JPWO2008152909A1 - レーザー透過性樹脂成形品及びその複合成形品 - Google Patents
レーザー透過性樹脂成形品及びその複合成形品 Download PDFInfo
- Publication number
- JPWO2008152909A1 JPWO2008152909A1 JP2009519215A JP2009519215A JPWO2008152909A1 JP WO2008152909 A1 JPWO2008152909 A1 JP WO2008152909A1 JP 2009519215 A JP2009519215 A JP 2009519215A JP 2009519215 A JP2009519215 A JP 2009519215A JP WO2008152909 A1 JPWO2008152909 A1 JP WO2008152909A1
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- Prior art keywords
- resin
- laser
- molded product
- brominated
- resins
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000011347 resin Substances 0.000 title claims abstract description 204
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- -1 phosphorus compound Chemical class 0.000 claims abstract description 105
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 53
- 229910000410 antimony oxide Inorganic materials 0.000 claims abstract description 34
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims abstract description 34
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- 238000003466 welding Methods 0.000 claims description 76
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 20
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 claims description 12
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- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 claims description 6
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- 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 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
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Images
Classifications
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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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- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/82—Testing the joint
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- 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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Abstract
Description
ベース樹脂であるポリエステル系樹脂は、ジカルボン酸成分とジオール成分との重縮合、オキシカルボン酸又はラクトンの重縮合、またはこれらの成分の重縮合などにより得られるホモポリエステル又はコポリエステルである。
本発明では、アンチモン酸化物(C)と組み合わせる難燃剤として、特定の臭素系難燃剤、すなわち、臭素含有(メタ)アクリル系樹脂(又は臭素化(メタ)アクリル系樹脂、例えば、臭素化ポリベンジル(メタ)アクリレート系樹脂(例えば、ポリ(ペンタブロモベンジル(メタ)アクリレート)などの臭素化ポリベンジル(メタ)アクリレート、ポリ(ペンタクロロベンジル(メタ)アクリレート)などのハロゲン化ベンジル(メタ)アクリレートの単独又は共重合体など)などの臭素化ポリ(メタ)アクリレート)、臭素含有スチレン系樹脂[又は臭素化スチレン系樹脂、例えば、臭素化ポリスチレンなどのスチレン系樹脂の臭素化物(又はスチレン系樹脂を臭素化処理した臭素化物)、臭素化スチレン系単量体の単独又は共重合体など;例えば、ポリ臭素化スチレンなど]、臭素含有ポリカーボネート系樹脂(又は臭素化ポリカーボネート系樹脂、例えば、臭素化ビスフェノールA型ポリカーボネート樹脂などの臭素化ビスフェノール型ポリカーボネート樹脂)、および臭素含有エポキシ系樹脂[又は臭素化エポキシ系樹脂、例えば、臭素化ビスフェノール型エポキシ樹脂(臭素化ビスフェノールA型エポキシ樹脂など)などの臭素化エポキシ樹脂;臭素化ビスフェノール型フェノキシ樹脂(臭素化ビスフェノールA型フェノキシ樹脂など)などの臭素化フェノキシ樹脂など]から選択された少なくとも1種の臭素系化合物(B)を使用する。
代表的な臭素化ポリ(メタ)アクリレート系樹脂には、臭素化ポリベンジル(メタ)アクリレート系樹脂[例えば、臭素化ベンジル(メタ)アクリレート(例えば、ペンタブロモベンジル(メタ)アクリレート、テトラブロモベンジル(メタ)アクリレート、トリブロモベンジル(メタ)アクリレート)を重合成分とする樹脂、例えば、臭素化ベンジル(メタ)アクリレートの単独又は共重合体、臭素化ベンジル(メタ)アクリレートと共重合性単量体との共重合体など]などが含まれる。
代表的な臭素含有スチレン系樹脂(又は臭素化スチレン系樹脂)には、臭素化スチレン系単量体(例えば、ジブロモスチレン、トリブロモスチレンなどの臭素化スチレン)を重合成分とする樹脂、例えば、臭素化スチレン系単量体の単独又は共重合体(臭素化ポリスチレンなど)、臭素化スチレン系単量体と共重合性単量体との共重合体などが含まれる。共重合性単量体としては、前記例示の共重合性単量体などが含まれる。共重合性単量体は単独又は2種以上組み合わせてもよい。
上記式のRおよびR′において、炭化水素基としては、例えば、炭素数1〜10のアルキル基(メチル基、エチル基、プロピル基、イソプロピル基など)などのアルキル基が挙げられる。また、Xにおいて、炭化水素基としては、二価のC1−10炭化水素基(メチレン、エチレン、2−プロピリデン基などのC1−4炭化水素基)などが挙げられる。
代表的な臭素含有エポキシ樹脂(臭素化エポキシ樹脂)には、臭素含有ビスフェノール類(又は臭素化ビスフェノール類、例えば、テトラブロモビスフェノールAなどの臭素化ビス(ヒドロキシフェニル)C1−10アルカンなど)を重合成分(又はジオール成分)とするエポキシ樹脂、例えば、臭素化ビスフェノールA型エポキシ樹脂などの臭素化ビスフェノール型エポキシ樹脂(例えば、テトラブロモビスフェノールAとエピクロロヒドロリンとの反応物)が含まれる。なお、臭素化エポキシ樹脂のジオール成分は、単独又は2種以上組み合わせてもよく、臭素化されていないジオール成分(例えば、ビスフェノールAなどのビス(ヒドロキシフェニル)C1−10アルカン)を含んでいてもよい。また、臭素含有エポキシ樹脂の末端は、前記式のT2の場合と同様に、末端封止処理されていてもよい。特に、テトラブロモビスフェノールAを重合(ベース)成分とするエポキシ樹脂(又はテトラブロモビスフェノールA・ジグリシジルエーテルを含有するエポキシ樹脂)は、配合量が多すぎると成形品中に黒斑状の異物が増え、機械特性及び/又は電気特性を損ない、レーザー溶着時に異常過熱が生じ、溶着性を損なう可能性があるため、末端封止処理されているのが好ましい。
アンチモン酸化物には、例えば、酸化アンチモン[三酸化アンチモン(又は三酸化二アンチモン、Sb2O3など)、五酸化アンチモン(又は五酸化二アンチモン、xNa2O・Sb2O5・yH2O(x=0〜1、y=0〜4)など)など]、アンチモン酸塩[アンチモン酸金属塩(例えば、アンチモン酸ナトリウムなどのアルカリ金属塩、アンチモン酸マグネシウムなどのアルカリ土類金属塩など)、アンチモン酸アンモニウムなど]などが挙げられる。
本発明の樹脂組成物は、ポリカーボネート系樹脂を含んでいてもよい。
前記樹脂組成物(又はレーザー透過性樹脂成形品)には、結晶性やレーザー透過性を安定化させる目的で、さらに、リン系化合物(又はリン含有化合物)を添加してもよい。リン系化合物の好ましい例は、ホスファイト類{例えば、トリス(2,4−ジ−t−ブチルフェニル)ホスファイト、ビス(2−t−ブチルフェニル)フェニルホスファイトなどのモノ乃至トリス(分岐鎖状C3−6アルキル−フェニル)ホスファイト;ビス(2,6−ジ−t−ブチルフェニル)ペンタエリスリトールジホスファイト、ビス(2,4−ジ−t−ブチルフェニル)ペンタエリスリトールジホスファイト、テトラキス(2,4−ジ−t−ブチルフェニル)−4,4´−ビフェニレンジホスファイトなどの脂肪族多価アルコールの(分岐鎖状C3−6アルキル−アリール)ホスファイトなど}、ホスフォナイト類(テトラキス(2,4−ジ−t−ブチルフェニル)−4,4′−ビフェニレンジホスフォナイトなど)など]、ホスフェート類[例えば、トリス(2,4−ジ−t−ブチルフェニル)ホスフェートなどのトリフェニルホスフェート系化合物]、リン酸塩(例えば、第一リン酸カルシウム、第一リン酸ナトリウム一水和物などのアルカリ又はアルカリ土類金属リン酸塩(又はその水和物)などのリン酸金属塩)が挙げられる。これらのリン系化合物のうち、脂肪族多価アルコールの(分岐鎖状C3−6アルキル−アリール)ホスファイト、リン酸金属塩などが好ましい。
前記樹脂組成物(又はレーザー透過性樹脂成形品)には、同じく結晶性、レーザー透過性を安定化させる目的で、レーザー透過性を損なわない範囲で結晶化促進剤を添加してもよい。結晶化促進剤としては、例えば、ロジンなどの有機核剤であってもよいが、無機核剤、例えば、金属酸化物(シリカ、アルミナ、ジルコニア、酸化チタン、酸化鉄、酸化亜鉛など)、金属炭酸塩(炭酸カルシウム、炭酸マグネシウム、炭酸バリウムなど)、ケイ酸塩(ケイ酸カルシウム、ケイ酸アルミニウム、タルクなど)、金属炭化物(炭化ケイ素など)、金属窒化物(窒化ケイ素、窒化ホウ素、窒化タンタルなど)などを好適に使用できる。これらの結晶化促進剤は、単独で又は二種以上組み合わせて使用できる。結晶化促進剤は、粉粒状又は板状であってもよい。
などの変形楕円も含む)、半円、扇形(円弧)、多角形(三角形、方形(矩形、台形など)など)、又はこれらの類似形などが挙げられる。
05〜3重量部、好ましくは0.01〜1.5重量部(例えば、0.02〜1重量部)、さらに好ましくは0.05〜0.5重量部程度であってもよい。なお、酸化防止剤の割合が多すぎると、樹脂への分散性が低下したり、成形品表面に酸化防止剤が染み出す虞があるとともに、染み出しに伴って成形品の外観が低下する場合がある。
本発明のレーザー透過性樹脂成形品は、前記樹脂組成物(すなわち、レーザー溶着における透過側部材用樹脂組成物)で形成されており、レーザー溶着における透過側部材を形成するために使用される。
00〜1500nm、さらに好ましくは800〜1200nm(例えば、800〜1100nm)程度の波長を有するレーザー光が使用できる。
(A1)ポリブチレンテレフタレート(固有粘度=0.69dL/g、ウィンテックポリマー(株)製)
(A2)変性ポリブチレンテレフタレート(テレフタル酸と1,4−ブタンジオールとの反応において、テレフタル酸の一部(12.5モル%)に代えて、共重合成分としてのジメチルイソフタル酸(DMI)12.5モル%を用い、調製した変性ポリブチレンテレフタレート、固有粘度=0.76dL/g)
(A3)ポリブチレンテレフタレート−ポリカプロラクトンエラストマー(ポリブチレンテレフタレートとポリカプロラクトンとの共重合体、帝人ファイバー(株)製、Q4110)。
(B1)臭素化ポリアクリレート(ポリ(ペンタブロモベンジルアクリレート)、デッドシーブロミングループ社製、FR1025)
(B2):臭素化ポリスチレン(アルベマール(株)製、PyroChek 68PB)
(B3):臭素化ポリカーボネート(臭素化ビスフェノールA型ポリカーボネート,帝人化成(株)製、ファイヤガード FG−7500)
(B4):臭素化エポキシ樹脂(臭素化ビスフェノールA型エポキシ樹脂、阪本薬品工業(株)製、SRT5000)
(B5):エチレンビステトラブロモフタルイミド(SAYTEX BT−93、アルベマール(株)製)。
(C1)五酸化アンチモン(平均粒子径3.8μm、日産化学工業(株)製、サンエポック NA−1030)
(C2)三酸化アンチモン(平均粒子径6.3μm、日本精鉱(株)製、PATOX−L)
(C3)三酸化アンチモン(平均粒子径1.2μm、日本精鉱(株)製、PATOX−M)
なお、アンチモン酸化物の粒径は、レーザー回折/散乱式粒度分布測定装置((株)堀場製作所製 LA−920)を用い、分散媒として蒸留水を用いて測定し、得られたメジアン径を粒径とした。
(D1)ポリカーボネート樹脂(三菱エンジニアリングプラスチックス(株)製、ユーピロンS−3000)。
(E1)リン酸二水素ナトリウム(米山化学工業(株)製、リン酸一ナトリウム)
(E2)テトラキス(2,4−ジ−t−ブチルフェニル)−4,4′−ビフェニレンジホスフォナイト(クラリアントジャパン(株)製、Sandostab P−EPQ)。
(F1)窒化ホウ素(水島合金鉄(株)、窒化硼素FS−1)
(F2)タルク(林化成(株)製、タルカンパウダーPK−NN)。
(G1)ガラス繊維(直径13μm、日本電気硝子(株)製、ECS 03 T−187)
(G2)ガラス繊維(直径10μm、日本電気硝子(株)製、ECS 03 T−187H)
(G3)ガラスフレーク(日本板硝子(株)製、REFG−108)。
(H1)ポリテトラフルオロエチレン(旭硝子(株)製、アフロンPTFE C D076)
(H2)ポリテトラフルオロエチレン−アクリルコアシェルポリマー(三菱レイヨン(株)製、メタブレンA−3800)。
(1)ペレットの調製
表1〜3に示すポリエステル系樹脂(A)に、各成分[臭素系化合物(B)、アンチモン酸化物(C)、及び/又は、ポリカーボネート系樹脂(D)、リン系化合物(E)、結晶化核剤(F)]を表1〜3に示す割合で配合し、Vブレンダーにて均一に混合した。得られた混合物を、30mmφの2軸押出機を用いて、表1に示す割合の充填材(G)、フッ素含有樹脂(H)を、バレル温度260℃にて溶融混合し、ダイスから吐出されるストランドを冷却後切断して、ペレットを得た。なお、このペレットは、フェノール系酸化防止剤(チバ(株)製、「イルガノックス1010」)0.3重量部と離型剤(クラリアント(株)製、「ワックスE」)0.5重量部とを含んでいる。
上記(1)で得られたペレットを用いて射出成形機((株)東芝製)により、シリンダー温度260℃及び金型温度80℃の条件で樹脂成形品A(縦8cm×横1cm×厚さ1.0mm)を成形した。また、樹脂成形品Aに溶着するための樹脂成形品(被着体)Bとして、前記ペレット100重量部及び黒色着色用カーボンブラック(ウィンテックポリマー(株)製,商品名「2020B」)3重量部を用いる以外、樹脂成形品Aと同様にして、着色した樹脂成形品Bを作製した。なお、樹脂成形品Bはレーザー光による発熱体として作用する。
図1及び図2に示すように、樹脂成形品B(4)に対して樹脂成形品A(3)を、一部を重ねて接触させた状態で、石英ガラス板(5)と金属板(6)とで挟んで固定し、ライスター社製レーザー溶着機(MODULAS Cタイプ)を用い、波長940nmのレーザー光で、光源(1)からレーザー光(2)を樹脂成形品Aと樹脂成形品Bとの接触面に線幅W(2mm)で集光させ、樹脂成形品A(3)側から、レーザー出力10〜50Wの範囲で5W刻み、及び走査速度10mm/秒の条件でレーザー光を照射して溶着実験を行った。溶着実験後の成形品について引張試験機(オリエンテック社製、RTC−1325)を用いて、レーザー溶着した樹脂成形品Aと樹脂成形品Bとを5mm/分で引張せん断し、せん断強度が300Nを超えているものを「溶着」と判断した。また、溶着面と垂直方向に切断し、溶着面の炭化及び発泡状態を実体顕微鏡にて観察し過溶着の有無を判定した。以上の結果から溶着が認められ、炭化及び発泡状態の無いものを「3」、発泡状態は認められるが溶着が認められるものを「2」、炭化が顕著でレーザー光透過不十分なものを「1」として2以上をレーザー溶着性良好と判断した。
アンダーライターズ・ラボラトリーズのサブジェクト94(UL94)の方法に準じて、実施例及び比較例の樹脂組成物で作製した5本の試験片(厚み;0.8mm)を用いて難燃性及び樹脂の燃焼時の滴下特性について試験した。難燃性はUL94に記載の評価方法に従ってV−0、V−1、V−2、及びこれらのVランクに該当しないもの(notV と表示)に分類した。
分光光度計(日本分光(株)製,V570 積分球付き)を用いて、波長940nmにおいて、樹脂成形品Aの光線透過率を測定した。
Claims (9)
- レーザー光を吸収可能なレーザー吸収性樹脂成形品と接触可能であり、レーザー光を透過して、前記樹脂成形品と接合するレーザー透過性樹脂成形品であって、ポリエステル系樹脂(A)と、臭素化(メタ)アクリル系樹脂、臭素化スチレン系樹脂、臭素化ポリカーボネート系樹脂、および臭素化エポキシ系樹脂から選択された少なくとも1種の臭素系化合物(B)と、平均粒子径2〜10μmを有するアンチモン酸化物(C)とで構成された樹脂組成物で形成されているレーザー透過性樹脂成形品。
- 厚み1mmにおいて、レーザー光透過率が20%以上である請求項1記載の成形品。
- アンチモン酸化物(C)が、三酸化アンチモン、五酸化アンチモンおよびアンチモン酸ソーダから選択された少なくとも1種である請求項1又は2に記載の成形品。
- ポリエステル系樹脂(A)100重量部に対して、臭素系化合物(B)の割合が10〜50重量部であり、アンチモン酸化物(C)の割合が5〜30重量部である請求項1〜3のいずれかに記載の成形品。
- さらに、ポリカーボネート系樹脂(D)及びリン系化合物(E)を含む請求項1〜4のいずれかに記載の成形品。
- さらに、結晶化促進剤(F)を含む請求項1〜5のいずれかに記載の成形品。
- 厚み0.8mmのとき、UL94規格に基づく難燃性評価がV−0である請求項1〜6のいずれかに記載の成形品。
- 請求項1〜7のいずれかに記載のレーザー透過性樹脂成形品と、レーザー光を吸収可能なレーザー吸収性樹脂成形品とがレーザー溶着により接合されている複合成形品。
- レーザー透過性樹脂成形品が、少なくともレーザー光が透過する厚み0.1〜1.0mmの部位を有する樹脂成形品であり、この部位でレーザー吸収性樹脂成形品と接合されている請求項8記載の複合成形品。
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