JP2007161774A - Styrenic flame-retardant resin composition for laser fusion bonding transmission - Google Patents
Styrenic flame-retardant resin composition for laser fusion bonding transmission Download PDFInfo
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- JP2007161774A JP2007161774A JP2005356609A JP2005356609A JP2007161774A JP 2007161774 A JP2007161774 A JP 2007161774A JP 2005356609 A JP2005356609 A JP 2005356609A JP 2005356609 A JP2005356609 A JP 2005356609A JP 2007161774 A JP2007161774 A JP 2007161774A
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000003063 flame retardant Substances 0.000 title claims abstract description 60
- 239000011342 resin composition Substances 0.000 title claims abstract description 31
- 230000005540 biological transmission Effects 0.000 title claims abstract description 23
- 230000004927 fusion Effects 0.000 title abstract 4
- 238000012360 testing method Methods 0.000 claims abstract description 19
- 238000002844 melting Methods 0.000 claims abstract description 17
- 230000008018 melting Effects 0.000 claims abstract description 17
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 74
- 238000003466 welding Methods 0.000 claims description 32
- 229920005989 resin Polymers 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 17
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000002834 transmittance Methods 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920001890 Novodur Polymers 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- 239000000463 material Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- NSUMXOSXCPDXEG-UHFFFAOYSA-N 2,3-dibromo-4-[2-(2,3-dibromo-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(Br)=C(Br)C=1C(C)(C)C1=CC=C(O)C(Br)=C1Br NSUMXOSXCPDXEG-UHFFFAOYSA-N 0.000 description 3
- BDFBPPCACYFGFA-UHFFFAOYSA-N 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine Chemical compound BrC1=CC(Br)=CC(Br)=C1OC1=NC(OC=2C(=CC(Br)=CC=2Br)Br)=NC(OC=2C(=CC(Br)=CC=2Br)Br)=N1 BDFBPPCACYFGFA-UHFFFAOYSA-N 0.000 description 3
- UAUKZBYFFAFGGZ-UHFFFAOYSA-N 2-[[2,3-dibromo-4-[2-[2,3-dibromo-4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenoxy]methyl]oxirane Chemical compound O1C(COC2=C(C(=C(C=C2)C(C)(C)C2=C(C(=C(C=C2)OCC2CO2)Br)Br)Br)Br)C1 UAUKZBYFFAFGGZ-UHFFFAOYSA-N 0.000 description 3
- 239000011358 absorbing material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920005669 high impact polystyrene Polymers 0.000 description 3
- 239000004797 high-impact polystyrene Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- BHYQWBKCXBXPKM-UHFFFAOYSA-N tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate Chemical compound BrCC(CBr)(CBr)COP(=O)(OCC(CBr)(CBr)CBr)OCC(CBr)(CBr)CBr BHYQWBKCXBXPKM-UHFFFAOYSA-N 0.000 description 3
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 2
- CVEPFOUZABPRMK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;styrene Chemical compound CC(=C)C(O)=O.C=CC1=CC=CC=C1 CVEPFOUZABPRMK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 1
- LLVVSBBXENOOQY-UHFFFAOYSA-N 1,2,3,4,5-pentabromobenzene Chemical compound BrC1=CC(Br)=C(Br)C(Br)=C1Br LLVVSBBXENOOQY-UHFFFAOYSA-N 0.000 description 1
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 1
- YUAPUIKGYCAHGM-UHFFFAOYSA-N 1,2-dibromo-3-(2,3-dibromopropoxy)propane Chemical compound BrCC(Br)COCC(Br)CBr YUAPUIKGYCAHGM-UHFFFAOYSA-N 0.000 description 1
- LXIZRZRTWSDLKK-UHFFFAOYSA-N 1,3-dibromo-5-[2-[3,5-dibromo-4-(2,3-dibromopropoxy)phenyl]propan-2-yl]-2-(2,3-dibromopropoxy)benzene Chemical compound C=1C(Br)=C(OCC(Br)CBr)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(OCC(Br)CBr)C(Br)=C1 LXIZRZRTWSDLKK-UHFFFAOYSA-N 0.000 description 1
- OUCSIUCEQVCDEL-UHFFFAOYSA-N 2,3,4-tribromophenol Chemical compound OC1=CC=C(Br)C(Br)=C1Br OUCSIUCEQVCDEL-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- CPBQJMYROZQQJC-UHFFFAOYSA-N helium neon Chemical compound [He].[Ne] CPBQJMYROZQQJC-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000010979 ruby Substances 0.000 description 1
- 229910001750 ruby Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、熱可塑性樹脂からなる成形品同士を接着するレーザー溶着技術の透過側に必要なレーザー溶着透過用スチレン系難燃性樹脂組成物に関するものである。 The present invention relates to a styrene-based flame retardant resin composition for laser welding and transmission, which is necessary on the transmission side of a laser welding technique for bonding molded products made of thermoplastic resins.
熱可塑性樹脂からなる成形品同士を相互に接合する方法としてレーザー溶着法がある。レーザー溶着法は、接合する一方をレーザー光吸収材料で構成し、他方をレーザー光透過性材料で構成し、これらを重ね密着させた後、透過材料側からレーザーを照射する事により、透過材料を透過したレーザー光のエネルギーにより吸収材料の表面が加熱して該材料を溶融させると同時に、熱伝達により透過材料も溶融し、その後冷却する事で双方の樹脂を接合する技術である（特許文献１参照）。レーザー光としては、ガラスレーザー、ＹＡＧレーザー、ルビーレーザー、ヘリウム−ネオンレーザー、クリプトンレーザー、アルゴンレーザー、水素レーザー、窒素レーザー、二酸化炭素レーザー、半導体レーザー等のレーザー光が挙げられ、そのうち、溶着装置の設計の自由度やメンテナンス性、コストで有利な半導体レーザーが選定されている。この方法は、レーザー技術の発展と低コスト化から１９００年代後半に実用化され糸引きや、粉、バリなどが発生せず、接合部の見栄えも良く、あらゆる成形品の接合に使用できる点で好都合である。しかしながら、この方法で接合を行うには、一方の成形品の材料にレーザー光を透過させる特徴が必須となる。レーザー光の透過率が低い材料を透過側に用いた場合、レーザー光出力を上げる、レーザー光走査スピードを下げるといった加工条件の対応が必要となり、実際の生産工程では設備費が増加や生産効率の低下といった事態を招く。最悪の場合には、レーザー光入射表面で成形品の溶融、発煙、発火といった不具合を生じ、溶着が実現出来ない可能性も有り得る。
スチレン系樹脂はその特性を生かし広範囲な用途に使用されている。中でもスチレン系樹脂に高度な難燃性を付与させた難燃性樹脂は、難燃特性を始め機械的特性、物理的特性、電気特性、寸法安定性に優れる事から、ワープロ、パーソナルコンピュータ、プリンター、複写機等のＯＡ機器、ＴＶ、ＶＴＲ、オーディオ等の家電製品等を初めとする多岐の分野で使用されている。しかしながら、これらのスチレン系難燃性樹脂材料は、難燃化剤や難燃助剤等の各種添加剤を添加の影響と、スチレン系樹脂の配合の影響で、レーザー光の透過性が極めて低くなる為、従来のレーザー溶着法の検討ではレーザー光吸収材料にしか使用されてこなかった。 Styrenic resins are used in a wide range of applications by taking advantage of their properties. Of these, flame retardant resins, which have a high degree of flame retardancy added to styrene resins, have excellent mechanical properties, physical properties, electrical properties, and dimensional stability, including flame retardant properties, and are therefore word processors, personal computers, and printers. It is used in various fields including office automation equipment such as copying machines, home appliances such as TVs, VTRs, and audio. However, these styrene-based flame retardant resin materials have extremely low laser light transmittance due to the effects of adding various additives such as flame retardants and flame retardant aids, and the effects of blending with styrene resins. For this reason, the conventional laser welding method has been used only for laser light absorbing materials.
本発明の課題は、高速でかつ低出力のレーザー溶着が可能なレーザー光透過性を有する、レーザー溶着透過用スチレン系難燃性樹脂組成物を提供するものである。 An object of the present invention is to provide a styrene-based flame-retardant resin composition for laser welding and transmission, which has laser beam transparency capable of high-speed and low-power laser welding.
本発明は、スチレン系難燃性樹脂組成物の難燃化に使用される添加剤の粒子状態とレーザー光透過性の検討結果から、さらに詳しくは臭素系難燃化剤の溶融温度と難燃化助剤の粒子径に着目し鋭意研究検討を重ねた結果、臭素系難燃化剤の溶融温度が当該樹脂組成物の製造時の樹脂温度（加工温度）以下であり、難燃化助剤の粒子径及びその粒度分布が一定範囲にある場合に、スチレン系難燃性樹脂組成物がレーザー溶着するのに十分なレーザー光を透過することを見出し、本発明の完成に至った。 The present invention is based on the results of examination of the particle state of the additive used for flame retarding of the styrene-based flame retardant resin composition and the laser light transmittance, and more specifically, the melting temperature and flame retardancy of the brominated flame retardant. As a result of intensive research and investigation focusing on the particle size of the chemical conversion aid, the melting temperature of the brominated flame retardant is equal to or lower than the resin temperature (processing temperature) at the time of production of the resin composition. When the particle size and the particle size distribution of the styrene flame retardant resin composition are within a certain range, it was found that the styrene-based flame retardant resin composition transmits laser light sufficient for laser welding, and the present invention was completed.
すなわち、本発明は、（１）スチレン系樹脂（Ａ）１００質量部に対し、融点または軟化点が２５０℃以下の臭素系難燃化剤（Ｂ）を１０〜２５質量部含有してなり、２ｍｍの厚さで成形した試験片における波長９４０ｎｍのレーザー光による透過率が４５％以上であるレーザー溶着透過用スチレン系難燃性樹脂組成物、（２）体積平均粒子径が０．０１〜０．０５μmの難燃化助剤(Ｃ)を０．１〜１．５質量部添加することを特徴とする、（１）記載のレーザー溶着透過用スチレン系難燃性樹脂組成物、（３）臭素系難燃化剤（Ｂ）として、下記の一般式（I〜III）で表されるものを単独、又は２種以上を組み合わせて使用することを特徴とする、（１）又は（２）記載のレーザー溶着透過用スチレン系難燃性樹脂組成物、
-CH2-CH-CH2-O-R' （Ｒ'は低級アルキル基、及び／又は臭素、塩素原子で置換されてもよいフェニル基を示す。）Ｘは臭素又は塩素原子、ｊは１〜４の整数、ｎは０〜３０の整数を示す。」
—CH 2 —CH—CH 2 —OR ′ (R ′ represents a lower alkyl group and / or a phenyl group which may be substituted with a bromine or chlorine atom.) X is a bromine or chlorine atom, j is 1 to 4 , N represents an integer of 0-30. "
本発明に関わる、スチレン系難燃性樹脂組成物はレーザー光の透過率に優れており、この利点を活かして、ワープロ、パーソナルコンピュータ、プリンター、複写機等のＯＡ機器、ＴＶ、ＶＴＲ、オーディオ等の家電製品等、電気、電子関連機器、精密機械関連機器、事務用機器、自動車、車両関連部品、建材、包装材、家具、日用雑貨などの各種レーザー溶着法にて製造される成形品に使用でき、今後のレーザー溶着技術の発展に寄与すると共に、その産業上の利用価値は極めて大である。 The styrene-based flame retardant resin composition according to the present invention is excellent in laser light transmittance. Taking advantage of this, office automation equipment such as word processors, personal computers, printers, copiers, TVs, VTRs, audios, etc. Products manufactured by various laser welding methods such as electrical appliances, electronic equipment, precision machinery equipment, office equipment, automobiles, vehicle-related parts, building materials, packaging materials, furniture, daily goods, etc. It can be used and contributes to the development of laser welding technology in the future, and its industrial utility value is extremely large.
本発明を構成する成分の特徴は次の通りである。
スチレン系樹脂（Ａ）は、ポリスチレン樹脂（ＧＰＰＳ）、耐衝撃性ポリスチレン樹脂（ＨＩＰＳ）、スチレンメタアクリレート樹脂（ＭＳ）、耐衝撃ゴム含有スチレンメタアクリルアクリレート樹脂（ＭＢＳ）、スチレンブタジエンブロック共重合体（ＳＢＳ）等で、これらの単独又は２種類以上を用いることができる。スチレン系樹脂（Ａ）により成形された２ｍｍ厚の試験片における波長９４０ｎｍのレーザー光の透過率は、４５％以上が必要であり、好ましくは５０％以上を必要とする。
The characteristics of the components constituting the present invention are as follows.
Styrene resin (A) is polystyrene resin (GPPS), high impact polystyrene resin (HIPS), styrene methacrylate resin (MS), high impact rubber containing styrene methacrylate resin (MBS), styrene butadiene block copolymer (SBS) or the like can be used alone or in combination of two or more. The transmittance of laser light having a wavelength of 940 nm in a 2 mm-thick test piece molded from the styrene-based resin (A) needs to be 45% or more, preferably 50% or more.
臭素系難燃化剤（Ｂ）は、融点または軟化点が２６０℃以下であり、好ましくは融点又は軟化点が２３０℃以下である。 The brominated flame retardant (B) has a melting point or softening point of 260 ° C. or lower, preferably a melting point or softening point of 230 ° C. or lower.
具体例としては、ヘキサブロモシクロドデカン、2,4,6−トリス(2,4,6−トリブロモフェノキシ)−1,3,5−トリアジン、テトラブロモビスフェノールA、トリス（トリブロモネオペンチル）ホスフェート、トリブロモフェノール・2,2-ビス（ジブロモ-4-ヒドロキシフェニル）プロパン・2,2-ビス［ジブロモ-4-（2,3-エポキシプロポキシ）フェニル］プロパン重付加物、2,2−ビス（4-（2,3-ジブロモプロポキシ）-3,5-ジブロモフェニル）プロパン、ＴＢＡ−ビス（２-ヒドロキシエチルエーテル）、ＴＢＡ−ビス（２,３−ジブロモプロピルエーテル、ＴＢＡカーボネートオリゴマー、ＴＢＡエポキシオリゴマー・ポリマー等が挙げられる。
好ましくは、2,4,6−トリス(2,4,6−トリブロモフェノキシ)−1,3,5−トリアジンとトリブロモフェノール・2,2-ビス（ジブロモ-4-ヒドロキシフェニル）プロパン・2,2-ビス［ジブロモ-4-（2,3-エポキシプロポキシ）フェニル］プロパン重付加物、及びトリス（トリブロモネオペンチル）ホスフェートが挙げられ、これら臭素系難燃化剤を単独、又は２種以上を組み合わせて使用することも可能である。
Specific examples include hexabromocyclododecane, 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine, tetrabromobisphenol A, tris (tribromoneopentyl) phosphate. , Tribromophenol, 2,2-bis (dibromo-4-hydroxyphenyl) propane, 2,2-bis [dibromo-4- (2,3-epoxypropoxy) phenyl] propane polyadduct, 2,2-bis (4- (2,3-dibromopropoxy) -3,5-dibromophenyl) propane, TBA-bis (2-hydroxyethyl ether), TBA-bis (2,3-dibromopropyl ether, TBA carbonate oligomer, TBA epoxy An oligomer, a polymer, etc. are mentioned.
Preferably, 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine and tribromophenol, 2,2-bis (dibromo-4-hydroxyphenyl) propane, 2 , 2-bis [dibromo-4- (2,3-epoxypropoxy) phenyl] propane polyadduct, and tris (tribromoneopentyl) phosphate. These brominated flame retardants can be used alone or in combination A combination of the above can also be used.
難燃化助剤（Ｃ）は、微粒子の酸化アンチモンであることが好ましい。酸化アンチモンとしては、三酸化アンチモン、五酸化アンチモン等が挙げられるが、特に好ましくは三酸化アンチモンである。その最適な体積平均粒子径は０．０１〜０．０５μmである。 The flame retardant aid (C) is preferably particulate antimony oxide. Examples of the antimony oxide include antimony trioxide and antimony pentoxide, with antimony trioxide being particularly preferred. The optimum volume average particle diameter is 0.01 to 0.05 μm.
本発明に係わるスチレン系難燃性樹脂組成物を得る方法は、特に限定される訳では無く公知の混合技術を適用することが出来る。例えば、ミキサー型混合機、Ｖ型他ブレンダー、及びタンブラー型混合機等の混合装置であらかじめ混合しておいた混合物を、バンバリー型ミキサー、ニーダー、ロール、単軸押出機、特殊単軸押出機、及び二軸押出機等で溶融混練することが挙げられる。更に、押出機等の溶融混練装置の途中から難燃化剤等の添加剤を別途に添加する方法を利用することも出来る。各原材料の添加方法としては、スチレン系樹脂（Ａ）と臭素系難燃化剤（B）と必要により難燃化助剤（C）を直接上記のような混練機に投入して樹脂組成物を得てもよいし、本発明の趣旨を超えない範囲で予め樹脂等と臭素系難燃化剤（B）と難燃化助剤（C）等を混練してペレット状にしたマスターバッチを作製し、このマスターバッチとスチレン系樹脂を混練機に投入する方法でもよい。また重合時に添加する方法としては、スチレン系樹脂の重合開始前の溶液、重合途中の反応液、または重合終了後の溶融樹脂のいずれかの段階で臭素系難燃化剤（B）と必要により難燃化助剤（C）を添加して樹脂組成物を得る方法がある。 The method for obtaining the styrene-based flame retardant resin composition according to the present invention is not particularly limited, and a known mixing technique can be applied. For example, a mixture previously mixed with a mixing apparatus such as a mixer-type mixer, V-type blender, and tumbler-type mixer is used as a Banbury mixer, kneader, roll, single-screw extruder, special single-screw extruder, And melt-kneading with a twin screw extruder or the like. Furthermore, a method of separately adding an additive such as a flame retardant from the middle of a melt-kneading apparatus such as an extruder can be used. As a method for adding each raw material, a styrene resin (A), a brominated flame retardant (B), and, if necessary, a flame retardant aid (C) are directly charged into the kneader as described above to obtain a resin composition. A master batch in which a resin or the like, a brominated flame retardant (B), a flame retardant auxiliary (C), etc. are previously kneaded into a pellet form within a range not exceeding the gist of the present invention. It is also possible to prepare the master batch and styrene resin into a kneader. In addition, as a method of adding at the time of polymerization, bromine-based flame retardant (B) and if necessary, at any stage of the solution before the polymerization of the styrene resin, the reaction solution during the polymerization, or the molten resin after the polymerization is completed. There is a method of obtaining a resin composition by adding a flame retardant aid (C).
本発明のスチレン系難燃性樹脂には、本発明の要旨を超えない範囲で各種添加物、例えば染顔料、着色防止剤、老化防止剤、光安定剤、滑剤、潤滑剤、帯電防止剤、充填剤、離型剤、摺動性付与剤、相溶化剤等の公知の添加剤を添加できる。これらの添加方法は特に限定される訳では無く、公知の方法例えば、使用するスチレン系樹脂の重合開始前、重合途中の反応液に対して、または重合終了後、及び難燃化剤（B）と難燃化助剤（C）を配合する際、更には、押出機や成形機においても添加することができる。 The styrene-based flame retardant resin of the present invention includes various additives within a range not exceeding the gist of the present invention, such as dyes and pigments, anti-coloring agents, anti-aging agents, light stabilizers, lubricants, lubricants, antistatic agents, Known additives such as a filler, a release agent, a slidability imparting agent and a compatibilizing agent can be added. These addition methods are not particularly limited, and known methods, for example, before the start of polymerization of the styrenic resin to be used, with respect to the reaction solution in the middle of the polymerization, or after the completion of the polymerization, and the flame retardant (B) And the flame retardant aid (C) can be added in an extruder or a molding machine.
以下、実施例によって本発明を具体的に説明するが、本発明はこれらの実施例によって限定されるものではない。実施例、比較例に使用した材料を以下に示す。
「スチレン系樹脂（Ａ）」
スチレン系樹脂（Ａ）には、東洋スチレン社製ＨＩＰＳ樹脂Ｈ８７０と東洋スチレン社製ＧＰＰＳ樹脂Ｇ３２０Ｃを、７０：３０の樹脂配合で均一に混合したものを使用した。この配合の樹脂単体は、２ｍｍ厚での波長９４０ｎｍのレーザー光を約５５％透過した。
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by these Examples. The materials used in Examples and Comparative Examples are shown below.
"Styrene resin (A)"
As the styrene resin (A), a HIPS resin H870 manufactured by Toyo Styrene Co., Ltd. and a GPPS resin G320C manufactured by Toyo Styrene Co., Ltd. were uniformly mixed with a resin composition of 70:30. The resin alone with this blend transmitted about 55% of laser light having a thickness of 2 mm and a wavelength of 940 nm.
「臭素系難燃化剤（B）」
臭素系難燃化剤（B１）
第一工業製薬社製 ＳＲ２４５
化合物名：２，４，６-トリス（２，４，６-トリブロモフェノキシ）-１，３，５トリアジン 融点２３０℃
臭素系難燃化剤（B２）
東都化成社製 ＴＢ−６０A
化合物名：トリブロモフェノール・2,2-ビス（ジブロモ-4-ヒドロキシフェニル）プロパン・2,2-ビス［ジブロモ-4-（2,3-エポキシプロポキシ）フェニル］プロパン重付加物、軟化点１００℃
臭素系難燃化剤（B３）
大八化学社製 ＣＲ９００
化合物名：トリス（トリブロモネオペンチル）ホスフェート、融点１８２℃
臭素系難燃化剤（B４）
アルべマール社製 Sａｙｔｅｘ８０１０
エチレンビス（ペンタブロモベンゼン）、融点３６１℃
"Brominated flame retardant (B)"
Brominated flame retardant (B1)
SR245 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
Compound name: 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5 triazine Melting point 230 ° C.
Brominated flame retardant (B2)
TB-60A manufactured by Tohto Kasei Co., Ltd.
Compound name: Tribromophenol, 2,2-bis (dibromo-4-hydroxyphenyl) propane, 2,2-bis [dibromo-4- (2,3-epoxypropoxy) phenyl] propane polyadduct, softening point 100 ℃
Brominated flame retardant (B3)
CR900 made by Daihachi Chemical Co., Ltd.
Compound name: Tris (tribromoneopentyl) phosphate, melting point 182 ° C
Brominated flame retardant (B4)
Saytex 8010 manufactured by Albemarle
Ethylenebis (pentabromobenzene), melting point 361 ° C.
「難燃化助剤（Ｃ）」
難燃化助剤（Ｃ1）：日本精鉱社製の三酸化アンチモン ＰＡＴＯＸ−Ｕ、体積平均粒子径０．０４μｍ
難燃化助剤（Ｃ２）：日本精鉱社製の三酸化アンチモン PATOX−ＣＦ、体積平均粒子径０．７１μｍ
難燃化助剤（Ｃ３）：日本精鉱社製の三酸化アンチモン PATOX−M、体積平均粒子径１．０６μｍ
難燃化助剤（Ｃ４）：日本精鉱社製の三酸化アンチモン PATOX−Ｌ、体積平均粒子径７．０７μｍ
平均粒子径の測定方法は、島津製作所製レーザー回折式粒度分布測定装置ＳＡＬＤ―７０００を使用し、分散媒の純水に中性洗剤を数滴添加した分散媒３０ｍｌ中に微量の難燃化助剤をミクロスパーテルで２杯を投入し、トミー精工社製ＵＤ２０１超音波ホモジナイザー（200Ｗ）で３分間分散処理した試料を、測定器の予め分散媒で満たしたフローセルを用いて測定器の標準方法にて適性濃度に調整し測定した。
"Flame retardant aid (C)"
Flame retardant aid (C1): Nippon Seiko Co., Ltd. antimony trioxide PATOX-U, volume average particle size 0.04 μm
Flame retardant aid (C2): Nippon Seiko Co., Ltd. antimony trioxide PATOX-CF, volume average particle size 0.71 μm
Flame retardant aid (C3): Nippon Seiko Co., Ltd. antimony trioxide PATOX-M, volume average particle size 1.06 μm
Flame retardant aid (C4): Antimony trioxide PATOX-L manufactured by Nippon Seiko Co., Ltd., volume average particle size 7.07 μm
The average particle size is measured using a laser diffraction particle size distribution analyzer SALD-7000 manufactured by Shimadzu Corporation, and a small amount of flame retardant aid is added to 30 ml of a dispersion medium obtained by adding a few drops of neutral detergent to pure water of the dispersion medium. Two samples of the agent with microspatel were added, and the sample that had been dispersed for 3 minutes with the UD201 ultrasonic homogenizer (200 W) manufactured by Tommy Seiko Co., Ltd. was used as the standard method for the measuring instrument using the flow cell previously filled with the dispersion medium of the measuring instrument. And adjusted to an appropriate concentration.
実施例、比較例の樹脂組成物は次の方法にて製造され、各データは以下の測定法で求められたものである。
スチレン系難燃性樹脂組成物の調製
上記のスチレン系樹脂（Ａ）、臭素系難燃化剤（Ｂ）、及び必要により難燃助剤（Ｃ）を実施例・比較例に記載した配合割合（質量部）で秤量しタンブラーで混合し、得られた混合物をスクリューフィーダー付き２軸押出機（押出機：池貝ＰＣＭ３０）にて２４０℃で混練して樹脂組成物のペレットを製造した。
押出し条件
シリンダー設定温度：１８０℃(搬送部位)〜２４０℃(混練り〜計量部位)
スクリュー回転数：３５０ｒｐｍ
押出速度：１５ｋｇ／ｈ
樹脂温度：２５０〜２６０℃（加工温度）
The resin compositions of Examples and Comparative Examples were produced by the following method, and each data was obtained by the following measurement method.
Preparation of Styrenic Flame Retardant Resin Composition The above styrene resin (A), bromine flame retardant (B), and, if necessary, flame retardant aid (C) are blended in the examples and comparative examples. (Mass parts) was weighed and mixed with a tumbler, and the resulting mixture was kneaded at 240 ° C. with a twin screw extruder with a screw feeder (extruder: Ikegai PCM30) to produce pellets of a resin composition.
Extrusion conditions Cylinder set temperature: 180 ° C (conveying part) to 240 ° C (kneading to measuring part)
Screw rotation speed: 350rpm
Extrusion speed: 15kg / h
Resin temperature: 250-260 ° C (processing temperature)
この樹脂組成物それぞれに対し、射出成形機（射出成形機：東芝IS130F II-3A）を使用して評価用試験片を作製した。成形温度２３０℃、金型温度４０℃の条件で、２ｍｍ厚みの４０ｍｍ角形試験片及び三段ステッププレートを作製した。 Test pieces for evaluation were prepared for each of the resin compositions using an injection molding machine (injection molding machine: Toshiba IS130F II-3A). Under the conditions of a molding temperature of 230 ° C. and a mold temperature of 40 ° C., a 2 mm-thick 40 mm square test piece and a three-step step plate were produced.
各々の試験片について、以下に示す方法でレーザー光透過率の評価、溶着性評価としてレーザー溶着試験実施後の試験片のせん断強度を測定、及びＵＬ燃焼試験を実施した。これら結果を表１、２に示す。
レーザー光の透過率の評価
射出成形法により得られた厚さ２ｍｍの試験片を９４０ｎｍ、１０Ｗのレーザー光を透過させ、透過したレーザー光をパワーメーターにて測定し、透過前出力１０Ｗを１００％とし透過後のパワーメーター出力値を百分率で計算し透過率とした。
ファインディバイス社製 レーザー溶着機ＦＤ−２０００使用
オフィール社製ディスプレイＮＯＶＡヘッドＦ300Ａ パワーメーター使用
About each test piece, the shear strength of the test piece after laser welding test implementation was measured, and UL combustion test was implemented by the method shown below as laser light transmittance evaluation and welding property evaluation. These results are shown in Tables 1 and 2.
Evaluation of Laser Light Transmittance A test piece having a thickness of 2 mm obtained by the injection molding method transmits a laser beam of 940 nm and 10 W, and the transmitted laser beam is measured with a power meter. The power meter output value after transmission was calculated as a percentage and used as the transmittance.
Fine device laser welding machine FD-2000 used Offiel display NOVA head F300A Power meter used
溶着性評価（レーザー溶着後のせん断強度）
本発明の実施例及び比較例の樹脂組成物をレーザー光透過側材料として使用し、レーザー光吸収側材料は東洋スチレン製トーヨースチロールＦ２Ｃ（黒着色品）を使用した。この三段ステッププレート試験片は、肉厚が１ｍｍ、２ｍｍ、３ｍｍが連続した三段構造となっており、中央の２ｍｍ部でレーザー光透過側と吸収側の２つの試験片を重ね合わせ、下記条件で透過側からレーザーを照射してレーザー溶着を実施した。
ファインディバイス社製 レーザー溶着機ＦＤ−２０００を使用。
レーザー出力 ３０Ｗ
スピード １５０ｍｍ／ｓｅｃ
スポット径 ０．６ｍｍ
圧力 ０．５ｋｇf
溶着距離 ３０ｍｍ
溶着した試験片の肉厚３ｍｍ側の両端をチャックし引張試験を実施した時の、最大せん断剥離強度を測定し、実施例、比較例のレーザー溶着後のせん断強度（ｋｇｆ）として記載した。
引張試験 インテスコ社製５本掛精密万能材料試験機２００５-５型を使用。
試験速度 ５０ｍｍ／ｓｅｃ 、５０ｍｍ変位
Weldability evaluation (shear strength after laser welding)
The resin compositions of Examples and Comparative Examples of the present invention were used as laser light transmission side materials, and Toyostyrene F2C (black colored product) made by Toyo Styrene was used as the laser light absorption side material. This three-step step plate test piece has a three-stage structure with a continuous thickness of 1 mm, 2 mm, and 3 mm. Two test pieces on the laser light transmission side and absorption side are overlapped at the center 2 mm portion, Laser welding was performed by irradiating a laser from the transmission side under conditions.
Laser welding machine FD-2000 manufactured by Fine Devices is used.
Laser power 30W
Speed 150mm / sec
Spot diameter 0.6mm
Pressure 0.5kgf
Welding distance 30mm
The maximum shear peel strength when a tensile test was carried out by chucking both ends of the welded test piece on the thickness side of 3 mm was described as the shear strength (kgf) after laser welding in Examples and Comparative Examples.
Tensile test Uses 5-inch precision universal material testing machine 2005-5 manufactured by Intesco.
Test speed 50mm / sec, 50mm displacement
難燃性ＵＬ燃焼試験
米国アンダーライターズ・ラボラトリーズ社のサブジェクト９４号の垂直燃焼試験方法に準拠し、１．４ｍｍ、３ｍｍの厚みのサンプルで燃焼試験を実施した。この試験法でＶ−２以上の評価となった場合を合格とし、Ｖ−２に満たなかった場合を不合格とした。
Flame Retardancy UL Combustion Test A combustion test was conducted on samples of 1.4 mm and 3 mm thickness in accordance with the subject No. 94 vertical combustion test method of US Underwriters Laboratories. In this test method, a case where the evaluation was V-2 or higher was accepted, and a case where the evaluation was less than V-2 was rejected.
ビカット軟化温度（50Ｎ荷重）は、ＪＩＳ Ｋ７２０６に準拠した方法により２３℃で測定を行った。 Vicat softening temperature (50N load) was measured at 23 ° C. by a method based on JIS K7206.
シャルピー衝撃強度は、ＪＩＳ Ｋ７１１１に準拠した測定法により２３℃で測定を行った。（Ｖノッチあり）。 The Charpy impact strength was measured at 23 ° C. by a measuring method based on JIS K7111. (V notch).
実施例１〜３、比較例１
スチレン系樹脂（Ａ）の１００質量部に対し、融点２５０℃以下の臭素系難燃化剤のみを表１に示す配合で押出し調製した。比較例１は、表２に示す配合で融点２６０℃以上の臭素系難燃化剤（Ｂ４）を用いた。
Examples 1-3, Comparative Example 1
With respect to 100 parts by mass of the styrene resin (A), only a brominated flame retardant having a melting point of 250 ° C. or less was extruded and prepared with the formulation shown in Table 1. In Comparative Example 1, a brominated flame retardant (B4) having a melting point of 260 ° C. or higher with the formulation shown in Table 2 was used.
実施例４〜９、比較例２
スチレン系樹脂（Ａ）の１００質量部に対し、臭素系難燃化剤と難燃化助剤（Ｃ１）を表１、２に示す配合で押出し調製した。実施例４、７、８、９は臭素系難燃化剤（Ｂ１）、実施例５は臭素系難燃化剤（Ｂ２）、実施例６は臭素系難燃化剤（Ｂ３）を用いた、比較例２は、表２に示す配合で融点２６０℃以上の臭素系難燃化剤（Ｂ４）を用いた。
Examples 4-9, Comparative Example 2
A brominated flame retardant and a flame retardant auxiliary (C1) were extruded and prepared with the formulations shown in Tables 1 and 2 with respect to 100 parts by mass of the styrene resin (A). Examples 4, 7, 8, and 9 used brominated flame retardant (B1), Example 5 used brominated flame retardant (B2), and Example 6 used brominated flame retardant (B3). In Comparative Example 2, a brominated flame retardant (B4) having a melting point of 260 ° C. or higher with the formulation shown in Table 2 was used.
比較例３〜８
スチレン系樹脂（Ａ）の１００質量部に対し、融点２５０℃以下の難燃化剤（B１）と粒子径の大きい難燃化助剤を表２に示す配合で押出し調製した。比較例３は難燃化助剤（Ｃ２）、比較例４は難燃化助剤（Ｃ３）、比較例５は難燃化助剤（Ｃ４）を用いた。
Comparative Examples 3-8
For 100 parts by mass of the styrene resin (A), a flame retardant (B1) having a melting point of 250 ° C. or less and a flame retardant assistant having a large particle diameter were prepared by extrusion blending as shown in Table 2. Comparative Example 3 used a flame retardant aid (C2), Comparative Example 4 used a flame retardant aid (C3), and Comparative Example 5 used a flame retardant aid (C4).
実施例１０
スチレン系樹脂（Ａ）の１００質量部に対し、融点２５０℃以下の臭素系難燃化剤（Ｂ１）と（Ｂ２）を併用し、難燃化助剤（Ｃ１）を表１に示す配合で押出し調製した。
Example 10
The brominated flame retardants (B1) and (B2) having a melting point of 250 ° C. or less are used in combination with 100 parts by mass of the styrene resin (A), and the flame retardant aid (C1) is blended as shown in Table 1. Prepared by extrusion.
表1から明らかなように、実施例１〜１０は、本発明のレーザー溶着透過用スチレン系難燃性樹脂組成物であり、本発明の目的とするレーザー光の透過率、溶着性に優れていることがわかる。特に、実施例４はレーザー光の透過率、溶着性に優れており更には、ビカット軟化温度とシャルピー衝撃強度が高くバランスの良いレーザー溶着透過用スチレン系難燃性樹脂組成物で有ることが明らかである。 As is clear from Table 1, Examples 1 to 10 are styrene-based flame retardant resin compositions for laser welding and transmission of the present invention, which are excellent in laser light transmittance and welding properties of the present invention. I understand that. In particular, Example 4 is excellent in laser light transmittance and weldability, and further has a well-balanced styrene-based flame retardant resin composition for laser welding transmission with a high Vicat softening temperature and Charpy impact strength. It is.
これらの実施例に対し表２の比較例１と比較例２は、本発明より臭素系難燃化剤の融点が高いもので、スチレン系難燃性樹脂組成物の中に溶解しない固体粉末の大粒子が存在し、この粒子の遮蔽効果によってレーザー光透過率を０％となり溶着が実現出来なかった。 For these examples, Comparative Example 1 and Comparative Example 2 in Table 2 have a higher melting point of the brominated flame retardant than the present invention and are solid powders that do not dissolve in the styrene flame retardant resin composition. Large particles existed, and the laser light transmittance was 0% due to the shielding effect of the particles, and welding could not be realized.
また比較例３〜８は、本発明の請求範囲を超えて難燃化助剤の粒子径が大きい為に、スチレン系難燃性樹脂組成物のレーザー光透過率を低下させている。比較例２〜４は、溶着出来ず燃焼試験が不合格で実用性が無い。比較例５は、溶着は可能なもののせん断強度が弱く、燃焼試験が不合格である。比較例６〜８も同様に、溶着が不可能であった。 Moreover, since the comparative example 3-8 exceeds the claim of this invention and the particle diameter of a flame-retarding adjuvant is large, the laser beam transmittance | permeability of a styrene-type flame retardant resin composition is reduced. Comparative Examples 2 to 4 cannot be welded, and the combustion test fails and is not practical. In Comparative Example 5, although welding is possible, the shear strength is weak and the combustion test is unacceptable. Similarly, Comparative Examples 6 to 8 could not be welded.
Claims (4)
-CH2-CH-CH2-O-R'（Ｒ'は低級アルキル基、及び／又は臭素、塩素原子で置換されてもよいフェニル基を示す。）Ｘは臭素又は塩素原子、ｊは１〜４の整数、ｎは０〜３０の整数を示す。」
—CH 2 —CH—CH 2 —O—R ′ (R ′ represents a lower alkyl group and / or a phenyl group which may be substituted with a bromine or chlorine atom) X is a bromine or chlorine atom, j is 1 The integer of -4 and n show the integer of 0-30. "
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| WO2009012645A1 (en) * | 2007-07-24 | 2009-01-29 | Kingfa Science & Technology Co., Ltd. | Bromotriazine-containing polystyrenic resin composite and the method for preparating the same |
| JP2011529112A (en) * | 2008-07-22 | 2011-12-01 | ブロミン・コンパウンズ・リミテツド | Flame retardant composition of styrene-containing polymer |
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| JP2004250621A (en) * | 2003-02-21 | 2004-09-09 | Toray Ind Inc | Resin material for laser welding and composite molding using the same |
| JP2005314602A (en) * | 2004-04-30 | 2005-11-10 | Techno Polymer Co Ltd | Molding material for molded article to be fused by laser |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2004250621A (en) * | 2003-02-21 | 2004-09-09 | Toray Ind Inc | Resin material for laser welding and composite molding using the same |
| JP2005314602A (en) * | 2004-04-30 | 2005-11-10 | Techno Polymer Co Ltd | Molding material for molded article to be fused by laser |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2009012645A1 (en) * | 2007-07-24 | 2009-01-29 | Kingfa Science & Technology Co., Ltd. | Bromotriazine-containing polystyrenic resin composite and the method for preparating the same |
| JP2011529112A (en) * | 2008-07-22 | 2011-12-01 | ブロミン・コンパウンズ・リミテツド | Flame retardant composition of styrene-containing polymer |
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