JP2021535002A - プラスチック部品の部分的な着色のための改良された方法 - Google Patents
プラスチック部品の部分的な着色のための改良された方法 Download PDFInfo
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- JP2021535002A JP2021535002A JP2021509901A JP2021509901A JP2021535002A JP 2021535002 A JP2021535002 A JP 2021535002A JP 2021509901 A JP2021509901 A JP 2021509901A JP 2021509901 A JP2021509901 A JP 2021509901A JP 2021535002 A JP2021535002 A JP 2021535002A
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Images
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- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/40—Manufacture
- B42D25/405—Marking
- B42D25/41—Marking using electromagnetic radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
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Abstract
Description
i) プラスチック部分(A)を着色浴(B)に浸漬する工程、
ii) i)からのプラスチック部品(A)を集束非電離電磁放射線(C)で照射する工程、
ここで、部分的な着色が、工程ii)で照射された部位のみで実質的に行われ、
ここで、集束非電離電磁放射線(C)の波長範囲が、DIN EN ISO/IEC 17025に従うUV−VIS−NIR−MIR法に従い決定される、選択された放射線について、着色浴(B)の放射線透過率が≧0.1%から≦99%、好ましくは≧0.5%から≦99%、より好ましくは≧0.9%から≦99%、より好ましくは≧2%から≦99%、より好ましくは≧30%から≦95%、特に好ましくは≧40%から≦93%であるように選択され、
着色浴(B)の温度が、≦99℃から≧−60℃、好ましくは≦99℃から≧0℃、より好ましくは≦70℃から≧10℃、特に好ましくは≦50℃から≧15℃であり、着色浴(B)の温度が、好ましくは上記方法の持続期間にわたって一定の温度を有しており、そして、集束非電離電磁放射線(C)が、プラスチック部品(A)に衝突する前に、1つ以上の放射線デカップリング材料を含むシート(D)を通過することを特徴とする方法によって達成された。
あるいは、着色浴(B)が、プロセスの持続期間にわたって、10℃を超える、好ましくは20℃まで、より好ましくは50℃まで、特に好ましくは100℃までの温度変化を受けてもよい。
HO−Z−OH (I)
ここで、Zは、6〜34個の炭素原子を有する芳香族基であり、これは、1つ以上の置換されていてもよい芳香族環および脂肪族または脂環式基またはアルキルアリールまたはヘテロ原子を架橋メンバーとして含有していてもよい。
R1及びR2は、互いに独立して、水素、ハロゲン、好ましくは塩素又は臭素、C1〜C8−アルキル、C5〜C6−シクロアルキル、C6〜C10−アリール、好ましくはフェニル、C7〜C12−アラルキル、好ましくはフェニル−C1〜C4−アルキル、特にベンジルを表し、
mは、4から7の整数、好ましくは4又は5であり、
R3及びR4は、それぞれのXについて独立して選択可能であり、互いに独立して、水素又はC1〜C6−アルキルを表し、
Xは、炭素を表し、
ただし、少なくとも一つの原子Xについて、R3及びR4はともにアルキルを表す。式(Ia)において、1つまたは2つの原子Xについて、特には1つの原子Xについてのみ、R3及びR4がともにアルキルを表すことが好ましい。
R、R’及びR”は、互いに独立して、同一または異なるものであり、H、線状または分岐のC1〜C34−アルキル、C7〜C34−アルキルアリールまたはC6〜C34−アリールを表し、Rは、さらに、−COO−R’’’を表すものでもよく、ここで、R’’’は、H、線状または分岐のC1〜C34−アルキル、C7〜C34−アルキルアリールまたはC6〜C34−アリールを表す。
RAは、線状または分岐のC1〜C34−アルキル、C7〜C34−アルキルアリール、C6〜C34−アリールまたは−COO−RDを表し、ここで、RDは、H、線状または分岐のC1〜C34−アルキル、C7〜C34−アルキルアリール、C6〜C34−アリールを表し、
RB、RCは、互いに独立して、同一または異なるものであり、H、線状または分岐のC1〜C34−アルキル、C7〜C34−アルキルアリールまたはC6〜C34−アリールを表す。
a)溶媒および/または分散剤、好ましくは水および/または有機溶媒、特に好ましくは水
b)着色剤、好ましくは染料、特に好ましくはカラーインデックス分類に従う溶媒染料および/または分散染料からの染料
を含む。
c)構造式(IV)の少なくとも1つのさらなる溶媒
R−[(O−(CH2)m)n−]OH (IV)
ここで、Rは、エチル、プロピルまたはブチル基であり
mは、2、3または4であり、
nは、1、2または3であり、
ただし、Rがブチルである場合、mは2または4である
d)構造式(V)の少なくとも1つのレベリング剤:
H−[(O−(CH2)m)n−]OH (V)
ここで、mは、2、3または4であり、
nは、1、2または3である
を含む。
a)50.0重量%〜99.99重量%、好ましくは62.5重量%〜90.0重量%、特に好ましくは65.0重量%〜85.0重量%、
b)0.01重量%〜15.0重量%、好ましくは0.1重量%〜5.0重量%、特に好ましくは0.2重量%〜4.0重量%、
c)0重量%〜35.0重量%、好ましくは1.0重量%〜30.0重量%、特に好ましくは5.0重量%〜25.0重量%、
d)0重量%〜30.0重量%、好ましくは1.0重量%〜20.0重量%、特に好ましくは3.0重量%〜15.0重量%。
a)50.0重量%〜99.99重量%、好ましくは62.5重量%〜90.0重量%、特に好ましくは65.0重量%〜85.0重量%、
b)0.01重量%〜25重量%、好ましくは0.1重量%〜20重量%、特に好ましくは0.2重量%〜18重量%、
c)0重量%〜35.0重量%、好ましくは1.0重量%〜30.0重量%、特に好ましくは5.0重量%〜25.0重量%、
d)0重量%〜30.0重量%、好ましくは1.0重量%〜20.0重量%、特に好ましくは3.0重量%〜15.0重量%。
上述したような少なくとも1つの熱可塑性プラスチックを含有する少なくとも1つの層、および
上述したような少なくとも1つの熱可塑性プラスチックおよび少なくとも1つのレーザー感受性添加剤、好ましくは黒色顔料、特に好ましくはカーボンブラックを含有する少なくとも1つのさらなる層を含む。このような層構造は、例えば、WO−A 2010/089035から知られており、白黒でのレーザー彫刻、特にセキュリティ文書、非常に特に識別文書のパーソナライズレーザー彫刻に適している。
i’) プラスチック部品(A)の少なくとも部分的領域上に着色層b)を作る工程;
ii’) i’)からのプラスチック部品(A)を非電離電磁放射線(C)で照射する工程、
ここで、部分的な着色が、工程i’)の着色層b)で覆われた部位のみ又は工程ii’)で照射された部位のみで実質的に行われ、ここで、非電離電磁放射線(C)の波長範囲が、DIN EN ISO/IEC 17025に従うUV−VIS−NIR−MIR法によって決定される選択された放射線について、着色層b)の放射線透過率が≧0.1%から≦99%、好ましくは≧0.5%から≦95%、特に好ましくは≧0.9%から≦93%であるように選択される、方法をさらに提供する。工程ii)での照射の前、最中または後に、プラスチック部品(A)の温度は、≦99℃から≧−60℃、好ましくは≦70℃から≧−40℃、特に好ましくは≦50℃から≧−15℃の範囲であり、ここで、プラスチック部品(A)の温度は、方法の持続期間にわたって100℃の温度範囲で変化することができる。着色層b)は、好ましくは0.001mm〜10mm、特に好ましくは0.005mm〜5mm、非常に特に好ましくは0.01mm〜1mmの厚さを有する。集束非電離電磁放射線(C)は、好ましくは、プラスチック部品(A)に衝突する前に、1つ以上の放射線デカップリング材料を含むシート(D)を通過する。
A−1:二次元プラスチック部品、好ましくは熱可塑性プラスチック部品、特に好ましくは層構造を含む熱可塑性プラスチック部品
A−2:三次元プラスチック部品、好ましくは熱可塑性三次元プラスチック部品
B:着色浴または液体の着色層
C:集束非電離電磁放射線
D:1つ以上の放射線デカップリング材料を含むシート
E:集束非電離電磁放射線用の放射線源
b:浸漬深さまたは着色層厚さ
フィルム2:IR吸収剤を含む厚さ100μmの透明ポリカーボネートフィルムを以下のように製造した:
マスターバッチ:高濃度IRマスターバッチの配合
フィルム2の製造のためのマスターバッチの製造は、ポリカーボネートに慣用の250℃〜330℃のプロセス温度で、慣用の二軸配合押出機(ZSK32)を用いて実施した。
以下の組成を有するマスターバッチを配合し、続いて粒状にした:
・ 94.69重量%のCovestro Deutschland AGのポリカーボネートMakrolonTM3108
・ 0.75重量%の住友製YMDS 874 IR吸収剤
・ 4.5重量%のCovestro Deutschland AGのMakrolonTM3108粉末
・ 0.006重量%(60ppm)の 平均粒径95nmを有するランプブラック101(Evonik−Degussa GmbHからのカーボンブラック)
押出フィルムを製造するために使用される装置は、以下を含む:
・ 直径(D)が60mmで長さが33Dのスクリューを有する少なくとも1つのポリカーボネートを含有する層の押出用の押出機。スクリューは脱気ゾーンを有する;
・ 溶融ポンプ;
・ クロスヘッド;
・ 幅450mmのスロットダイ;
・ 水平ローラー配向を有する3ローラー平滑化カレンダー、ここで、第3のローラーは、水平に対して+/−45°旋回することができる;
・ ローラーコンベヤー;
・ 厚さ測定手段;
・ 保護膜の両面塗布手段;
・ 引き取り装置;
・ 巻き取りステーション。
ラミネーションは、Buerckle 50/100ラミネーションプレスで行った。フィルム1および2を、以下のプレス設定で積層した:
プレスを170〜180℃に予熱する
15N/cm2の圧力で8分間プレスする
100N/cm2の圧力で2分間プレスする
プレスを38℃まで冷却し、プレスを開く。
69.31重量%の水
0.99質量%のMacrolexTMBlue 3R(染料、Lanxess AG Deutschland)
19.8重量%のエチレングリコールブチルエーテル(EGBE)(溶媒、The Dow Chemical Company)
9.9重量%のジエチレングリコール(DEG)(レベリング剤、Merck KGaA)
30重量%の水
20質量%のMacrolexTMBlue 3R(染料、Lanxess AG Deutschland)
50重量%のイソプロパノール。
ラミネートAを、上記の組成の着色浴(B)中に置いた(透明側(フィルム2)を上に向けた)。
レーザー照射は、レーザー出力約7.5W、パルス動作のレーザー周波数8kHzおよび電流30AのFoba D84 NdYAGレーザーを用いて行った。レーザーの進入速度、浸漬深さ及び着色浴(B)の温度を表1に報告する。
フィルムを含む着色浴を、Foba D84S レーザー装置のワークピースキャリア上に置いた。レーザー(E)をフィルム表面に集光した。浸漬深さを表1に報告する。本発明の文脈において、浸漬深さは、部分的な着色が適用されるプラスチック部品の表面までの着色浴への使用された放射線の侵入深さを意味すると理解される。レーザー光による照射を開始した。
ラミネートA(A−1)を、上記の組成の着色浴(B)中に配置した(透明側(フィルム2)を上に向けた)。ラミネートA’は、印刷により着色層でコーティングされた。
ラミネートA上に、厚さ3mmのシリケートガラスからなるガラスシート(D)を置いた。スペーサを用いてラミネートAとガラスシート(D)の間の距離(浸漬深さ)を1mmとした。着色浴(B)は、ガラスシート(B)の上部には着色液が残らないように充填した。
ラミネートA’をホルダーにクランプした。
レーザー照射は、レーザー出力約7.5W、ラミネートAでは8kHz、ラミネートA’では30kHzのパルス動作のレーザー周波数および電流30AのFoba D84 NdYAGレーザーを用いて行った。レーザーの進入速度、浸漬深さ/着色層厚さ(b)及び着色浴(B)の温度を表2に報告する。
レーザー(E)は、ガラスシートを通してラミネートA’のフィルム表面上に集光された。本発明の文脈において、浸漬深さ/着色層厚さ(b)は、部分的な着色が適用されるプラスチック部品の表面までの着色浴(B)/着色層b)への使用された放射線の侵入深さを意味すると理解される。レーザー光による照射を開始した。
Claims (18)
- プラスチック部品の部分的な着色のための方法であって、以下の工程を含み、
i) プラスチック部分(A)を着色浴(B)に浸漬する工程、
ii) i)からの前記プラスチック部品(A)を集束非電離電磁放射線(C)で照射する工程、
ここで、前記部分的な着色が、工程ii)で照射された部位のみで実質的に行われ、
ここで、前記集束非電離電磁放射線(C)の波長範囲が、DIN EN ISO/IEC 17025に従うUV−VIS−NIR−MIR法によって決定される選択された放射線について、前記着色浴(B)の放射線透過率が≧2%から≦99%、好ましくは≧30%から≦95%、特に好ましくは≧40%から≦93%であるように選択され、
前記着色浴(B)の温度が、≦99℃から≧−60℃、好ましくは≦99℃から≧0℃、より好ましくは≦70℃から≧10℃、特に好ましくは≦50℃から≧15℃であり、前記着色浴(B)の温度が、好ましくは前記方法の持続期間にわたって一定の温度を有しており、そして、前記集束非電離電磁放射線(C)が、前記プラスチック部品(A)に衝突する前に、1つ以上の放射線デカップリング材料を含むシート(D)を通過することを特徴とする方法。 - 前記集束非電離電磁放射線(C)が、≧0.1μmから≦1000μmの範囲、好ましくは≧1.0μmから≦50μmの範囲、特に好ましくは≧1.0μmから≦2.5μmの範囲の波長を有するレーザー放射線である、請求項1に記載の方法。
- 前記プラスチック部品(A)の表面から前記シート(D)の距離が、≦120mm、好ましくは≧0.01から≦100mm、特に好ましくは≧0.1から≦20mm、非常に特に好ましくは≧0.1から≦5.0mmである、請求項1または2に記載の方法。
- 前記シート(D)の前記放射線デカップリング材料が、≧80−50から≦10−10、好ましくは≧60−40から≦20−10のISO 10110−8に従って決定されるスクラッチ−ディグ値と、≧0.5から≦500nm、好ましくは≧0.7から≦100nm、特に好ましくは≧1nmから≦10nmのISO 10110−8に従って決定される表面粗さRqと、≧50%から≦99.95%、好ましくは≧60%から≦99.9%、特に好ましくは≧70%から≦99.89%のDIN EN ISO/IEC 17025に従うUV−VIS−NIR−MIR法に従い決定される選択された放射線についての放射線透過率とを示す、請求項1〜3のいずれかに記載の方法。
- 前記シート(D)の前記放射線デカップリング材料が、ガラス、放射線透過性プラスチック、鉱物ガラス、合成ガラス、放射線透過性セラミック材料および/または上記化合物の少なくとも2つの混合物の群からの少なくとも1つ以上の化合物を含む、請求項1〜4のいずれかに記載の方法。
- 前記プラスチック部品(A)が、エチレン性不飽和モノマーのポリマーおよび/または二官能反応性化合物の重縮合物および/または二官能反応性化合物の重付加生成物から選択される熱可塑性プラスチックを含有する、請求項1〜5のいずれかに記載の方法。
- 前記プラスチック部品(A)が、使用される前記集束非電離電磁放射線の波長範囲に吸収極大を有する少なくとも1つの添加剤を含むか、または、前記プラスチック部品が、使用される前記集束非電離電磁放射線の波長範囲に吸収極大を有するコーティング組成物の形態の少なくとも1つの添加剤でコーティングされている、請求項1〜6のいずれかに記載の方法。
- 前記添加剤が、少なくとも1種以上の有機および/または無機IR吸収剤を含む、請求項7に記載の方法。
- 前記着色浴(B)が、少なくとも1つの着色剤、好ましくは少なくとも1つの染料、またはそれらの混合物を含む、請求項1〜8のいずれかに記載の方法。
- 前記着色浴(B)が、カラーインデックス分類に従う溶媒染料および/または分散染料あるいはこれら染料の混合物の群からの少なくとも1つの染料を含む、請求項1〜9のいずれかに記載の方法。
- 前記着色浴(B)が、
a)溶媒および/または分散剤、好ましくは水および/または有機溶媒、
b)少なくとも1つの着色剤、好ましくは少なくとも1つの染料、特に好ましくはカラーインデックス分類に従う溶媒染料および/または分散染料あるいは上記染料の混合物からの少なくとも1つの染料
を含む、請求項1〜10のいずれかに記載の方法。 - プラスチック部品の、好ましくは熱可塑性プラスチック部品の、非常に特に好ましくは層構造を含む熱可塑性プラスチック部品の、部分的な着色、特にカラーレーザー彫刻のための代替方法であって、少なくとも以下の工程を含み、
i) プラスチック部品(A)の少なくとも部分的領域上に着色層b)を作る工程;
ii) i)からの前記プラスチック部品(A)を非電離電磁放射線(C)で照射する工程
ここで、前記部分的な着色が、工程i)の前記着色層b)で覆われた部位のみ又は工程ii)で照射された部位のみで実質的に行われ、ここで、前記非電離電磁放射線(C)の波長範囲が、DIN EN ISO/IEC 17025に従うUV−VIS−NIR−MIR法によって決定される選択された放射線について、前記着色層b)の放射線透過率が≧0.1%から≦99%、好ましくは≧0.5%から≦95%、特に好ましくは≧0.9%から≦93%であるように選択される、方法。 - 前記プラスチック部品(A)が層構造を含み、ここで、この層構造が少なくとも1つの熱可塑性プラスチックの層を含む、請求項1〜12のいずれかに記載の方法。
- 前記層構造が、少なくとも1つの熱可塑性プラスチックを含有する少なくとも1つの層と、少なくとも1つの熱可塑性プラスチックおよび少なくとも1つの黒色顔料、好ましくはカーボンブラックを含有する少なくとも1つの更なる層とを含む、請求項13に記載の方法。
- 工程i)の前および/または工程ii)の後に、着色浴の非存在下において、工程ii)と同様に、集束非電離電磁放射線(C)を照射することを含む、請求項14に記載の方法。
- 請求項1〜15のいずれかに記載の方法によって得られるセキュリティ文書。
- 着色浴(B)と、1つ以上の放射線デカップリング材料を含むシート(D)と、集束非電離電磁放射線(C)を生成するための放射線源(E)とを含む装置であって、前記着色浴(B)の温度が、好ましくは≦99℃から≧−60.0℃、より好ましくは≦99℃から≧0.0℃、より好ましくは≦70℃から≧10℃、特に好ましくは≦50℃から≧15℃であり、ここで、前記温度が、前記装置の始動時に、100℃の温度範囲で変化してもよいし、または一定のままであってもよく、前記集束非電離電磁放射線(C)が、プラスチック部品(A)に衝突する前に、1つ以上の放射線デカップリング材料を含む前記シート(D)を通過することを特徴とする、装置。
- 前記着色浴(B)の温度が、≦99℃から≧−60℃、好ましくは≦99℃から≧0℃、より好ましくは≦70℃から≧10℃、特に好ましくは≦50℃から≧15℃であり、ここで、前記温度が、好ましくは、前記装置の始動時に、一定のままである、請求項17に記載の装置。
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