 2012100408543A CN 201210040854 A CN201210040854 A CN 201210040854A CN 102850730 A CN102850730 A CN 102850730A
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China
Prior art keywords
resin
laser
transmitting
molding
brominated
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Granted
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CN2012100408543A
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Chinese (zh)
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CN102850730B (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
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B29C65/1629—Laser beams characterised by the way of heating the interface
    • B29C65/1635—Laser beams characterised by the way of heating the interface at least passing through one of the parts to be joined, i.e. laser transmission welding
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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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
    • B29C65/16—Laser beams
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    • B29C65/1612—Infrared [IR] radiation, e.g. by infrared lasers
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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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    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • 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
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/733—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the optical properties of the material of the parts to be joined, e.g. fluorescence, phosphorescence
    • B29C66/7332—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the optical properties of the material of the parts to be joined, e.g. fluorescence, phosphorescence at least one of the parts to be joined being coloured
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    • 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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    • B29C66/739—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 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)
  • Chemical & Material Sciences (AREA)
  • Electromagnetism (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Toxicology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Laminated Bodies (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 be that May 27, application number in 2008 are 2008800186427 the applying date, denomination of invention divides an application for the patent application of " laser-transmitting resin molding and composite formed article thereof ".
Technical field
The present invention relates to laser-transmitting high and excellent in flame retardance, by laser welding with can be used as of forming of the transmissive side parts of the laser welding (with) resin combination to the laser welding of the transmissive side parts of laser with molding (laser-transmitting side molding) and the composite formed article that uses this molding.
Background technology
Polyester based resin such as polybutylene terephthalate (PBT) is resin owing to having the excellent various characteristicses such as 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 the 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, increase because the impact of the faults such as unusually overheated, short circuit causes danger on fire, are seeking to improve flame retardant resistance.
Be that the flame retardant resistance of the polyester based resins such as resin is studied with regard to improving PBT 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 the TOHKEMY 2000-256545 communique (patent documentation 1).Put down in writing in the document, 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, record in the Japanese kokai publication sho 61-66746 communique (patent documentation 2), in polybutylene terephthalate, use aromatic series bromine compounds (bromine 5～10 substitution compounds of phenyl ether as 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 more than the median size 1 μ m as flame retardant (more than the preferred 2 μ m, 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 after forming parts, engage with miscellaneous part.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, when using tackiness agent, have 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 owing to heat, vibration etc. might damage goods.In contrast, do not have to damage goods because follow the heat of welding or vibration with the method for joining of laser welding, and the welding operation is also very simple and easy.Therefore, the recently application of laser welding method is more extensive, attracts attention as the welding process of various resin components.
Yet, take PBT be resin as the polyester based resin of representative because the transmissivity of laser is low, have the problem that is difficult to welding, this has been proposed 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, using the transmissivity of every 1mm thickness of the molding mensuration of being made by foregoing is more than 10%.Put down in writing in the document, in order to improve flame retardant resistance, can add fire retardant and flame retardant.In addition, a kind of method that manufactures body is disclosed in the TOHKEMY 2001-26656 communique (patent documentation 4), comprise by molding (A) and other molding (B) being carried out welding processing making it integrated, described molding (A) by be selected from fusing point be 170～220 ℃ PBT based copolymer, polyethylene terephthalate based copolymer that fusing point is 200～250 ℃ and fusing point be 210～260 ℃ the Polyethylene Naphthalate based copolymer at least a polyester based copolymer (a) consist of.Put down in writing in the document, in the scope of not damaging the 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 putting down in writing in these documents, lack the transmissivity to laser, be difficult to carry out fully laser welding.
In addition, a kind of polyester and resin composition is disclosed in the Japanese Unexamined Patent Application Publication 2006-509893 communique (patent documentation 5), but it is the polyester and resin composition of the laser welding of flame retardant resistance, comprises phenol polymer and (D) thermoplastic acrylic copolymer of 1～25 % by weight of phosphonium flame retardant, (C) 1～25 % by weight of thermoplastic polyester, (B) 1～35 % by weight of (A) 10～90 % 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 because take phenol polymer as essential composition, therefore the problem that exists is, the 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 then 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, the page 2 bottom right 18 row～upper left hurdle of page 39 row, the upper left hurdle of page 3 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 the laser-transmitting resin molding is provided and uses this molding, although it for basic, can have high-caliber laser welding (laser-transmitting) and flame retardant resistance take polyester based resin (especially the polyaromatic such as polybutylene terephthalate acid alkylene ester (polyalkylene arylate) is resin) concurrently.
Another object of the present invention is, provides to have high-caliber laser welding and flame retardant resistance concurrently, and has the laser-transmitting resin molding of excellent color harmony thermostability and the composite formed article that uses this molding.
Another purpose of the present invention is, provides to have excellent laser-transmitting, also can keep the laser-transmitting resin molding of high flame retardant resistance and the composite formed article that uses this molding when shaping is very thin simultaneously.
A further object of the present invention is, but provides the molding that will have a high flame retardant resistance by laser welding to engage the composite formed article that forms with the resin forming product of absorbing laser.
For the scheme of dealing with problems
The inventor etc. conduct in-depth research in order to realize aforementioned problems, found that, when forming the 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 finish the present invention.
Namely, laser-transmitting resin molding of the present invention (or laser-transmitting side molding) but be to contact with the laser absorption resin forming product of 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 the laser welding sometimes by resin combination, laser welding (the 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 a bromine based compound (B) (or bromide fire retardant (B)) in resin and the brominated epoxy resin and the sb oxide (C) with greater particle size (median size is 2～10 μ m approximately).
This molding has excellent laser-transmitting, and for example when thickness 1mm (or molding of thickness 1mm), the 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) especially can be to be selected from least a in ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide and the 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 about 10～50 weight parts, with respect to 100 weight part polyester based resins (A), the ratio of sb oxide (C) can be about 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, when thickness 0.8mm (or molding of thickness 0.8mm), can be V-0 usually based on the flame retardant resistance evaluation of UL 94 standards.
The present invention also comprises by laser welding but aforementioned laser transmitting resin molding is engaged the composite formed article that forms with the laser absorption resin forming product of absorbing laser.This composite formed article can be: the laser-transmitting resin molding have at least make laser-transmitting, thickness is the resin forming product at the position of 0.1～1.0mm, and the composite formed article that engages with the laser absorption resin forming product at this position.Aforementioned composite formed article for example can by the contact surface to laser-transmitting resin molding and laser absorption resin forming product, be made from the direction irradiating laser that aforementioned laser-transmitting resin molding side direction the laser absorption resin forming product.
The invention effect
In laser-transmitting resin molding of the present invention, because the sb oxide combination with polyester based resin (polybutylene terephthalate is resin etc.), specific bromine based compound (bromide fire retardant) and specified particle diameter, therefore although for basic, can have high-caliber laser welding (laser-transmitting) and flame retardant resistance take polyester based resin (especially polybutylene terephthalate is that the polyaromatic acid alkylene ester such as resin is resin) 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, therefore laser-transmitting resin molding of the present invention, has high-caliber laser welding and flame retardant resistance concurrently owing to can be substantially devoid of phenol polymer etc., 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 keep high flame retardant resistance.Therefore, can obtain the molding (especially thin molding) by will having high flame retardant resistance but be engaged the composite formed article that forms by laser welding with the resin forming product of absorbing laser.
Description of drawings
Fig. 1 is the schematic side view for the laser welding of explanation embodiment and comparative example.
Fig. 2 is the diagrammatic top view for the laser welding of explanation embodiment and comparative example.
Embodiment
Laser-transmitting resin molding of the present invention (or laser-transmitting side molding) but be to contact with the laser absorption resin forming product of 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, also comprise the specific polyester resin composition (resin combination of the transmissive side parts in the laser welding, laser welding (the transmissive side parts are used) flame retardant resin composition) that this laser welding is used among the present invention.
Aforementioned resin (sometimes be referred to as laser welding with resin combination, laser welding with flame retardant resin composition, polyester resin composition, transmissive side parts with resin combination, resin combination etc.) comprises polyester based resin (A), specific bromine based compound (B) and specific sb oxide (C).
(polyester based resin (A))
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 the polyester based resin of base resin.
As the 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, preferred C 4-14Dicarboxylic acid), the 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 acids 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 the dicarboxylic acid composition, may be used 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, preferred 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～four 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, may be used 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 the polyester based resin, from the laser welding consideration, low-crystalline or amorphism aromatic polyester resin are preferred.
It is resin that preferred polyester based resin comprises saturated polyester, especially the aromatic series saturated polyester is resin, and usually 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, preferred 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 that uses in the polyaromatic acid alkylene ester based copolymer (especially polyalkylene terephthalates based copolymer), can list glycols [C corresponding to alkylidene unit different from the alkylidene unit (such as ethylidene, tetramethylene etc.) in the polyaromatic acid alkylene ester based polymer 2-6Aklylene glycol (for example, the straight or branched aklylene glycols such as ethylene glycol, trimethylene, 1,2-PD, hexylene glycol etc.) has the approximately poly-C of 2～4 alkylidene oxide unit of repeat number 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 at the asymmetric position of aromatic hydrocarbon ring, 1,4-cyclohexanedimethanol etc.], hydroxycarboxylic acid (the illustrative compound in front etc.), lactone (the illustrative compound in front such as caprolactone) 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) for example is 30mol% following (for example 0～30mol%), for example can in the scope of about 0.01～30mol%, select, usually 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, consider from the viewpoint of improving flame retardant resistance, mechanical properties, 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.
Consider from the viewpoint of laser welding, PBT is that the fusing point of resin for example is approximately more than 190 ℃ (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.Limiting viscosity is crossed when hanging down, and physical strength might reduce, and when limiting viscosity was too high, flowability even plasticity might reduce.In addition, limiting viscosity (IV) for example can be measured under the condition of 35 ℃ of temperature in orthomonochlorphenol.
Polyester based resin can use commercially available product, also can prepare such as transesterify, direct esterification etc. with method commonly used.For example, but PBT is resin can prepare by allow the monomer of terephthalic acid or its reactive derivatives and BDO and copolymerization as required carry out copolymerization with above-mentioned method commonly used.
(bromine based compound (B))
Among the present invention, as with the fire retardant of sb oxide (C) combination, use specific bromide fire retardant, namely, use is selected from brominated (methyl) acrylic resin (or bromination (methyl) acrylic resin, gathering (methyl) benzyl acrylate such as bromination is 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 carry out bromide that bromination process to phenylethylene resin series), brominated styrene are 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 Resins, epoxy (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 a bromine based compound (B).
By with this specific bromine based compound and the sb oxide combination with specified particle diameter described later, can give simultaneously high flame retardant resistance and laser-transmitting for aforementioned resin (or laser-transmitting resin molding).
In the bromine based compound, overall with respect to the bromine based compound, the ratio of bromine atoms (part by weight) can be selected in the scope of (for example approximately 35～90 % by weight) more than 30 % by weight usually, 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 the 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.The bromination polyacrylic ester is that resin can be the compound that for example represents with following formula.
[Chemical formula 1]
Figure BDA0000137151100000121
(in the formula, m represents the integer more than 2, 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, with (methyl) vinylformic acid cylite ester ((methyl) vinylformic acid pentabromo-benzyl ester for example, (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.
Gathering (methyl) benzyl acrylate in bromination is in the 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 the 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 for more than the 50mol% (for example approximately 55～99.5mol%), being 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) for example is approximately 1000～300000, is preferably approximately 3000～200000, more preferably approximately 5000～150000.
In addition, brominated phenylethylene resin series (or brominated styrene is resin) for example can be the resin that represents with following formula.
[Chemical formula 2]
Figure BDA0000137151100000131
(in the formula, j represents the integer more than 2, and m represents 1～4 integer.)
It is that monomer (brominated styrenes such as Dowspray 9, phenylstilbene bromide) is as the resin of polymerization composition that representative brominated phenylethylene resin series (or brominated styrene is resin) comprises take brominated styrene, be homopolymer or the multipolymer (brominated Polystyrene etc.) of monomer such as brominated styrene, 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, be in the multipolymer of monomer and co-polymerized monomer at brominated styrene, with respect to whole formation monomers, brominated styrene is that the ratio of monomer can be for more than the 50mol% (for example approximately 55～99.5mol%), being 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 for example can be 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) for example can be the resin that represents with following formula.
[chemical formula 3]
Figure BDA0000137151100000141
(in the 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 the integer more than 2.)
In the R and R ' of above-mentioned formula, as alkyl, such as alkyl such as the alkyl that can list carbon number 1～10 (methyl, ethyl, propyl group, sec.-propyl etc.).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 is 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 with 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 for example can be approximately 1000～40000, is preferably approximately 2000～30000.
Brominated Resins, epoxy (brominated epoxy resin) for example can be the resin that represents with following formula.
[chemical formula 4]
Figure BDA0000137151100000151
[in the formula, X represents bromine atoms, and i and j represent 1～4 integer, and n represents the integer more than 0, T 1And T 2Can be identical or different, the expression glycidyl or-CH 2CH (OH) CH 2OPh (in the formula, Ph represents to have substituent halogenated phenyl).]
Representative brominated Resins, epoxy (brominated epoxy resin) comprises that (or brominated bisphenol class is such as two (hydroxyphenyl) C of the brominations such as tetrabromo-bisphenol with brominated bisphenols 1-10Alkane etc.) be the Resins, epoxy of polymerization composition (or diol component), such as the brominated bisphenol type Resins, epoxy such as brominated bisphenol a type epoxy resin (for example reaction product of tetrabromo-bisphenol and Epicholorohydrin).In addition, the diol component of brominated epoxy resin can use separately or with 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 T of the end of brominated Resins, epoxy and aforementioned formula 2Situation similarly can carry out termination process.Especially, the Resins, epoxy of (basis) composition take tetrabromo-bisphenol as the polymerization Resins, epoxy of tetrabromo-bisphenol and diglycidylether (or contain) is when use level is too much, the foreign matter of the blackspot shape in the molding increases, infringement mechanical characteristics and/or electrical characteristic, when laser welding, produce unusually overheated, might damage weldability, therefore preferably carry out termination process.
The number-average molecular weight of brominated Resins, epoxy for example can be approximately 1000～40000, is preferably approximately 2000～30000, more preferably approximately 3000～20000.
In these brominated resins, from the viewpoint of stability with excellent laser welding, especially preferably use that to be selected from poly-(methyl) acrylic ester resin of bromination (especially bromination polypropylene acid benzyl ester is that the bromination polyacrylic ester such as resin is resin) and brominated styrene be at least a in the 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) for example is about 5～70 weight parts, be preferably approximately 8～60 weight parts, more preferably about 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 keep 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 use 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.
Among the present invention, as sb oxide, use the sb oxide with specified particle diameter.The median size of sb oxide can be selected in the scope more than the 2 μ m, for example is about 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, when using bromide fire retardant commonly used and sb oxide, the laser-transmitting reduction of resin combination or laser-transmitting resin molding can not be carried out laser welding.Yet, among the present invention, by sb oxide and specific aforementioned bromine based compound and the usefulness with this specified particle diameter, 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, when 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, possiblely be, the infringement laser-transmitting, polyester based resin (A) itself is decomposed, perhaps promote the reaction of polyester based resin (A) and halogen-containing resin system fire retardant (B), the infringement 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) for example can be about 3～40 weight parts, is preferably approximately 5～30 weight parts, more preferably about 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, might damage the intrinsic mechanical characteristics of polyester based resin, shaping processing characteristics, perhaps scattering and the screening effect owing to laser reduces 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/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 the resin that obtains of the reaction by carbonic ethers such as dihydroxy compound and phosgene or diphenyl carbonates normally.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 the 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 for example can be about 5～100 weight parts, is preferably approximately 10～70 weight parts, more preferably about 10～50 weight parts.When the use level of polycarbonate-based resin is too much, might lose crystallinity by polyester based resin (for example PBT is resin), and chemical-resistant, thermotolerance reduce.
(phosphorus series compound (E))
For stable crystalline, laser-transmitting, can further add phosphorus series compound (or P contained compound) in the aforementioned resin (or laser-transmitting resin molding).The preferred embodiment of phosphorus series compound can list phosphorous acid esters { list～three (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, the 6-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2, the 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 two phenylene diphosphites 3-6Alkyl-aryl) phosphorous acid ester etc. }, phosphiinic acid ester (four (2, the 4-di-tert-butyl-phenyl)-4,4 '-two 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 0.01～3 weight part for example, is preferably 0.03～2 weight part, more preferably 0.05～1.0 weight part.When use level is few, can not help the stable of crystallinity, laser-transmitting, and when use level is too much, might ooze out, the insulativity of molding reduces, and has around in the situation of metal, and the detrimentally affect of metallic corrosion, short circuit might occur.
(crystallization promoter (F))
For stable crystalline, laser-transmitting, can in not damaging the laser-transmitting scope, add crystallization promoter in the aforementioned resin (or laser-transmitting molding) equally.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.) for example is about 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 0.001～10 weight part for example, is preferably 0.01～7 weight part.
Aforementioned resin (or laser-transmitting molding) can also comprise packing material (or supporting material), as long as apply in the dysgenic scope in the transmissivity to laser not.
This packing material (or weighting agent) comprises fibrous packing material [inorganic fibre (glass fibre for example for example, silica fibre, sapphire whisker, the 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) for example can be about 1～50 μ m (being preferably 3～30 μ m), and mean length (average fiber length) for example can (be preferably 300 μ m～1mm) for about 100 μ m～3mm.In addition, the median size of tabular or granular packing material for example can be about 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 the wavelength of laser, 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 collecting agent or surface treatment agent commonly used.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 with can process with above-mentioned collecting agent or surface treatment agent in advance before other compositions (composition (A), (B) and (C) etc.) mix, also can with packing material with process by interpolation collecting agent or surface treatment agent when other compositions mix.With respect to 100 weight part packing materials (glass fibre etc.), the ratio of collecting agent or surface treatment agent for example is about 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 about 0～200 weight part, is preferably approximately 5～150 weight parts, more preferably about 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, might 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 the multipolymer of multipolymer, aforementioned fluorochemical monomer and other co-polymerized monomers (acrylic monomers such as the ethylene series monomers such as ethene, propylene, (methyl) acrylate 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, prevent under the drop of resin of the melting along with burning effect).In addition, carry out radioactive rays processing or the heat treated fluorine resin more than 200 ℃ 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 about 0～3 weight part (for example 0.01～3 weight part), is preferably approximately 0.05～2 weight part, more preferably about 0.1～1.5 weight part.Wherein, when aforementioned ratio is too much, possiblely be, the viscosity of resin combination raises, and plasticity reduces, and produces white dot in molding, the infringement outward appearance, and local laser-transmitting rate reduces, the laser welding strength decreased.
Depend on the needs, in the scope of not damaging effect of the present invention, according to purposes etc., in aforementioned resin (or laser-transmitting resin molding), can add various additives, for example stablizer (antioxidant, UV light absorber, photostabilizer, thermo-stabilizer etc.), other fire retardants (sulfur-bearing fire retardant for example, Silicone-containing Flame Retardant, the 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 based on the non-halogen flame retardant except the halogen flame retardants such as bromide fire retardant also proposed, such as may be used the phosphorus flame retardant shown in Japanese kokai publication hei 5-70671 communique, the Japanese kokai publication hei 8-73720 communique etc.
As aforementioned antioxidant, can list antioxidant commonly used, be that antioxidant, bulky amine are that antioxidant, quinhydrones are antioxidant etc. such as sterically hindered phenol.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, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], two～four [3-(3,5-, two-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 for example is about 0.005～3 weight part, is preferably approximately 0.01～1.5 weight part (for example 0.02～1 weight part), more preferably about 0.05～0.5 weight part.In addition, when the antioxidant ratio is too much, might the dispersiveness in resin reduce, antioxidant oozes out on the molding surface, and the outward appearance of molding might variation along with oozing out.
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 such as ethylene glycol, polyoxyethylene glycol etc. (gathering) aklylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, anhydro sorbitol etc.), 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～three esters, Zerol for example, glycerol tripalmitate etc.), trimethylolpropane fatty acid ester (monoesters～three esters, such as TriMethylolPropane(TMP) monopalmitate etc.), pentaerythritol fatty ester (monoesters～four esters, pentaerythritol stearate etc.), fatty acid esters of sorbitan (monoesters～four esters is 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 for example is about 0.005～3 weight part, is preferably approximately 0.01～1.5 weight part.Wherein, when the ratio of releasing agent is too much, might the dispersiveness in resin reduce, releasing agent oozes out on the molding surface, and the outward appearance of molding might variation along with oozing out.
In addition, in the radioparent scope of significantly not damaging the laser that is used for welding, aforementioned resin can also contain tinting material (such as the tinting material of putting down in writing in TOHKEMY 2000-309694 communique, the 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 use separately, also multiple colorant combination can be used to be adjusted into required tone.For example, the utilization mixing (combination of the combination of multiple dyestuff and pigment such as yellow dyes and pigment and purple dye and pigment, yellow dyes 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 about 0.001～5 weight part, is preferably approximately 0.005～3 weight part, more preferably about 0.01～2 weight part.
Aforementioned resin (or laser-transmitting resin molding) has excellent flame retardant resistance, the molding that forms with resin combination is generally V-0 based on the flame retardant resistance evaluation of UL94 standard (Subject 94 of Underwriters Laboratories) when thickness 0.8mm.And, aforementioned resin (or laser-transmitting resin molding) is even be shaped the very thin high flame retardant resistance that also has, even the thickness of aforementioned molding is approximately below the 0.8mm, for example be about 0.3～0.8mm, be preferably approximately 0.4～0.75mm, also can reach V-0 based on the flame retardant resistance evaluation of UL94 standard.
Aforementioned resin can be bulk material mixture or molten mixture (pellet etc.).This resin combination can be by preparing polyester based resin (A), bromine based compound (B) and sb oxide (C) (with in addition as required other compositions) mixing or mixing (melting mixing) with method commonly used.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 by preparing each composition melting mixing with method commonly used.For example, aforementioned resin can be by the preparation of following method: (1) mixes each composition, and is mixing with forcing machine (single screw rod or twin screw extruder), extrude, and prepares pellet, the method that further forms as required; (2) preparation forms different pellets (masterbatch) for the time being, and the described pellet that mixes (dilution) specified amount is used 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 method of forming mill etc.In addition, the molding such as pellet can prepare 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 cooperate equably each composition, can with a part of micronization of resinous principle (polyester based resin etc.), then the gained powder be mixed with other compositions.In addition, resin combination of the present invention can be with the form former state of mixture (for example bulk material or molten mixture) for the manufacture of molding.
Aforementioned resin (or laser-transmitting resin molding) has high light transmissivity although formed by polyester based resin 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) for example is approximately more than 20% (for example approximately 20～100%), be preferably approximately more than 25% (for example 25～80%), more preferably approximately more than 30% (for example 30～50%) is generally approximately 20～40% (for example 20～30%).In addition, aforementioned resin (or laser-transmitting resin molding) can have the laser-transmitting rate of above-mentioned scope for the optical maser wavelength that is used for laser welding (for example any wavelength (for example wavelength 940nm) in the aftermentioned laser wavelength range).
Like this, although the base resin of resin combination of the present invention is polyester based resin (PBT is resin etc.), but have high-caliber flame retardant resistance and laser-transmitting, therefore can be used as the laser welding resin combination, can be used for forming the transmissive side parts in the 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 transmissive side parts in the laser welding are with resin combination (sometimes be referred to as laser-transmitting resin molding with resin combination, be used to form resin combination that the resin combination of laser-transmitting resin molding, transmissive side parts in the laser welding use etc.).In addition, aforementioned laser transmitting resin molding (sometimes being referred to as laser-transmitting molding, laser-transmitting side resin forming product, laser-transmitting side molding, laser-transmitting resin parts, laser-transmitting parts etc.) but be to contact with the laser absorption resin forming product of absorbing laser as previously mentioned, make laser-transmitting, the molding that engages with the aforementioned resin molding, and be the molding that forms with 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 the laser welding), can be used for forming the transmissive side parts of laser welding.
This molding (laser-transmitting resin molding) is as mentioned above with aforementioned resin (or each composition) melting mixing, be shaped with common methods such as extrusion molding, injection molded, compression molding, blow molding, vacuum forming, spinning-shaping, gas injection shapings, but usually be shaped by injection molded.Molding especially can be the molding (injection molding product) that is 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 approximately under 250～280 ℃ with the resin combination melting mixing, prepare as required pellet, by injection molding machine injection molded under the condition of approximately 200～300 ℃ of barrel zone temperatures (for example 250～280 ℃).In addition, die temperature can be selected in the scope of approximately 40～100 ℃ (for example 40～90 ℃), from keeping 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 ℃), especially be preferably approximately 50～85 ℃ (for example 46～80 ℃).
Shape to molding does not have specific limited, in order to engage and to use with compounding ingredient (other resin forming products) by laser welding, normally has at least the shape (for example tabular) on contact surface (plane etc.).In addition, molding of the present invention has the (position of laser welding, position that makes laser-transmitting at least, the laser welding position), the thickness at this position (thickness of the direction of laser-transmitting) for example is 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 zone.
The present invention also comprises the composite formed article (or composite molded product or compound forming component or combined shaping resin component) that forms with aforementioned laser transmissivity molding.This composite formed article is will engage the molding that forms 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 by the aforementioned laser transmitting resin molding (or first molding) that aforementioned resin forms by laser welding, and two molding are mutually integrated.In addition, the first resin forming product has the position (laser welding position) of laser-transmitting as previously mentioned at least, 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 usually ground integrated by being engaged to small part.
The resin that consists of aforementioned the second resin forming product there is not 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 use and the base resin identical type that consists of aforementioned the first resin forming product (aforementioned resin) or the resin of same system, be 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, among the present invention, the first resin forming product is owing to having excellent flame retardant resistance, even do not utilize fire retardant etc. that the second resin forming product is carried out fire-retardant finish, 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 the wavelength of laser, 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, usually can use black pigment or dyestuff, especially carbon black.The median size of carbon black can be about 10～1000nm usually, is preferably approximately 10～100nm.With respect to whole the second resin forming products, the ratio of tinting material is about 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 clamping contain the resin sheet (PBT series resin sheet etc.) of the laser absorbents such as carbon black or tinting material, perhaps be coated with laser absorbent, with two molding driving fits, then engage by laser radiation.In addition, about the aforementioned details that contains the resin sheet of tinting material, such as speciallyying permit No. 1829720 communique etc. with reference to Japan.
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 the 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 driving fit (fusion), cool off and engage.In this composite formed article, if use molding of the present invention, can obtain high bond strength by fusion, can with by irradiating laser not the non-fusion parts of fusion keep equal height fusion intensity.
The irradiation of laser is carried out towards the direction of the second molding from the first resin forming product side (transmitting member side) usually.And, by this laser radiation, make the interface heating of the second molding that contains absorption agent or tinting material, thereby make the first molding and the fusion of the second molding.In addition, as required, utilize the lens system, laser is gathered on the interface of the first molding and the second molding, contact interface is fused.Among the present invention, because transmissive side parts, namely the first resin forming product is that aforementioned resin by aforementioned laser transmissivity excellence forms, and therefore can carry out effectively laser welding 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 to be about 600～2000nm, is preferably approximately 700～1500nm, more preferably about 800～1200nm (laser of 800～1100nm) for example.
As the laser source of the laser welding that can be used for 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, usually utilize pulse laser.
In addition, the laser scanning speed of laser welding (laser irradiating position is in the mobile speed of sample) is not had specific limited, can at random select.In order to prevent that welding is bad and to improve heat seal strength, the aforementioned laser sweep velocity for example is preferably approximately 0～150mm/ second, about 1～100mm/ second more preferably, more preferably about 2～50mm/ second.
Therefore aforementioned molding can easily engage with the resin forming product of compounding ingredient by laser welding usually owing to having excellent laser welding.In addition, as required, can be with laser welding and other burning-on methods (such as vibration welded method, ultrasonic welding method, hot plate burning-on method etc.) combination.
Utilizability on the 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 especially are 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
Followingly illustrate in greater detail the present invention according to embodiment, 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. makes)
(A2) the 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 makes polybutylene terephthalate-polycaprolactone elastomerics, Q4110).
Bromine based compound (B):
(B1): the bromination polyacrylic ester (poly-(vinylformic acid pentabromo-benzyl ester), デ ッ De シ one Block ロ ミ Application グ Le one プ company makes, FR 1025)
(B2): brominated Polystyrene (make, PyroChek68PB) by ァ Le ベ マ one Le (strain)
(B3): brominated polycarbonate (brominated bisphenol A type polycarbonate, Supreme Being people changes into (strain) and makes, Fire Guard FG-7500)
(B4): brominated epoxy resin (brominated bisphenol a type epoxy resin, make, SRT5000) by this pharmaceutical industries of slope (strain)
(B5): ethylenebis (tetrabromo phthalimide) (SAYTEX BT-93, ァ Le ベ マ one Le (strain) is made).
Sb oxide (C):
(C1) antimony pentaoxide (median size 3.8 μ m, daily output chemical industry (strain) is made, サ Application ェ Port ッ Network NA-1030)
(C2) ANTIMONY TRIOXIDE SB 203 99.8 PCT (median size 6.3 μ m, make, PATOX-L) by Japanese concentrate (strain)
(C3) ANTIMONY TRIOXIDE SB 203 99.8 PCT (median size 1.2 μ m, make, 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, LA-920), measures as dispersion medium with distilled water, and the 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) makes, ュ one ピ ロ Application S-3000).
Phosphorus series compound (E):
(E1) SODIUM PHOSPHATE, MONOBASIC (rice mountain chemical industry (strain) is made, SODIUM PHOSPHATE, MONOBASIC)
(E2) four (2,4-di-tert-butyl-phenyl)-4,4 '-two phenylene two phosphinates (Network ラ リ ァ Application ト ジ ャ パ Application (strain) is made, 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 makes, TALCAN PAWDER PL-NN)
Packing material (G):
(G1) glass fibre (diameter 13 μ m, NEG (strain) is made, ECS 03T-187)
(G2) glass fibre (diameter 10 μ m, NEG (strain) is made, ECS 03T-187H)
(G3) glass flake (make, REFG-108) by NHTechno (strain).
Fluorine resin (H):
(H1) tetrafluoroethylene (Asahi Glass (strain) is made, Aflon PTFE C D076)
(H2) tetrafluoroethylene-vinylformic acid core-shell polymer (Mitsubishi Rayon Co., Ltd. makes, 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 cooperated with the polyester based resin (A) shown in table 1～3, mix equably with V-type mixing machine.Use the twin screw extruder of 30mm φ with packing material (G), fluorine resin (H) melting mixing under 260 ℃ cylinder temperature of ratio shown in gained mixture and the table 1, will after the wire rod cooling of die head ejection, cut off, obtain pellet.In addition, to contain 0.3 weight part phenol be antioxidant (チ バ (strain) make, " Irganox 1010 ") and 0.5 weight part releasing agent (Network ラ リ ァ Application ト (strain) makes, " 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 (manufacturings 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 resin forming product (adherend) B that is used for resin forming product A welding, (Win Tech Polymer Ltd. makes with carbon black except using the aforementioned pellet of 100 weight parts and 3 weight part black colorants, 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 that resin forming product A (3) and resin forming product B (4) mode overlapping with a part contacts, grip with quartz glass plate (5) and metal sheet (6), laser welding machine (MODULAS C type) with the manufacturing of ラ ィ ス タ one company, laser with wavelength 940nm, from light source (1) with 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, in the Laser output scope of 10～50W, irradiating laser under the condition of 5W step-length and sweep velocity 10mm/ second carries out the welding experiment.For the molding after the welding experiment, use tensile testing machine (ORIENTEC CO., LTD. makes, RT C-1325), with 5mm/ minute resin forming product A and the resin forming product B tensile shear with laser welding, shearing resistance surpassed 300N and then is judged as " welding ".In addition, cutting off with the face of weld vertical direction, with carbonization and the foamed state of stereoscopic microscope observing face of weld, be determined with without excessively welding.Judge welding from above result, Non-carbonized and foamed state then are chosen as " 3 ", and the in sight but welding of foamed state also is identified then and is chosen as " 2 ", and carbonization is remarkable, laser-transmitting is insufficient then is chosen as " 1 ", is judged as laser welding more than 2 good.
The 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 94 (UL94) of Underwriters Laboratories, use 5 test films that the resin combination of embodiment and comparative example makes (thickness: the 0.8mm) characteristic of dripping the during burning of test flame retardant resistance and resin.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 putting down in writing among the UL 94.
(B) laser beam transmissivity
Use spectrophotometer (Japanese light splitting (strain) is made, and V570 is with integrating sphere) to measure the light transmittance of the resin forming product A under the wavelength 940nm.
Figure BDA0000137151100000351
Figure BDA0000137151100000361
Can find out from table 1 and table 2, in the embodiment that uses 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 also is excellent.In contrast, in the halogen contained compound and the comparative example of sb oxide that use in addition, even flame retardant resistance is high, can not welding, perhaps namely allow to engage by laser welding, flame retardant resistance also is low-down.

Claims (9)

1. laser-transmitting resin molding, but described laser-transmitting resin molding can contact with the laser absorption resin forming product of 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 selected from bromination (methyl) acrylic resin, brominated styrene is that resin and brominated polycarbonate are at least a bromine based compound (B) in the resin and 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) are to be selected from least a in ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide and the 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 evaluated as V-0 based on the flame retardant resistance of UL 94 standards when thickness 0.8mm.
8. composite formed article, but it engages each described laser-transmitting resin molding of claim 1～7 by laser welding and forms with the laser absorption resin forming product of absorbing laser.
9. composite formed article according to claim 8, wherein, described laser-transmitting resin molding be have at least make laser-transmitting, thickness is the resin forming product at the position of 0.1～1.0mm, and engages with the 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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